multifunctional chain exchange agent, process for preparing a multifunctional chain exchange agent,

专利摘要:
multifunctional chain exchange agent, process for preparing a multifunctional chain exchange agent, process for preparing a multifunctional composition, multifunctional composition, process for preparing a poly radical polyolefin, telequel polyolefin, multifunctional chain exchange agent, process for preparing a polyolefin with terminal functionality and battery separator in general, the invention relates to multifunctional chain exchange agents (csas), a process for preparing ces, a composition comprising a csa and a catalyst, a process for preparing the composition, processes for preparing polyolefins, terminally functional polyolefins, and telequelic polyolefins with the composition, and polyolefins, terminally functional polyolefins, and telequelic polyolefins prepared by the processes.
公开号:BR112012001942B1
申请号:R112012001942
申请日:2010-07-28
公开日:2019-10-22
发明作者:R Wilson David；E Kamber Nahrain；d hustad Phillip；B Klamo Sara；P Clark Thomas
申请人:Dow Global Technologies Llc；
IPC主号:

专利说明:

History of the invention
Field of the invention [0001] In general, the invention relates to chain exchange agents (CSAs), a process for preparing CSAs, a composition comprising a CSA, a process for preparing the composition, processes for preparing polyolefins, polyolefins with terminal functionality, and telehelic polyolefins with the composition, and polyolefins, polyolefins with terminal functionality, and telehelic polyolefins prepared by the processes.
Description of similar technique [0002] The reactions of exchange or redistribution of binder-metal complexes (for example, alkyl aluminum, aluminum aryloxy, alkyl zinc, alkoxy zinc, and the like) containing or derived from polymerization catalysts are known. For example, see Healy M.D. et al., Sterically crowdwd aryloxide compounds of aluminum, Coordination Chemistry Reviews, 1994, 130 (1-2): 63-135; and
Stapleton R.A. et al., Olefin Polymerization, Organometallics, 2006; 25 (21): 5083-5092.
[0003] Examples of telekele polymers include polymer chains containing a hydroxyl group at each end
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2/113 of chain. Telehelic polymers can be used as binders for rocket fuels and as ingredients in coatings, sealants, and adhesives.
[0004] Telekele polymers have been prepared by a number of methods. U.S. Patent No. 5,247,023 mentions telekeletal polymers prepared from hydrocarbon polymers containing borane groups at chain ends or in polymer main chains. Such telekeletal polymers have a statistical (that is, essentially random) distribution of terminal functional groups.
[0005] Examples of polyolefin polymers include polyolefin homopolymers and polyolefin block copolymers. Polyethylene (also known as polyethylene or poly (methylene)), polypropylene, and poly (ethylene / alpha-olefin) are examples of polyolefins (also known as polyalkenes) widely used in industry. They are desirable to produce, for example, containers, pipes, films and foils for packaging, and synthetic lubricants.
[0006] Block copolymers often have properties superior to the properties of random copolymers and polymer mixtures. Properties, characteristics and, therefore, applications of block copolymers are influenced, among other things, by how block copolymers are prepared and by the structure and characteristics of catalysts used to prepare them.
[0007] One method for preparing block copolymers is live polymerization. Domski et al. re-examine block copolymers prepared from olefin monomers using
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3/113 live polymerization catalysts (Domski, G.J .; Rose, J.M .; Coates, G.W .; Bolig, A.D .; Brookhart, M., in Prog. Polym. Sci., 2007; 32: 30-92). Live polymerization processes employ catalysts having a single type of active site. Those live polymerization processes that produce high yields of block copolymers essentially involve only initiation and propagation steps and essentially lack side chain termination reactions. The processes of live polymerization are characterized by an initiation rate that exceeds or is in the order of the propagation rate, and essentially by the absence of transfer or termination reactions. A block copolymer prepared by live polymerization can have a narrow or extremely narrow molecular weight distribution and can be essentially monodispersed (i.e., the molecular weight distribution is essentially one).
[0008] Examples of block copolymers that can be prepared by live polymerization are olefin block copolymers (for example, poly (ethylene / alpha-olefin) block copolymers and, especially, copolymers in amphiphilic diblocks. comprise hydrophilic and hydrophobic polymer chains Copolymers in amphiphilic diblocks are useful, among other things, for surfactants, dispersants, emulsifiers, stabilizers, and antifoaming agents for aqueous mixtures; surface modifiers for plastics; and compatibilizers in composites and polymer mixes (Lu Y. et al., Syntheses of diblock copolymers polyolefin-bpoly (ε-caprolactone) and their applications as the polymeric compatilizer, Polymer, 2005; 46: 10585-10591). Lu Y. et al.
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4/113 report a batch polymerization process to prepare copolymers in polyolefin-b-poly (εcaprolactone) diblocks. The batch polymerization process polymerizes a selected olefin with a metallocene catalyst system and a chain transfer agent, and isolates a resulting intermediate polyolefin having a terminal hydroxyl group. Then, in a different reactor, the batch polymerization process converts the terminal hydroxyl group of the intermediate polyolefin into an aluminum alkoxide derivative with diethyl aluminum chloride, subsequently uses the aluminum alkoxide derivative as an initiator for ring-opening polymerization anionic ε-caprolactone to give the copolymer in polyolefin-b-poly diblocks (ε-caprolactone).
[0009] Reporting a significant advance in the preparation of olefin block copolymers (OBCs), Arriola D.J. et al. mention a catalytic system that produces block olefin copolymers with alternating semicrystalline and amorphous segments and a number of desirable material properties (Arriola DJ, et al., Catalytic Production of Olefin Block Copolymers via Chain Shuttling Polymerization, Science, 2006; 312: 714-719). The catalytic system can use a chain exchange agent to transfer polymer chains between two different catalysts with different selectivities of monomers in a single polymerization reactor. The catalytic system produces CBOs in an economically favorable continuous polymerization process.
[0010] As a result, chain exchange agents and olefin block copolymers have recently been an important area of research. Publications of applications for
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5/113 international patent PCT numbers WO 2005/073283 Al, WO 2005/090425 Al, WO 2005/090426 Al, WO 2005/090427 A2, WO 2006/101595 Al, WO 2007/035485 Al, WO 2007/035492 Al, and WO 2007/035493 A2 mention certain CSAs, catalytic systems, and olefin polymer compositions prepared therefrom. For example, WO 2007/035493 A2 mentions multicentre CSAs and a process that uses multicentre CSAs to prepare olefinic polymer compositions characterized solely by a wide range, especially a multimodal molecular weight distribution. The multicentre CSAs of WO 2007/035493 A2 are compounds or molecules containing two or more chain exchange portions
joined by a multipurpose linking groups. [0011] There is need in technique of new agents in exchange chain, processes from polimeri organization that use the same for prepare polyolefins, polyolefins with
terminal functionality, and telekeletal polyolefins, and polyolefins, terminal functional polyolefins, and thus prepared telekeletal polyolefins, process for preparing copolymers in amphiphilic diblocks and multiblocks, and articles comprising polyolefins, terminal functionality polyolefins, telekyl polyolefins, and diol copolymers. and amphiphilic multiblocks.
Brief summary of the invention [0012] The present specification presents a new inventive concept of a multifunctional chain exchange agent. The multifunctional chain exchange agent comprises a single distinguishable compound or molecule because it is capable of functioning in such a way that at least one olefin-containing polymer chain can be exchanged between two or
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6/113 more catalytic sites of an olefin polymerization catalyst having two or more catalytic sites or between two or more olefin polymerization catalysts and independently: (a) a non-olefin polymerization reaction may be initiated by the chain exchange agent multifunctional; (b) a functional group of the multifunctional exchange agent can be distinguished as being protected with a protecting group during the chain exchange, and then incorporated into the olefin-containing polymer chain; or (c) a non-olefin polymerization reaction can be initiated by the functional group after it has been incorporated into the olefin-containing polymer chain.
[0013] In a first preferred embodiment, the multifunctional chain exchange agent comprises a compound having one or more portions capable of exchanging chains, one or more portions of protecting or initiating polymerization, and at least one polyvalent linker group. The chain exchange plots are different from the polymerization protection / initiation plots. Each polymerization initiation chain exchange portion independently comprises a metal cation, each metal of the metal cations being, independently, tin or metal from any of Groups 2, 12, and 13 of the Periodic Table of the Elements. Each polyvalent linker group independently comprises 2 to 20 carbon atoms; 0, 1, or 2 carbonocarbon double bonds; and from 1 to 4 hetero atoms, each hetero atom being, independently, an oxygen atom, a sulfur atom, a hydrogen substituted nitrogen atom (ie, N (H)), a hydrocarbyl substituted nitrogen atom, an atom phosphorus substituted by hydrogen (ie
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7/113
Ρ (Η)), or a hydrocarbyl-substituted phosphorus atom. Each metal cation if a chain exchange portion independently binds to a different carbon atom of the same polyvalent linker group or to a carbon atom of a different polyvalent linker group and each metal cation to an initiation portion of The polymerization binds, independently to a heteroatom other than the same polyvalent linker group or to a heteroatom of a different polyvalent linker group, the metal cations are thus spaced from each other by at least one polyvalent linker group.
[0014] In a second embodiment, the present invention provides a process for preparing the inventive multifunctional chain exchange agent, which comprises the steps of: contacting a polyvalent group containing vinyl and hydroxy, thiol (i.e., -SH), hydrocarbilamino, amino, hydrocarbilphosphine, or phosphine (i.e., -PH ₂ ) to an alkyl-perhydrocarbon metal to prepare an organometallic intermediate, which is a hydrocarbyl metal vinyl alkoxide, hydrocarbyl metal vinyl hydride, hydrocarbyl vinyl amine metal, vinyl hydrocarbyl amine metal, vinyl (hydrocarbyl) hydrocarbyl metal, or vinyl hydrocarbyl metal phosphine; and contacting the organometallic intermediate with a hydrocarbyl metal monohydride, thereby preparing the multifunctional chain exchange agent, each metal being independently a tin or metal cation of any of Groups 2, 12, and 13 of the Periodic Table of the Elements.
[0015] In a third embodiment, the present invention provides a process for preparing a composition
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8/113 multifunctional, comprising the steps of: contacting the ingredients comprising the chain exchange agent as defined by any of claims 1 to 6, an original olefin polymerization catalyst, and an original cocatalyst, the contact being performed in conditions of preparation of catalyst, thus preparing the multifunctional composition, and the multifunctional composition being able to function as a multifunctional chain exchange agent and as an olefin polymerization catalyst.
[0016] In a fourth embodiment, the present invention provides the multifunctional composition prepared by the process of the third embodiment.
[0017] In a fifth embodiment, the present invention provides a process for preparing a chain exchange agent containing (poly-radical-polyolefin), which comprises the steps of: contacting the reactants comprising one or more olefin polymerization catalysts and at least at least one olefin monomer, one or more olefin polymerization catalysts comprising the multifunctional composition as defined by the fourth incorporation and the contact step being performed under olefin polymerization conditions, thereby preparing a multifunctional chain exchange agent containing poly- radical-polyolefin, the multifunctional chain exchange agent containing poly-radical polyolefin being a reaction product of the reactants.
[0018] In a sixth embodiment, the present invention provides the multifunctional chain exchange agent containing polyradical-polyolefin.
[0019] In a seventh embodiment, the present invention provides a process for preparing telekeletal polyolefin (i.e.,
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9/113 with terminal functionality), which comprises a step of: terminally functionalizing the poly-radical-polyolefin of the multifunctional chain exchange agent containing polyradical-polyolefin, thus preparing a telekelic polyolefin.
[0020] In an eighth embodiment, the present invention provides the telehelic polyolefin prepared by the process of the seventh incorporation, the telehelic polyolefin distinguishable by having, the telehelic polyolefin being distinguishable by having first and second functional groups spaced, the process deriving the first terminal functional group of a chain exchange portion, each such portion being of the multifunctional chain exchange agent containing poly-radical-polyolefin, the first and second terminal functional groups being structurally different from each other.
[0021] In a ninth embodiment, the present invention provides an article comprising the eighth embodiment telekelic polyolefin.
[0022] In a tenth embodiment, the present invention provides a process for preparing a terminal functional polyolefin, comprising the step of: terminating the poly-radical polyolefin of the multifunctional chain exchange agent containing poly-radical-polyolefin as defined by claim 11 , thus preparing a polyolefin with terminal functionality of formula (III):
H-polyolefin-CH ₂ -RL- (XH) _w (III) in which w is an integer equal to 1 or 2; each RL is independently C1-C19 alkylene or alkenylene _C2-C19; and each X is independently O, S, N (Η), N (hydrocarbyl
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10/113 of C1-C20) ι P (Η), or Ρ (C1-C20 hydrocarbyl) · [0023] In an eleventh embodiment, the present invention provides the polyolefin with terminal functionality prepared by the tenth incorporation process.
[0024] In a twelfth embodiment, the present invention provides an article comprising the polyolefin with terminal functionality of the eleventh embodiment.
[0025] In a thirteenth embodiment, the present invention provides a process for preparing an interpolymer in polyolefin / polyester, polyolefin / polyether, polyolefin / polyamide, or polyolefin / polyisocyanate multiblocks, the process comprising a step of: contacting the ingredients comprising the multifunctional chain exchange agent containing poly-radical-polyolefin and a polyester, polyether, polyamide or polyisocyanate-forming monomer, the contact step being performed under polyester, polyether, polyamide, or polyisocyanate-forming conditions, thereby preparing an interpolymer in polyolefin / polyester multiblocks, a polyolefin / polyether multiblock interpolymer, a polyolefin / polyamide multiblock interpolymer, or a polyolefin / polyisocyanate multiblock interpolymer.
[0026] Multifunctional chain exchange agents are characterized by having at least two mutually compatible and yet different functional activities. One of the functional activities comprises a chain exchange function. Another of the functional activities comprises a protective / initiating polymerization function, which comprises a protective group function or, in some embodiments, a function of initiating polymerization, or in some incorporations, both. Depending on the circumstances of the use of
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11/113 multifunctional chain exchange, the chain exchange function comprises protecting a chain of poly-radical polyolefin and transferring it to one or more different olefinic polymerization catalysts and finally returning again to protect. The function of initiating polymerization is essentially to initiate forming reactions of polyester, polyether, polyamide, or polyisocyanate, especially live polymerization reactions comprising forming reactions of polyester, polyether, polyamide, or polyisocyanate by ring opening.
[0027] An advantage of multifunctional chain exchange agents is, for example, the inventive incorporation of two functionally different portions containing metal in a single molecule or compound. Another advantage is that one of the functionally different plots containing metal is capable of functioning as a chain exchange group and the other of the functionally different plots containing metal is capable of functioning as a protecting group or a polymerization initiator group in a continuous polymerization process .
[0028] Another advantage of the multifunctional CSA refers to the design of the compound or molecule, which separates the two functionally different portions containing metal by a mutually compatible linker group. The design provides a means for the functionally different metal containing portion employed for chain exchange to successfully perform functional chain exchange activity in the presence of the functional group containing metal employed as a protecting group or polymerization initiator. The design also provides a means to terminally functionalize the poly-radical-polyolefin of poly-multifunctional chain exchange agents containing poly
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12/113 radical-polyolefin or a means to initiate functional activity of initiating polymerization in the presence of the metal-containing functional group for chain exchange. Such mutual compatibility between what may have until now been considered potentially conflicting activities or functional parcels, is particularly valuable for preparing copolymers in amphiphilic diblocks or multiblocks, especially in a continuous polymerization process.
[0029] An additional advantage is that the present invention provides new processes for preparing polyolefins, telealkic polyolefins, and copolymers in amphiphilic diblocks and copolymers in amphiphilic multiblocks.
[0030] Another advantage is that at least some of the interpolymers in polyolefin / polyester, polyolefin / polyether, polyolefin / polyamide, or polyolefin / polyisocyanate multiblock are characterized by having at least one unique characteristic such as, for example, polydispersion ( indicated by the polydispersity index) and related unique applications (eg battery separators). Additional advantages of the present invention are described below.
[0031] Polyolefin / polyester, polyolefin / polyether, polyolefin / polyamide, or polyolefin / polyisocyanate multiblock interpolymers prepared by a process of the present invention are useful, among other things, for surfactants, dispersants, emulsifiers, stabilizers, and agents defoamers for aqueous mixtures; surface modifiers for plastics; and compatibilizers in composites and polymeric mixtures. Polyolefin (which includes homopolymers and block copolymers
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13/113 of poly (olefin monomer / olefin comonomer) described later), teleelectric polyolefin, and interpolymers in polyolefin / polyester, polyolefin / polyether, polyolefin / polyamide, or polyolefin / polyisocyanate multiblocks, are also useful in numerous articles and applications such as, for example, manufacture of battery separators, elastic films for hygiene applications (for example, diaper liners); flexible molded products for household items, tools, consumer products (for example, toothbrush handles), sports products, building and construction applications, automotive and medical applications; flexible profiles and gaskets for household items (for example, refrigerator door profiles and gaskets); automotive, building and construction applications; packaging adhesives (for example, for use in the manufacture of corrugated cardboard boxes), hygiene applications, tapes, and tags / labels; and foams for sporting goods (eg foam mats), packaging, consumer goods, and automotive applications.
[0032] The remainder of this report describes additional incorporations, including the claims. Detailed description of the invention [0033] In some embodiments, the polyvalent linker group comprises, independently from 2 to 12, more preferably from 2 to 10, and even more preferably from 2 to 8 carbon atoms; and from 1 to 4 hetero atoms, each hetero atom being, independently, an O, S, N (H) atom, hydrocarbyl-substituted nitrogen atom, P (H), or hydrocarbyl-substituted phosphorus atom.
[0034] In a preferred embodiment of the oil exchange agent
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14/113 multifunctional chain is a compound of formula (I):
{((R ¹ ) yL4 ¹ [{(-CH2) _r ) _t -R ^L - [(X-) s} q} mM ² (R ² ) z] p] n (D
or a product in exchange of same, at what: my M number integer equal to2, 3, or 4; re one number all equal to 1 or 2; each one i from n, p, q. what if one number all equal to
1; and when r is 1, then each R ^L will independently be a C1-C19 alkylene or a C2-C19 alkenylene; or when (a) r is 1 et is 2, or (b) r is 2 et is 1, or (c) each month is 2 and each ret is 1, then each R ^L is independently a trivalent radical a C3-C19 alkane or a C3-C19 alkene; or n is an integer equal to 1, 2, or 3; is an integer equal to 1 or 2; p is an integer equal to 1 or 2; each of m, q, r, et is an integer equal to 1; and when each of sep is equal to 1, then each R ^L will independently be a C1-C19 alkylene or a C2-C19 alkenylene; or when (a) s is 1 and p is 2, or (b) s is 2 and p is 1, then each R ^L is independently a trivalent radical of a C3-C19 alkane or a C3-C19 alkene; or q is an integer equal to 2 or 3; each of m, n, p, r, s, et is an integer equal to 1; and each R ^G is independently a C1 -C19 alkylene or C2 alkenylene ^_ CI9; or each of m, n, eq is an integer equal to 1; each of p, r, s, et is an integer equal to 1 or 2; and R ¹ is a tetravalent radical of a C3-C19 alkane or of a C3-C19 alkene, where one retether of other retes is 2 and a depeséleo of other depesé2; y is an integer equal to 0, 1, or 2 and is chosen such that the sum of [y plus the multiplicative product of (n times q times r] is equal to the formal oxidation state of M ¹ , that is, (the state of
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15/113 formal oxidation of M ¹ ) = y + (n »q» r); z is an integer equal to 0, 1, or 2 and is chosen such that the sum of [z plus the multiplicative product of (m times q times s] is equal to the formal oxidation state of M ¹ , that is, ( the formal oxidation state of M ¹ ) = z + (m * q * s); each X is independently 0, S, N (Η), N (C1-C20 hydrocarbyl) r P (H), P (hydrocarbyl C1-C20); each M ¹ is a Group 2, 12, or 13 metal in the Periodic Table of Elements, the Group 13 metal being in a formal oxidation state equal to +3 and the Group 2 or 12 metal being in a state of formal oxidation equal to +2, each M ² is tin or a metal of Group 12 or 13 of the Periodic Table of the Elements, the metal of Group 12 being in a state of formal oxidation equal to +2, the metal of Group 13 being in a state of formal oxidation equal to +3, and the tin being in a state of formal oxidation equal to +2 or +4; each R ¹ is independently a C1-C20 hydrocarbyl; or when y is 2, an R ¹ will be hydrocarbyl of C1-C20 θ one R ¹ will be R ³ N (H) (R ³ ) 2N-, R ³ P (H) -, (R ³ ) 2P-, R ³ S-, or R ³ 0- or the two R ¹ come together to form a C2-C20 hydrocarbilene; and each R ² is independently a hydrogen, C1-C20 hydrocarbyl or C1-C20 -Dhydrocarbyl; or, when z is 2 or 3, two R ² come together to form a C2-C20 hydrocarbilene; each D shown in the C1-C20 -D-hydrocarbyl is independently -C (= 0) -C (= 0) -0-, -0-0 (= 0) -, -C (= 0) -N (hydrocarbyl of Ci-C ₆ ) -,
N (Ci-Cg hydrocarbyl) -C (= 0) -S (= 0) -, -S (= 0) 2-, or Si (Ci-C2o hydrocarbyl) ^_ 2; each R ³ is independently a C1-C20 hydrocarbyl or (C1-C2o hydrocarbyl) 3Si-; each of the C1-C19 alkylene, C2-C19 alkenylene, C3-C19 alkane, C3-C19 alkene, C1-C20 hydrocarbyl, and the above mentioned C2-C20 hydrocarbene is the same or different and is
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16/113 independently unsubstituted or substituted with one or more substituents R ^s ; and each R ^s is independently halogen, polyfluorine, perfluor, unsubstituted C1 -C1 alkyl, or unsubstituted C1-C19 heteroaryl.
[0035] A more preferred embodiment of the multifunctional chain exchange agent is a compound of formula (IA):
{(R ¹ ) yM ¹ - [CH2-R ^l - [X-} mM ² (R ² ) _z ] p] _n (IA) or an exchange product of the same, in which: m is an integer equal to l , 2, 3, or 4, each of nep is an integer equal to 1, and each R ^L is independently one of the C1-C19 alkylene or a C ₂ -Cig alkenylene; or n is an integer equal to 1, 2, or 3, each of mep is an integer of 1, and each R ^L is independently a C1-C19 alkylene or a C ₂ -Cig alkenylene; or p is an integer equal to 2, each of men is an integer equal to 1, and R ^L is a trivalent radical of a C3-C19 alkane or a trivalent radical of a C3-C19 alkene; y is an integer equal to 0, 1, or 2 and is chosen such that the sum of y + n is equal to the formal oxidation state of M ¹ ; z is an integer equal to O, 1, or 2 and is chosen such that the sum of z + m is equal to the formal oxidation state of M ² ; and X, Μ ¹ , M ² , R ¹ , and R ² are as defined above for formula (I); or each of m, n, p is equal to 1, (R ¹ ) _y M ¹ is absent, and M ² , R ² and z are as defined above for formula (I); or each of m, n, p is 1, (R ¹ ) _and M ¹ are absent and M ² , R ² and z are as defined above for formula (I).
[0036] In the divalent radical D, and the like, -C (= 0)
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17/113 means carbonyl, -C (= 0) -0- means a divalent carboxyl radical (radicals C and 0, the radical C being linked to M), —0 — C (= 0) - means a divalent carboxyl radical ( radicals o
and C, the radical 0 being attached to M), -C (= 0) N (Ci-Cg hydrocarbyl) - means a bivalent carboxamido radical substituted by -N (Ci-Cg hydrocarbyl) (radicals C and N, the radical C being linked to M), N (Ci-Cg hydrocarbyl) -C (= 0) - means a bivalent carboxamido radical substituted by -N (CiCg hydrocarbyl) (radicals N and C, radical C being linked to M ), S (= 0) - means sulfinyl (also called thionyl), S (= 0) ₂ - means sulfonyl, and -Si (Ci-C ₂ o hydrocarbyl) ₂ means a divalent silyl radical substituted by di (hydrocarbyl of Ci-Cg).
[0037] In some incorporations, where each of m, n, epe 1, (R) _and M is absent M joins with CH ₂ in formula (IA) to form a multifunctional chain exchange agent of formula (II ):
{CH ₉ -M ² (R ² ) hi; ¹ R ^l -X), (II) or an exchange product thereof, where g is an integer equal to O, 1, or2e is chosen such that the sum of (g + 2q) is equal to the formal oxidation state of M; q is defined as it was for the compound of formula (I), and R ^L , X, M, and R are as defined above for the compound of formula (IA). In solution, the multifunctional chain exchange agent of formula (II) can be characterized by forming an acyclic oligomeric structure. [0038] In the multifunctional chain exchange agent of
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18/113 formula (I) each (R ¹ ) yM ¹ -CH2 group comprises an example of the portion containing the chain exchange metal cation, the CH ₂ group derived from the CH ₂ -R ^L polyvalent linker group. Each group XM (R) _z comprises an example of the portion containing a metal cation for protection / polymerization initiation. The protecting group portion comprises a protecting group for OH, -SH, -NH ₂ , N (H) (Ci-C ₂₀ hydrocarbyl), -PH ₂ , or
P (H) (C ₁ -C ₂ hydrocarbyl). Preferably, the protecting group comprises M (for example, M (R) _z or exchange product thereof). The R ^L portion of the polyvalent linker group, CH ₂ -R ¹ , binds compatiblely to one or more chain exchange portions to one or more protective / polymerization initiator portions.
[0039] In another embodiment, the present invention provides a process for preparing the compound of formula (I):
{((R ^ yM ^ Í (-CH ₂ ) _r ) _t -R ^L - [(X-) s} q} mM ² (R ² ) _z ] _p ] _n (D or an exchange product thereof, the process comprising the steps of: (a) contacting a perhydrocarbon alkyl metal of formula (1):
M ² (C 1 -C 20 alkyl) (R ² ) z (D in which M ² , R ² and z are previously defined in the first incorporation, and a polyvalent group containing vinyl and hydroxy, thiol, amino, hydrocarbilamino, phosphine or phosphine hydrocarbon of formula (2):
[H ₂ C = C (R ⁴ )] r — R ^l1 - [XH] P (2) in which R ⁴ is hydrogen or a C 1 -C ₅ alkyl group and R ^{L 1} is absent or is a polyvalent radical of a hydrocarbon
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19/113 of Ci-Cis, the Ci-Cis hydrocarbon being saturated, or mono or di-unsaturated, and R ⁴ and R ^L1 being selected so that the number t of groups C (R ⁴ ) and R ^L1 have a total number of carbon atoms from 1 to 19 carbon atoms; and X, per are defined previously in the first incorporation, to give a vinyl alkoxide / sulfide / amide / phosphide of formula (3): [H2C = C (R ⁴ )] r — R ^l1 - [X — M ² (R ² ) _z ] p (3) and (b) contact the vinyl alkoxide / sulfide / amide / hydrocarbyl metal phosphide of formula (3) with n molar equivalents of a hydrocarbyl metal monohydride of formula (4):
HM ¹ (R ^ y (4) [0040] in which y, M ¹ , and R ¹ are defined previously in the first incorporation to give the multifunctional chain exchange agent of formula (I):
{((R ¹ ) yM ¹ [{(-CH2) _r ) _t -R ^L - [(X-) s} q} mM ² (R ² ) _z ] _p ] _n (D or exchange product thereof, where R, X, R, R, Μ, M, m, n, p, q, r, s, t, y, and z are previously defined.
[0041] In some embodiments, the multifunctional chain exchange agent containing poly-radical-polyolefin is characterized as being able to function as a chain exchange agent, as a polymerization initiating agent, as a protective agent, or any combination of the same. In some embodiments, the multifunctional chain exchange agent containing poly-radical polyolefin is characterized as being capable of functioning as an intermediary in a process to prepare telekeletal polyolefin, polyolefin, the multi-block interpolymer of
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20/113 polyolefin / polyester, polyolefin / polyether, polyolefin / polyamide, or inventive polyolefin / polyisocyanate.
[0042] The term poly-radical-polyolefin means a polymeric group comprising residues of at least one olefin monomer and two or more radicals. Formally, the poly-radical-polyolefin is obtained by removing one hydrogen atom from each of at least two carbon atoms. In some embodiments, the poly-radical-polyolefin of the multifunctional chain exchange agent containing polyradical-polyolefin comprises from 2 to 5 radicals, more preferably 2 or 3 radicals, and even more preferably 2 radicals.
[0043] In some embodiments, the reagents in the fifth incorporation process further comprise an associated olefin polymerization catalyst and an olefin comonomer, the associated olefin polymerization catalyst being characterized by being chemically different from and having different selectivities for the monomer olefin that, the original olefin polymerization catalyst; the multifunctional chain exchange agent containing polyradical-polyolefin being a multifunctional chain exchange agent containing poly-radical-poly (olefin monomer / olefin comonomer). In some embodiments, the associated olefin polymerization catalyst is activated with the original co-catalyst. In some embodiments, the reagents further comprise an associated co-catalyst, the associated co-catalyst being for activating the associated olefin polymerization catalyst. The terms original olefin polymerization catalyst and
Petition 870190071820, of 7/26/2019, p. 12/26
21/113 olefin polymerization catalyst combined for convenience to distinguish between two (or more) different catalysts when describing certain embodiments of the inventive process. Likewise, the terms original co-catalyst and associated co-catalyst for convenience are used to distinguish between two (or more) different co-catalysts when describing certain embodiments of the inventive process.
[0044] Where the reagents in the fifth incorporation process further comprise the associated olefin polymerization catalyst and the olefin comonomer described above, the multifunctional chain exchange agent containing poly-radical-polyolefin thus produced and that of the sixth incorporation is a multifunctional chain exchange agent containing poly-radical-poly (olefin monomer / olefin comonomer). Thus come up preferred aspects of the seventh to the thirteenth embodiment which are respectively: (7a): A process for preparing a poly (olefin monomer / comonomer olefin) telechelic; (8 ^a ): the telekelic poly (olefin monomer / olefin comonomer), the telekelic poly (olefin monomer / olefin comonomer) being characterized by having a non-statistical distribution of terminal functional groups;
(9 ^a): an article comprising the poly (olefin monomer / comonomer olefin) telechelic; (10a): A process for preparing a poly (olefin monomer / comonomer olefin) with terminal functionality; (11 ^a ): the poly (olefin monomer / olefin comonomer) with terminal functionality; (12a): an article comprising the poly (olefin monomer / comonomer olefin) with
Petition 870190071820, of 7/26/2019, p. 12/27
22/113 terminal functionality; and (13a): A process for preparing an interpolymer of multiblock poly (monomer olefin / comonomer olefin) / polyester, poly (monomer olefin / comonomer olefin) / polyether, poly (monomer olefin / comonomer olefin) / polyamide, or poly (olefin monomer / olefin comonomer) / polyisocyanate.
[0045] In any embodiment, preferably each poly-radical-polyolefin is a poly (olefin monomer / olefin comonomer) -poly-radical, and each polyolefin is a multi-block copolymer of poly (olefin monomer / olefin comonomer) .
[0046] Preferably, the multifunctional chain exchange agent containing poly-radical-polyolefin comprises a composition of formula (IV):
{(R ¹ ) yM ¹ - [(poly-radical-polyolefin) -CH2-R ^L - [X-} mM ² (R ² ) _z ] p] n (IV) or exchange product thereof, and the multifunctional chain exchange agent containing poly (olefin monomer-olefin poly-radical) comprises a composition of formula (IVa):
{(R ¹ ) yM ¹ - [(poly (olefin monomer-olefin poly-radical) CH2-R ^L - [X-} mM ² (R ² ) _z ] _p ] _n (IVa) or product exchange same, where in formulas (IV) and (IVa): R ¹ , R ² , y, M ¹ , R ^l , X, m, M ² , z, p, en are defined in the first incorporation, or a reaction product of two or more of the reagents in the process of the fifth incorporation. An example of the reaction product is the composition of formula (IV) or (IVa) where R ¹ , R ² , or R ¹ and R ² are, independently, residues of a reaction product of the olefin monomer. Another example is the composition of formula (IVa), where one or
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23/113 both of R ¹ and R ² are, independently, residues of a reaction product of the olefin comonomer.
[0047] As mentioned for step (a) of the fifth incorporation process, the process also employs, and the multifunctional composition of the fourth incorporation further comprises, the associated olefin polymerization catalyst. In such embodiments, the original olefin polymerization catalyst and the associated olefin polymerization catalyst are independently employed in the same or different amounts of co-catalyst; and the invention of a multifunctional chain exchange agent being characterized, without limitation, as functioning in step (a) in such a way that the polymer chains are transferred back and forth between the original olefin polymerization catalyst and the catalyst of associated olefin polymerization.
[0048] Sometimes, inventive polymers are collectively referred to herein as the present interpolymers. Here, the term poly block copolymer (ethylene / alpha-olefin) is used to allow exchange or replacement with the terms olefin block copolymer, OBC, ethylene / aolefin block interpolymer, and ethylene block copolymer. / a-olefin. Here, the terms alpha-olefin and α-olefin are used to allow for exchange or substitution.
[0049] For United States patent practice purposes and other patent practices that allow incorporation of object material by reference, the entire contents - unless otherwise stated - of each US patent, US patent application, order publication patent
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11/24
U.S., international PCT patent application and equivalent WO publication thereof, mentioned in this summary or in the detailed description herein are incorporated by reference. In the case where there is a conflict between what is written in this specification and what is written in a patent, patent application, or patent application publication, or a portion of which is incorporated by reference, what is written in this descriptive report dominates.
[0050] In the present patent application, any lower limit of a range of numbers, or any preferred lower limit of the range, can be combined with any upper limit of the range, or any upper limit of the range, to define a preferred aspect or embodiment the track. Each number range includes all numbers, both rational and irrational, grouped within that range (for example, the range from about 1 to about 5 includes, for example, 1, 1.5, 2, 2.75, 3 , 3.80, 4, and 5).
[0051] In the case where there is a conflict between the name of a compound and its structure, the structure dominates.
[0052] In the case where there is a conflict between a unit value that is mentioned without parentheses, for example, 5 centimeters, and a corresponding unit value that is mentioned in parentheses, for example, (2 inches), the unit value mentioned without parentheses dominates.
[0053] When used herein, the terms one, one, o, a, at least one (a) and one (a) or more are used in order to allow for exchange or replacement. In any aspect or embodiment of the present invention described herein, the term about (or approximately) in a phrase that refers to
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25/113 a numerical value can be removed from the sentence to give another aspect or embodiment of the present invention. In the aspects or forming incorporations that use the term about (or approximately), the meaning of about can be constructed from the context of its use. Preferably, about (or approximately) 90 percent to 100 percent of the numerical value, 100 percent to 110 percent of the numerical value, or 90 percent to 110 percent of the numerical value. In any aspect or embodiment of the present invention described herein, the open terms comprising, comprises, and the like (which are synonymous with including, having, and characterized by) can be replaced by the respective partially closed phrases consisting essentially of, consists essentially of, and similar or by the respective closed phrases consisting of, consists of, and the like to give another aspect or embodiment of the present invention. In the present patent application, when referring to a preceding list of elements (for example, ingredients), the phrases mixture of them, combination of them, and the like means any two or more, including all, of the elements listed. The term or using in a list of members, unless otherwise stated, refers to members listed individually as well as in any combination, and supports additional incorporations that mention any of the individual members (for example, in an incorporation mentioning the phrases greater than or equal at 10 percent and 10 percent or more, the term or supports another merger mentioned 10 percent and yet another merger mentioned more than 10 percent). The term plurality
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26/113 means two or more, with each plurality being selected independently, unless otherwise indicated.
[0054] Unless noted differently, the phrase Table
Periodic Table of the Elements refers to the Official Periodic Table, version dated June 22, 2007 by the International Union of Pure and Applied Chemistry (IUPAC). Likewise, any references to Group or Groups will be in relation to Group or Groups reflected in this Periodic Table of the Elements.
[0055] Unless otherwise noted, the general term hydrocarbyl is preferably C1-C20 hydrocarb · When used here, the term C1-C20 hydrocarbyl means a divalent hydrocarbon radical containing from 2 to 20 carbon atoms, each radical being monovalent and divalent hydrocarbon is independently aromatic or non-aromatic, saturated or unsaturated, normal chain or branched chain, cyclic (including monocyclic and polycyclic, fused and non-fused polycyclic) or acyclic, or a combination of two or more of the same; and each monovalent and divalent hydrocarbon radical is the same or different from another monovalent and divalent hydrocarbon radical, respectively, and independently substituted by one or more R ^s or, preferably, unsubstituted.
[0056] Preferably, C1-C20 hydrocarbyl is independently, C1-C2o alkyl, C3-C2o cycloalkyl, C1-C10 cycloalkylalkyl, Cg-C2o aryl, ° Cg-Cio aryl -C1-C10 alkylene substituted or unsubstituted. More preferably, each of the groups
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27/113 above has, independently, a maximum of 18 carbon atoms (for example, C1-C1 alkyl, C3-C18 cycloalkyl, Cs-Cg-C1 alkylene cycloalkyl, Cg-Cis aryl, or Cg-C10-C1-alkylene of C1-Cs), even more preferably a maximum of 12 carbon atoms (e.g., C1-C12 alkyl, C3-C12 cycloalkyl, Cg-Cs-C1-C4 alkylene, aryl of Cg-C12, or C-C-alkylene of C1-Cg).
[0057] The term C1-C20 alkyl means a normal or branched chain saturated hydrocarbon radical of 1 to 20 carbon atoms that is unsubstituted or substituted by one or more R ^s . Preferably, C1-C20 alkyl has a maximum of 18 carbon atoms, more preferably 12 carbon atoms, even more preferably 8 carbon atoms. Examples of unsubstituted C1-C20 alkyl include unsubstituted C1-C1 alkyl; unsubstituted C1-C10 alkyl; unsubstituted C1-C5 alkyl; methyl; ethyl; 1-propyl, 2-propyl, 1-butyl; 2-butyl; 3-methyl-propyl; 1,1-dimethyl-ethyl; 1-pentyl; 1-hexyl; 1-heptyl; 1-nonyl; and 1-decila. Examples of substituted C1-C20 alkyl include substituted C1-C1 alkyl, substituted C1-C10 alkyl, trifluoromethyl, and C25 alkyl. Preferably, each C1-C5 alkyl is, independently, methyl, ethyl, 1propyl, or 2-methyl-propyl.
[0058] The term C6-C20 aryl means an unsubstituted or substituted mono, bi or tricyclic aromatic hydrocarbon radical (with one or more R ^s ) of 6 to 20 total carbon atoms, of which at least 6 to 14 are ring carbon atoms, and the mono, bi or tricyclic radical comprises, respectively, 1, 2 or 3 rings, the 2 of which
Petition 870190071820, of 7/26/2019, p. 12/33
28/113 or 3 rings are, independently, fused or non-fused and the 1 ring is aromatic and at least one of the 2 or 3 rings is aromatic. Preferably, Cg-Cso aryl has a maximum of 18 carbon atoms, more preferably 10 carbon atoms, even more preferably 6 carbon atoms. Examples of aryl Cg-Cso include non-substituted aryl of C ₆ -C ₈ non-substituted, alkyl-C 2 -C ₅ -fenila, 2,4-bis (alkyl _Ci-C5) -fenila 2.4 , 6-tris (C1-C5 alkyl) phenyl, phenyl, fluorenyl, tetrahydro-fluorenyl, indacenyl, hexahydro-indacenyl, indenyl, dihydro-indenyl, naphthyl, tetrahydro-naphthyl, anthracenyl, and phenanthrenyl. Examples of substituted Cg-Cso aryl include substituted Cg-Cis aryl, 2,4-bis (Cg alkyl) -phenyl, poly-fluorophenyl, and fluoren-9-one-l-yl.
[0059] The term C3-C20 cycloalkyl means a saturated cyclic hydrocarbon radical of 3 to 20 carbon atoms that is unsubstituted or substituted by one or more R ^s . Preferably, C3-C20 cycloalkyl has a maximum of 18 carbon atoms, more preferably 12 carbon atoms, even more preferably 6 carbon atoms. Examples of unsubstituted C3-C20 cycloalkyl include unsubstituted C3-C12 cycloalkyl, unsubstituted C3-C10 cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl . Examples of substituted C3-C20 cycloalkyl include substituted C3-C12 cycloalkyl, substituted C3-C10 cycloalkyl, cyclopentanon-1-yl, and 1-fluoro-cyclohexyl.
[0060] Therefore, C2-C20 hydrocarbilene means an unsubstituted or substituted bivalent radical analog of
Petition 870190071820, of 7/26/2019, p. 12/34
29/113 Cg-Cso aryl, C ₃ -C2o cycloalkyl, or C ₂ -C20 alkyl, that is, Cg-Cso arylene, C ₃ -C2o cycloalkylene, θ C2-C20 alkylene, respectively . More preferably, each of the aforementioned groups independently has a maximum of 20 carbon atoms (for example, Ce ^- Cis arylene, C _{3 -} C ₂ cycloalkylene, θ C 2 - C 12 alkylene). In some embodiments, the divalent radicals are on adjacent carbon atoms (i.e. 1,2-divalent radicals), or spaced by one, two, or more intermediate carbon atoms (for example, respectively, 1,3-divalent radicals, 1,4-bivalent radicals, etc.). 1,2-, 1,3-, 1,4-, or alpha, bivalent omega-radicals, more preferably 1,2-bivalent radical is preferred.
[0061] The term C1-C19 alkylene means a normal or branched chain saturated bivalent radical of 1 to 19 carbon atoms that is unsubstituted or substituted by one or more R ^s . Examples of unsubstituted C1-C19 alkylene include unsubstituted C1-C12 alkylene, including unsubstituted C1-C12 alkylene and unsubstituted C1-C7 alkylene. Examples of unsubstituted C1-C7 alkylene include -CH ₂ -, -CH ₂ CH ₂ -, - (CH ₂ ) ₃ -,
I
-CH ₂ -CHCH ₃ , - (CH ₂ ) ₄ -, - (CH ₂ ) ₅ -, - (CH ₂ ) ₆ -, and (CH ₂ ) 5C (H) (CH ₃ ) -. Examples of substituted C1-C19 alkylene include substituted C1-C10 alkylene, substituted C1-C7 alkylene, -CF ₂ -, and - (CH ₂ ) _i4 C (CH ₃ ) ₂ (CH ₂ ) ₅ (ie 6 , 6-dimethyl-1,220-eicosylene).
[0062] The term C2-C19 alkenylene means a normal or branched saturated, mono- or di-unsaturated bivalent radical of 2 to 19 carbon atoms, which is not
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30/113 replaced or replaced by one or more R ^s . Preferably, C2-C19 alkenylene is mono-unsaturated, that is, it contains a carbon-carbon double bond.
[0063] The terms, C3-C19 alkane and C3-C6 alkane, mean a hydrocarbon molecule comprising 3 to 19 or 3 to 6 carbon atoms, respectively, the molecule being unsubstituted or substituted, saturated, acyclic or cyclic, normal or branched chain.
[0064] The term C3-C19 alkene means a mono-, or di-unsaturated hydrocarbon molecule comprising from 3 to 19 carbon atoms, the molecule being unsubstituted or substituted, acyclic or cyclic, of normal or branched chain. Preferably, the C3-C19 alkene is monounsaturated, that is, it contains a carbon-carbon double bond.
[0065] The term C1-C9 heteroaryl means an unsubstituted or substituted mono or bicyclic heteroaromatic cyclic radical (with one or more R ^s ) of 1 to 9 ring atoms and 1 to 4 ring hetero atoms, the hetero atoms being , independently, oxygen, nitrogen, phosphorus, or sulfur. The monocyclic and bicyclic heteroaromatic radicals comprise, respectively, 1 or 2 rings, the 2 rings of the bicyclic heteroaromatic radical being, independently, fused or non-fused to each other and at least one of the 2 rings is aromatic. Preferably, the C1-C9 heteroaryl is a 5 or 6 membered monocycle or a 9 or 10 membered bicycle. Examples of unsubstituted C1-C9 heteroaryl include unsubstituted C1-C4 heteroaryl, pyrrol-1-yl, furan-3-yl, thiophen-2-yl, pyrazol-1-yl, isoxazol-2-yl, isothiazol-5-yl, imidazol-l-yl, oxazol-4yl, thiazol-2-yl, 1,2,4-triazol-l-yl, 1,3,4-oxadiazole-2
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11/313 ila, 1,3,4-thiadiazol-2-yl, tetrazol-1-yl, pyridin-2-yl, pyrimidin-2-yl, pyrazin-2-yl, indole-1-yl, benzimidazole-1yl , quinolin-2-yl, and isoquinolin-2-yl.
[0066] The term halogen means fluorine (-F), chlorine (-C1), bromine (-Br), or iodine (-1). Preferably, halogen is fluorine or chlorine, more preferably fluorine. The term halide means fluoride anion (F ^- ), chloride (Cl ^- ), bromide (Br ^- ), or iodide (I ^- ).
[0067] Preferably, there is no 0-0, SS, or 0-S bond, other than 0-S bond in a functional group of bivalent radical S (0) or S (0) ₂ , in the multifunctional CSA of formula (D · [0068] The term saturated means devoid of carbon-carbon double bonds, carbonocarbon triple bonds, and (in groups containing heteroatom) devoid of carbon-nitrogen, carbon-phosphorus, and carbon-silicon double bonds. is substituted by one or more R ^s substituents, one or more double and / or triple bonds optionally may or may not be present in R ^s substituents. The term unsaturated means containing one or more carbon-carbon double bonds, carbon-carbon triple bonds, and (in heteroatom - containing groups) containing carbon-nitrogen double bonds, carbon-phosphorus, carbon and silicon, not including any such double bonds which may be present in R ^are substituents, if any, or rings (h uterus) aromatics, if present.
[0069] The term chain exchange agent refers to a compound such as the multifunctional CSA of formula (I) or a mixture of such compounds that is capable of causing polymer change (i.e., polymer chain) between at least two
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11/32
sites in catalysts active of the catalyst in polimeri zation in olefin original and of the catalyst in polimeri zation in olefin associated under conditions in polimeri zation in olefin. That is, the transfer of one
polymer fragment occurs for both and one or more of the active sites of the olefin polymerization catalysts.
[0070] Unlike a chain exchange agent, a chain transfer agent causes termination of polymeric chain growth and quantities for a one-time transfer of polymer from a catalyst to the transfer agent. That is, the multifunctional CSA is characterized by functioning in such a way that there is a one-time transfer of polyolefin homopolymer product or random polyolefin copolymer formed in such a polymerization process from the olefin polymerization catalyst to the multifunctional CSA. In such embodiments, it is not necessary for the multifunctional CSA to exchange chain reversibly, since such incorporations typically employ only one olefin polymerization catalyst, which can have or use only one active catalyst site.
[0071] In some embodiments, the inventive multifunctional chain exchange agent is characterized by having a ratio of chain exchange activity Ra-b / Rb-a · In general, for any two catalysts (A) and (B), the Ra-b / Rb-a chain exchange activity ratio is calculated by dividing a chain transfer rate from an active catalyst (A) site to an active catalyst (B) R _a -b site by a chain transfer rate of an active site of
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33/113 catalyst (B) for an active site of a catalyst (A) R _B _ _A. For the inventive multifunctional chain exchange agent, preferably the Ra-b / Rb-a chain exchange activity ratio is 0.01 to 100, more preferably 0.1 to 10, even more preferably 0.5 to 2.0, and even more preferably from 0.8 to 1.2. Preferably, an intermediate formed between the inventive multifunctional chain exchange agent and the polymer polymer chain is sufficiently stable that chain termination is relatively rare. The multifunctional chain exchange agent containing poly-radical-polyolefin is an example of said intermediate.
[0072] Selected different combinations of olefin polymerization catalysts having different rates of comonomer incorporation (described here) as well as different activities, and combining the inventive multifunctional chain exchange agent with one or more additional chain exchange agents, the additional chain exchange agents comprising one or more multifunctional chain exchange agents of formula (I), or one or more non-inventive chain exchange agents, or a combination thereof, different multi-block copolymer products can be prepared poly (olefin monomer / olefin comonomer). Such different products may have segments of different densities or concentrations of monomer, different lengths of blocks, different numbers of such segments or blocks, or a combination thereof. For example, if the chain exchange activity of the inventive multifunctional chain exchange agent is relatively low in relation to a rate of spread of
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34/113 polymeric chain of one or more of the catalysts, copolymers can be obtained in multi-blocks of longer block lengths and mixtures of polymers as products. On the other hand, if the chain exchange is very fast in relation to a polymeric chain propagation rate, a product copolymer will be obtained having a random chain structure and shorter block lengths. In general, an extremely fast chain exchange agent can produce a multi-block copolymer having substantially random copolymer properties. By proper selection of both catalysts and the multifunctional chain exchange agent, relatively pure block copolymers products, copolymers containing relatively large blocks or segments, and or mixtures of the above with various homopolymers and / or ethylene copolymers can be obtained.
[0073] Where the invention comprises or employs at least one additional chain exchange agent as described above, preferably the invention will comprise or employ a total of less than or equal to 3, and more preferably a total of 2 chain exchange agents , at least one of the total number of chain exchange agents being the multifunctional chain exchange agent of formula (I). Preferably the invention does not comprise or employ any non-inventive chain exchange agent. However, in some embodiments, it may be desirable to employ one or more non-inventive chain exchange agents. Non-inventive chain exchange agents that are suitable for combining with inventive chain exchange agents include metal compounds or complexes
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35/113 of Groups 1, 2, 12 or 13 containing at least one C1-C20 hydrocarbyl group, preferably aluminum, gallium or zinc compounds substituted by C1-C2o hydrocarbyl, and reaction products thereof with a proton source . Preferred C 1 -C 20 hydrocarbyl groups are alkyl groups, preferably straight or branched C 1 -C 6 alkyl groups. The most preferred chain exchange agents for use in the present invention are compounds of trialkyl aluminum and dialkyl zinc, especially triethyl aluminum, tri (isopropyl) aluminum, tri (isobutyl) aluminum, tri (n-hexyl) aluminum, tri (n- octyl) aluminum, triethyl gallium and diethyl zinc. Additional suitable exchange agents include the mixture reaction product formed by combining the above organometallic compound, preferably a tri (C 1 -Cs alkyl) aluminum or di (C 1 -Cs alkyl) compound, especially triethyl aluminum, tri (isopropyl) ) aluminum, tri (isobutyl) aluminum, tri (n-hexyl) aluminum, tri (n-octyl) aluminum, or diethyl zinc, with a less than stoichiometric amount (in relation to the number of hydrocarbyl groups) of a primary amine or secondary, of a primary or secondary phosphine, thiol, or hydroxyl compound, especially bis (trimethyl silyl) amine, terciobutyl (dimethyl) silanol, 2hydroxymethyl pyridine, di (n-pentyl) amine, 2,6di (terciobutyl) phenol, ethyl (1-naphthyl) amine, bis (2,3,6,7dibenzo-1-azacycloheptanoamine, diphenyl phosphine, 2,6 (di (terciobutyl) thiophenol, or 2,6-diphenyl phenol. Desirably, it is used sufficient amine, phosphine, thiol, or hydroxyl reagent such that at least one hydrocarbyl group remains per I take metal. The main reaction product of the previous combinations highly desirable to
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36/113 use as exchange agents in the present invention are:
di (bis (trimethyl silyl) amide) of n-octyl aluminum, bis (dimethyl (terciobutyl) siloxide) of isopropyl aluminum and di (pyridinyl-2-methoxide) of n-octyl aluminum, bis (dimethyl (tert-butyl) siloxane) of isobutyl aluminum, di (bis (trimethyl silyl) amide) of isobutyl aluminum, di (pyridine-2-methoxide) of n-octyl aluminum, bis (di (n (pentyl) amide) isobutyl aluminum, bis (dimethyl (terciobutyl) siloxide) ethyl aluminum, bis (2,3,6,7-dibenzo-1-azacycloheptanoamine, ethyl aluminum, bis (2,3,6,7-dibenzo-1-azacycloheptanoamine of n-octyl aluminum, bis ( n-octyl aluminum dimethyl (terciobutyl), ethyl zinc 2,6-diphenyl phenoxide, and ethyl zinc terciobutoxide Other suitable non-inventive chain exchange agents are described in WO 2005/073283 Al, WO 2005 / 090425 Al, WO 2005/090426 Al, WO 2005/090427 A2, WO 2006/101595 Al, WO 2007/035485 Al, WO 2007/035492 Al, and WO 2007/035493 A2.
[0074] The term exchange product of the same (s) means an oligomeric molecule or substance derived by intramolecular redistribution of two or more ligands to M ¹ or M ² , or by at least one ligand to M ¹ and at least a linker for M ² , or by intermolecular redistribution between at least one of said linkers of a molecule of formula (I) and at least one of said linkers of another molecule of formula (I); or a combination of intramolecular and intermolecular redistributions. The ligands for M ¹ refer to R ¹ and CH ₂ in formula (I). The ligands for M ² refer to R ² and X in formula (I). The term exchange product can also be referred to here as a
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37/113 redistribution. The invention considers exchange products for any inventive multifunctional chain exchange agent, including the multifunctional chain exchange agent of any of formulas (I) and (IV).
[0075] Examples of products of exchange of the compound of formula (I) are the compounds of formula (IB) and (IC)
CH ₂ R ^l X m m ² ch ₂ -r 'x (R ¹ ) -M ¹ M ² (R ² ) _z (IB) ^s cii ₂ -r ^[ X (IC)
C1I <R ^L X the compounds of divalent formulas R ^l ; and compounds of (IB) and formulas (ID) a having groups (IK) m ₂ (R ') _y -M ^ _x R ¹ -XM ² (R ² ) _z (ID)
X (R ⁱ ) yM ⁱ -C'R ^L '^ M ² (R ² ) z
X
H-, (IE) (R ') _y -NÉ
H,
H,
C '^ R ^[ x M ² (R ² ) Z c X (1F1) (R') _v -M ^, -C ^ / ^X x _Ί
NU M ² (R ² ) (R ') _y -M' ~ C
H ₂ (IF2) h ₂ (R ¹ ) ζ ^Χ χ, _Ί < ^R > z (RÁ-Nf-C ^X X
II ₂ (1F3) h ₂ (R ') _V -M ¹ -C ^Z
IE _Z XM ² (R ² ) _Z
R ¹ '
XM ² (R ² ) _Z (IF4) (R ') _v -M' _z c
H ₂
R ^r -XM ² (R ² ) _Z (IG) h ₂ (R ^, ) _v -M ¹ -C -R · _Z X
LM ² (R ² ) _z ^X In (1H)
FE (R ¹ ) -M * -C • R ¹ (R ^ yM ^ C
-i m
x · -M ² (R ² ) _z (1J) H _{2 z} XM ² (R ² ),(R ^l ) yM -c -Laughm; and X- M ² (R ² ) ₂
from (IK) n in which the compounds formulas (ID), (IE), and (IG) to (IK) have trivalent R ^L groups and the compounds of formulas (IF1) a
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38/113 (IF4) have tetravalent R ^L groups. (Formula (II) was deliberately omitted, that is, pronounced an i of the immediately preceding structure designations in order to avoid confusion with the aforementioned formula (II), that is, where (II) is the Roman number two).
[0076] In some incorporations of the multifunctional CSA of formula (I), m is an integer equal to l, 2, 3, or 4; aft an integer equal to 1 or 2; t is an integer equal to 1 or 2; each of n, p, q, and s is an integer equal to 1, this is a multifunctional CSA of formula (Im):
{((R ¹ ) yM ¹ (-CH2) _r ) _t -R ^L -X-} mM ² (R ² ) z (lm) or a replacement product for it, and when r is 1, then each R ^l independently, it will be a C1-C19 alkylene or a C ₂ -Cig alkenylene; or when (a) r is 1 and t is 2, or (b) r is 2 and t is 1, or (c) each of months is 2 and each of ret is 1, then each R ^L is, independently, a trivalent radical of a C3-C19 alkane or a C3-C19 alkene; and y, z, X, Μ ¹ , M ² , R ¹ , and R ² are defined previously for formula (I).
[0077] In some incorporations of the multifunctional CSA of formula (I), n is an integer equal to l, 2, or 3; is an integer equal to 1 or 2; p is an integer equal to 1 or 2; each of m, q, r and t is an integer equal to 1, this is a multifunctional CSA of formula (In):
(R ¹ ) yM ¹ [-CH2-R ^l - [(X-) SM ² (R ² ) _z ] _p ] _n (ln) or an exchange product thereof, and when each of sep is 1, then each R ^L , independently, will be a C1-C19 alkylene or a C ₂ -Cig alkenylene; or when (a) s is 1 pe
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39/113 for 2, or (b) s for 2 and p for 1, then each R ^L will be, independently, a trivalent radical of a C310 1 0 alkane
C19 or a C3-C19 alkene; and y, z, X, Μ, M, R, and R are previously defined for formula (I).
[0078] In some incorporations of the multifunctional CSA of formula (I), q is an integer equal to 2 or 3; each of m, n, p, r, s, and t is an integer equal to 1, ie a multifunctional CSA of formula (Iq):
(R ¹ ) yM ¹ {-CH2-R ^L -X-} qM ² (R ² ) z (Iq) or an exchange product thereof, and each R ^L is, independently, a C1-C19 alkylene or a ^_ CI9 C2 alkenylene; and y, z, X, Μ ¹ , M ² , R ¹ , and R ² are defined previously for formula (I).
[0079] In some incorporations of the multifunctional CSA of formula (I), each of m, n, and q is an integer equal to 1; each of p, r, s and t is an integer equal to 1 or 2, that is a multifunctional CSA of formula (Ip):
((R ¹ ) yM ¹ (-CH2) _r ) _t -R ^L - [(X-) sM ² (R ² ) z] _p (Ip) or an exchange product thereof, and R ^L is a tetravalent radical of a C3-C19 alkane or of a C3-C19 alkene, where one dretre oil another of ret is 2 and one of feet is 1 and the other of feet is 2; and y, z, X, Μ ¹ , M ² , R ¹ , and R ² are defined previously for formula (I).
[0080] In some incorporations of the multifunctional CSA of formula (I), R ¹ and R ² are aprotic, that is, R ¹ and R ² do not contain a -OH, -NH, -PH, or -SH portion.
[0081] In some incorporations of the multifunctional CSA of formula (IA), each of m, n and p is an integer equal to
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40/113
1, and R ^L is a C1-C19 alkylene, such incorporations being a
Multifunctional CSA of formula (Ia):
(R ¹ ) yM ¹ -CH2-C1-C19-XM ² alkylene (R ² ) _z (Ia)
110 or an exchange product thereof, where R, y, Μ, X, M, R, and z are as defined for the compound of formula (IA).
[0082] We prefer the multifunctional CSA of formula (Ia) in which ye 2, z and 2, X and 0, and each of M and M and Al in a state of formal oxidation equal to +3 as shown in the formula ( Ia-1):
(la-l) [0083] The multifunctional CSA of formula (Ia) in which y is 2, z is 2, X is N (C 1 -Cs alkyl), and each of M ¹ and M and Al is preferred in a state of formal oxidation equal to +3 as shown in formula (Ia-2):
À1 (CH ₂ ) ₂ _2o ~ N — Al
R ¹ '
(q. ^ quna (Ia-2) [0084] In some incorporations of the multifunctional CSA of formula (IA), n is an integer equal to l, 2, or 3, each of mep is an integer equal to 1, and R ^L is a C1-C19 alkylene, such incorporations being a multifunctional CSA of formula (Ib):
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41/113 (R ¹ ) yM ¹ - [C1-C19-XM ² (R ² ) z] CH2-alkylene z] n (Ia) in which R, y, Μ, X, M, R, and z are as they are defined for the compound of formula (IA).
[0085] The multifunctional CSA of formula (Ib) in which n is 3, y is 0 (therefore R ¹ is absent), z is 2, each X is O, each R ^L is independently a C1- alkylene is preferred C19, and each of M and M and Al in a state of formal oxidation equal to +3 as shown in formula (Ib-1):
R ² R ²
R ^{2 1} rr r ^Alc * ^ui “O'Al η 7 i ¹ leno ^x ₂ leno ² Al
CII ₂ ( _C1 -C _l9 ; Alkylene ^υ
R ² (Ib-1)
The multifunctional CSA of formula (Ib) is preferred in
R ¹ is absent). z is 2, each X is
2, v is 0 [0086] which n is
O, each R ^L is independently a C1-C19 alkylene, M ¹ is Zn in a formal oxidation state equal to +2, and M and Al in a formal oxidation state equal to +3 as shown in the formula (Ib-2 ):
R ² R ²
Àl-O- (C ₁ .C ₁₉ ) ^A ^ - CII2-Zn-CII2- (C1-C19: ^A ^ -; - O-Al _v
R ² R ² (Ib-2) [0087] In some incorporations of the multifunctional CSA of formula (IA), n is 2, each of mep is an integer equal to 1, and R ^L is a trivalent radical of an alkane of C3-C6
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42/113 (RÕyM ^ CHs- (C ₃ -C ₉ alkane-trilyl) - [XM ² (R ² ) _z ] _n2 (Io) or exchange product thereof, in which R, y, Μ, X, M, R, and z are as defined for the compound of formula (IA).
[0088] The multifunctional CSA of formula (Ic) is preferred in which y is 2, each z is 2, each X is O, each R ^L is a tnvalent radical of a C3-C19 alkane, and each of M and M and Al in a state of formal oxidation equal to +3 as shown in formula (Ic-1):
R ²
R ² (€ ΙΙ ₂ ) _μ6 -Ο-Α1
Al — Ο— (€ Η ₂ ) μ ₆ —ÇH ^R
R ² _R i (Cll ₂ ) ₀ . ₆ -CH ₂ ^ _Ar ^R
R ¹ (Ic-1) [0089] The multifunctional CSA of formula (Ic-1) as shown in the formula (Ic-la) is preferred
R ²
R ² (CH ₂ ) ₂ Q-Al /
AI-O- (C1I ₂ ) ₂ —Cl ·!
^r2 1 1
CH ₂ -CII ₂ ^ _a1 ^ ^R
R ¹ (Ic-la) [0090] In some incorporations of the multifunctional CSA of formula (IA), m is an integer equal to l, 2, 3, or 4, each of nep is an integer equal to 1, and R ^L is a C1-C19 alkylene, such incorporations being a multifunctional CSA of formula (Id):
{(R ¹ ) yM ¹ -CH2-C1-C19-X-} alkylene _m M ² (R ² ) _z
Petition 870190071820, of 7/26/2019, p. 12/28
43/113 (Id) or an exchange product thereof, in which R, y, Μ, X, M, R, and z are as defined for the compound of formula (IA).
[0091] The multifunctional CSA of formula (Id) is preferred in which me3, ye2, zeO (therefore R is absent), each X and O, each R ^L is independently a C1-C19 alkylene, and each of M and M and Al in a state of formal oxidation equal to +3 as shown in the formula (Id-1):
Rl ^ Al-- _C [- [ ₂ ^ ( _C] _ _{C] 9} ) A ₁ q _U i- ^ _{0 0} , (C _r C _l9 Alqui — CH ₂ -á] leno / leno 1
Al K '_ _Ί (C | -C | ₉ ^a1c I ^u1_ ~ CI 1, - Al leno ²
R ^l (Id-1) [0092] In some incorporations of the multifunctional CSA of formula (IA), each of m, nep is an integer equal to 1, and R ^L is a C2-C19 alkenylene, such incorporations being a multifunctional CSA of formula (le):
(R ¹ ) yM ¹ -CH ₂ -C ₂ alkenylene -Ci ₉ -XM ² (R ² ) _z (le) or an exchange product thereof, in which R, y, Μ, X, M, R, and z are as defined for the compound of formula (IA).
[0093] We prefer the multifunctional CSA of formula (le) in which ye2, ze2, XeO, and each of M and M and Al in a state of formal oxidation equal to +3 as shown in formula (Ie-1) :
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44/113 ^R Λ
Al— (CH ₂ ) ₂ . _1o -C = C— (CII ₂ ) ₂ . ₈ —O-aÍ η Η H
RR (Ie-1) [0094] The multifunctional CSA of formula (le) is preferred in which y is 2, z is 2, X is N (C 1 -Cs alkyl), and each of M ¹ and
M and Al in a state of formal oxidation equal to +3 as shown in formula (Ie-2):
^R / ²
Al— (CH ₂ ) 7. _io -C = C— (CH ₂ ) ₂ N-Al
R '“ ^{Π Π} R ² (^ alkyl (Ie-2) [0095] In some incorporations of the multifunctional CSA of formula (IA), each of m, nep is 1, and (RQyM ¹ is absent, and joins M with CH2 in formula (IA) to form the multifunctional chain exchange agent of formula (II):
{CII ₂ -M ² (R ² ) _O
I ^B
R ^[ -X} _q (ii) or an exchange product of the same, in which g is an integer equal to O, 1, ou2e is chosen such that the sum of (g + 2q) is equal to the formal state of M ² , and R ^L , X, M ² , and R ² are as defined for the compound of formula (IA).
[0096] We prefer the multifunctional CSA of formula (II) in which gel, qel, R and (CH ₂ ) i-6, X and O and M and Al in a state of formal oxidation equal to +3 as shown in formula (Ha):
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45/113
H ₂ C ----- Al (CH ₂ ) j_ ₆ —O (lia) [0097] The multifunctional CSA of any of the formulas (I), (IA), (Ia), (Ia- 1), (Ib), (Ib-1), (Ib2), (Ic), (Ic-1), (Id), (Id-1), (le), (Ie-1), (II) , or (lia), or exchange product thereof, in which instead of X being O, at least one, and more preferably each X is N (C 1 -Cg alkyl) and any remaining X is as defined in the formula (I). The multifunctional CSA of any of the formulas (I), (IA), (Ia), (Ia-1), (Ib), (Ib1), (Ib-2), (Ic), (Ic) is also preferred -1), (Id), (Id-1), (le), (Ie-1), (II), or (Ha), or exchange product thereof, in which instead of X being O, at minus one, and more preferably each X is S, N (Η), P (H), or P (C1-C20 hydrocarbyl)> and any remaining X is as defined in formula (I).
[0098] In some incorporations of the multifunctional CSA of formula (I) (and therefore of any subgeneric formula such as, for example, (IA), (Ia), (Ia-1), (Ib), (Ib- 1), (Ib-2), (Ic), (Ic-1), (Id), (Id-1), (le), (Ie-1), and (lia)), certain R ^{L are} preferred, X, R ¹ , R ² , Μ ¹ , M ² , m, n, p, q, r, s, t, y, ez.
[0099] Preferably, M and M are, independently, a metal of Group 2, that is, magnesium (Mg) or calcium (Ca), Mg or Ca being in a state of formal oxidation equal to +2; tin (Sn), Sn being in a state of formal oxidation equal to +2 or +4; a Group 12 metal, that is, zinc (Zn), Zn being in a state of formal oxidation equal to +2; or a Group 13 metal, that is, boron (B), aluminum (Al), or gallium
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46/113 (Ga), B, Al, or Ga being in a state of formal oxidation equal to +3.
[0100] More preferably, each M ¹ is, independently, Al, B, or Ga, B, Al, or Ga being in a state of formal oxidation equal to +3; or Zn or Mg, Zn or Mg being in a state of formal oxidation equal to +2. In some embodiments, each M ¹ is, independently, Al, B, or Ga, B, Al, or Ga being in a state of formal oxidation equal to +3. In some embodiments, each M ¹ is Al in a state of formal oxidation equal to +3. In some embodiments, each M ¹ is, independently, Zn or Mg in a state of formal oxidation equal to +2. In some embodiments, each M ¹ is Zn in a state of formal oxidation equal to +2.
[0101] Also more preferably, each M ² is Al in a state of formal oxidation equal to +3; or Zn in a state of formal oxidation equal to +2; or Sn in a state of formal oxidation equal to +2 or +4. In some embodiments, each M ² is Al in a state of formal oxidation equal to +3. In some embodiments, each M ² is, independently, Zn in a state of formal oxidation equal to +2. In some embodiments, each M ² is, independently, Sn in a formal oxidation state equal to +2 or +4.
[0102] In some embodiments, each of M ¹ and M ² is Al in a state of formal oxidation equal to +3. In some embodiments, each of M ¹ and M ² is Zn in a state of formal oxidation equal to +2.
[0103] In some embodiments, each (CH ₂ ) ₂ _ ₂ o, C1-C19 alkylene, C ₂ -C9 alkenylene, trivalent radical of a C3-C19 alkane, or a trivalent radical of a C ₃ alkene C19 for R ^L is, independently, a (CH ₂ ) ₂ _i ₂ , alkylene of CiPetição 870190071820, of 07/26/2019, p. 52/128
47/113
C1, C2-C12 alkenylene, trivalent radical of a C3-C12 alkane, or a trivalent radical of a C3-C12 alkene, respectively; more preferably, (CH ₂ ) 2-io, C1-C10 alkylene, C2-C10 alkenylene, trivalent radical of a C2-C10 alkane, or a trivalent radical of a C2-C10 alkene, respectively; and even more preferably a (ΟΗ ₂ ) 2-8λ C2-C8 alkylene, C2-C8 alkenylene, trivalent radical of a C2-C8 alkane, or a trivalent radical of a C2-C8 alkene, respectively.
[0104] In some embodiments, each C2-C8 alkylene is non-branched C ₂ -C8 alkylene. In some embodiments, each non-branched C2-C8 alkylene is independently CH ₂ , CH ₂ CH ₂ , or (CH ₂ ) 3. In some embodiments, the unbranched C2-C8 alkylene is (CH ₂ ) 3. In some embodiments, non-branched C2-C8 alkylene is independently (CH ₂ ) ₄ , (CH ₂ ) s, or (CH ₂ ) 6 · In some embodiments, non-branched C2-C8 alkylene is , independently, (CH ₂ ) 8 · In some embodiments, each C 1 -C alkylene is, C ₁ or C ₂ alkylene (ie, CH ₂ or CH ₂ CH ₂ ).
[0105] In some embodiments, at least one C 1 -C 6 alkylene is branched C 3 -C 8 alkylene.
[0106] In some embodiments, the C3-C8 alkane trivalent radical is a Cg alkane trivalent radical. In some embodiments, the C3C alkane trivalent radical is a C5 alkane trivalent radical. In some embodiments, the trivalent radical of a C3 -C8 alkane is a trivalent radical of a C ₄ alkane. In some embodiments, the C3-C8 alkane trivalent radical is a C3 alkane trivalent radical. The trivalent radical
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48/113 Cg alkane is most preferred.
[0107] In some embodiments, each C ₂ -Cg alkenylene is an unbranched C ₂ -Cg alkenylene. In some embodiments, each non-branched C ₂ -Cg alkenylene is (CH ₂ ) ₅ -C (H) = C (H) -CH ₂ -.
[0108] In some embodiments, each R ² is, independently, a C1-C40 hydrocarbyl, θ most preferably, a C-C2q hydrocarbyl. In some embodiments, each R ² is, independently, a C1-C2- (= 0) C- hydrocarbyl (for example, acetyl, propionyl, or hexanoyl). In some embodiments, z is 2 or 3 and two R ² come together to form a C ₂ -C ₂ q hydrocarbilene.
[0109] In some incorporations, at least one
hydrocarbyl from C1-C40 it's alkyl of C1-C40. In some incorporations, R ¹ is alkyl of Ci-C ₂₀ . In some incorporations, R ² is alkyl of Ci-C ₂₀ . In some incorporations, each one of R ¹ and R ² is regardless
C ₁ -C ₂ alkyl q. In some embodiments, each hydrocarbyl θ C1 -C40 alkyl C ₂ -C q. In some embodiments, each C ₁ -C ₂ alkyl is independently C 1 -C 10 alkyl, more preferably C 1 -C 6 alkyl, and even more preferably C 1 -C 6 alkyl. In some embodiments, y is 2, R ¹ is C ¹ -C 2 hydrocarbyl, and an R ¹ is (R ³ ) 2N-, (R ³ ) 2P-, R ³ S-, or R ³ O-. In some embodiments, y is 2, and two R ¹ are joined to form C2-C ₂ hydrocarbilene q. R ³ is C1-C2q hydrocarbyl. In some embodiments, R ³ is (Ci-C2o hydrocarbyl) 3Si-.
[0110] In some incorporations, each X is N (H). In some incorporations, each X is S. In some incorporations, each X is P (H). In some incorporations, each X is P (hydrocarbyl of
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11/113
Ci-C ₂₀ ). In some embodiments, and more preferably, each X is 0. In some embodiments, and most preferably, each X is N (C1-C20 hydrocarbyl) · In some embodiments, each C1-C20 hydrocarbyl is C1-C20 alkyl · In some embodiments, each C1-C20 alkyl is C1-C12 alkyl.
[0111] In some embodiments, each of the aforementioned C1-C19 alkylene, C1-C19 alkenylene, C3-C19 alkane, C3-C19 alkene, C1-C20 hydrocarbyl, θ C2-C20 hydrocarbene are non- replaced (that is, all groups in the multifunctional CSA of formula (I) are not replaced). In some embodiments, at least one of the aforementioned C1-C19 alkylene, C1-C19 alkenylene, C3-C19 alkane, C3-C19 alkene, C1-C20 hydrocarbyl, C2-C20 hydrocarbene is replaced with one or more substituents R ^s , preferably 1 or 2 R ^s . In some embodiments, each R ^s is, independently, fluorine, unsubstituted C1-C9 alkyl, or unsubstituted C1-C9 heteroaryl, more preferably unsubstituted C1-C10 alkyl, or unsubstituted C1-C9 heteroaryl. Preferably, the unsubstituted C1-C9 heteroaryl is pyridinyl.
[0112] In some embodiments, polymerizable olefins (i.e., olefinic monomers and olefinic comonomers) useful in the processes of the invention are C2-C40 hydrocarbons consisting of carbon and hydrogen atoms and containing at least 1 and preferably no more than 3, and more preferably no more than 2 carbonocarbon double bonds, where the carbon-carbon double bonds do not include aromatic carbon-carbon bonds (for example, as in phenyl). In some incorporations, 1 to 4 are replaced
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50/113 hydrogen atoms of the C2-C40 hydrocarbons, each with a halogen atom, preferably fluorine or chlorine to give halogen-substituted C2-C40 hydrocarbons. C2-C40 (non-halogenated) hydrocarbons are preferred. Preferred polymerizable olefins useful for producing the polyolefins are: ethylene and polymerizable C3-C40 olefins. C3-C40 olefins include alpha-olefins, cyclic olefins, styrene, and a cyclic or acyclic diene. Preferably, the alpha-olefin comprises a C3-C40 alpha-olefin, more preferably, branched-chain C3-C40 alpha-olefin, even more preferably straight-chain C3-C40 alpha-olefin, even more preferably C3 alpha-olefin. -C40 linear chain alpha-olefin from C3-C40 linear chain of formula (A):
CH ₂ = CH ₂ - (CH ₂ ) kCH ₃ (A) [0113] in which k is an integer from 0 to 37, and even more preferably a straight chain C3-C40 alpha-olefin that is 1-propene , 1-butene, 1-pentene, 1-hexene, 1heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1hexadecene, 1-heptadecene , 1-octadecene, a C ₈ -C ₄₀ alpha-olefin, or a straight chain C2o ^- C24 alpha-olefin. Another preferred polyolefin is C8-C40 alpha-olefin which is aromatic or non-aromatic, aromatic C8-C40 alpha-olefin containing at least one benzene derivative (for example, styrene, alpha-methyl-styrene or divinylbenzene) or naphthalene (eg naphthalene vinyl). Similar to that mentioned above, the C8-C40 olefin can be optionally substituted to give a halogen substituted C8-C40 olefin (for
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51/113 (4-fluoro-styrene). Preferably, the cyclic olefin is a C3-C40 cyclic olefin. Preferably, the cyclic or acyclic diene is a C4-C40 diene, more preferably a conjugated diene at the 1,3 positions of C4-C40, and even more preferably 1,3-butadiene.
[0114] Polyolefins (for example, homopolymer polyolefins, telekeletal polyolefins, and terminally functional polyolefins) that can be prepared by the process of the invention include, for example, olefinic homopolymers, comprising residues of the olefinic monomers described in the immediately preceding paragraph. Examples of olefinic homopolymers are: polyethylene, polypropylene, poly (C3-C40 alpha-olefin), and polystyrene. Other polyolefins that can be prepared by the process of the invention include, for example, olefinic interpolymers, including olefinic copolymers, especially olefinic block copolymers, and telephonic olefinic interpolymers. In some embodiments, they are olefinic interpolymers comprising residues of ethylene and one or more polymerizable C3-C40 olefins such as, for example, a block copolymer of poly (olefin monomer / olefin comonomer). The preferred polymerizable C3-C40 olefins are C3-C40 alpha-olefins. Preferred olefinic interpolymers are those prepared by copolymerizing a mixture of two or more polymerizable olefins such as, for example, ethylene / propylene, ethylene / l-butene, ethylene / l-pentene, ethylene / l-hexene, ethylene / 4-methyl- l-pentene, ethylene / l-octene, ethylene / styrene, ethylene / propylene / butadiene, ethylene / propylene / hexadiene, ethylene / propylene / ethylidene
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52/113 norbornene, and other EPDM terpolymers. Preferably, the polyolefin is an ethylene homopolymer (e.g., a high density polyethylene), an ethylene / alpha-olefin interpolymer (i.e., poly (olefin monomer / olefin comonomer) copolymer such as, for example, a poly) (ethylene / l-octene)), or an ethylene / alpha-olefin / diene interpolymer (i.e., a poly (ethylene / alpha-olefin / diene terpolymer, such as, for example, a poly (ethylene / l-octene / 1,3-butadiene).) Polyolefins include non-block copolymers of poly (olefin monomer / olefin comonomer).
[0115] In some embodiments, the inventive polyolefin comprises a mixture of at least two different polyolefins, at least one of which can be prepared by the inventive process. Examples of such mixtures include a mixture of polypropylene homopolymer and a block copolymer of poly (olefin monomer / olefin comonomer). [0116] In some embodiments, the block copolymer of poly (olefin monomer / olefin comonomer) of the invention can be represented by the following formulas:
A-B or A-B-A where, A represents a hard block or segment and B represents a soft block or segment. Preferably, A and B bond in a linear fashion, not in a branched or star fashion.
[0117] Other embodiments of the invention can be represented by the following formulas:
A- [(BA) _n ] or A- [(BA) _n B] where n is at least 1, preferably an integer greater than 1, such as 2, 3, 4, 5, 10, 15, 20, 30 , 40, 50, 60,
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53/113
70, 80, 90, 1000, or greater, A represents a hard block or segment and B represents a soft block or segment. Preferably, A and B bond in a linear fashion, not in a branched or star fashion.
[0118] Additional embodiments of the invention can be represented by the following formulas:
A- (AB) _n -A or A- (AB) _n -B or B- (AB) _n -B where, n is at least 1, preferably an integer greater than 1, such as 2, 3, 4, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 1000, or greater, A represents a hard block or segment and B represents a soft block or segment. Preferably, A and B bond in a linear fashion, not in a branched or star fashion.
[0119] In other embodiments, the copolymer in poly (olefin monomer / olefin comonomer) block of the invention does not have a third type of block. In yet other incorporations, each of blocks A and blocks B have monomers or comonomers randomly distributed within the block. In other words, neither block A nor block B comprises two or more segments (or sub-blocks) of different composition, such as an end segment, which has a different composition than the rest of the block.
[0120] In other incorporations, block copolymers of poly (olefin monomer / olefin comonomer) from
invention have a third type of block or segment and can be represented by following formula:ABC where, A represents a block or hard segment, B represents a block or soft segment, and Ç represents or one block or hard segment or a block or segment soft.
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54/113
Preferably, the A, B, and C bond in a linear fashion, not in a branched or star shape.
[0121] Other embodiments of the invention can be represented by the following formulas:
A- (BC) n OR A- (BC) nB or A- (CB) _n or A- (CB) _n C where n is at least 1, preferably an integer greater than 1, such as 2, 3, 4 , 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 1000, or greater, A represents a block or hard segment, B represents a block or soft segment, and C represents or a block or hard segment or a block or soft segment. Preferably, the A, B, and C bond in a linear fashion, not in a branched or star shape. [0122] Additional embodiments of the invention can be represented by the following formulas:
A- (BC) _n -A or A- (BC) _n -B or A- (BC) _n -C or B- (AC) nA or B- (AC) nB or B- (AC) _n -C or C- (AB) _n -A or C- (AB) _n -B or C- (AB) _n -C where, n is at least 1, preferably an integer greater than 1, such as 2, 3, 4, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 1000, or greater, A represents a block or hard segment, B represents a block or soft segment, and C represents either a block or hard segment or a block or soft segment. Preferably, the A, B, and C bond in a linear fashion, not in a branched or star shape. [0123] Blocks or hard segments refer to crystalline or semi-crystalline blocks of polymerized units in which in some embodiments they contain ethylene, preferably ethylene is present in an amount greater than about 80 molar percent, and preferably in an amount greater than 88 percent molar. In other words,
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55/113 the comonomer content in the hard segments is less than 20 mol% and, preferably, less than 12 percent by weight. In some incorporations, the hard segments comprise all or substantially all ethylene. Such hard blocks are sometimes referred to here as blocks or segments rich in polyethylene.
[0124] On the other hand, blocks or soft segments refer to blocks of polymerized units in which the comonomer content is greater than 20 mole percent, preferably greater than 25 mole percent, up to 100 mole percent. In some incorporations, the comonomer content in the soft segments may be greater than 20 per
percent molar, bigger what 30 per percent molar, bigger what 35 per percent molar, bigger what 40 per percent molar, bigger what 50 per percent molar, or greater what 60 molar percent. Segments or
soft blocks can refer to amorphous segments or blocks or with crystallinity levels lower than those of hard blocks or segments.
[0125] Additional embodiments include copolymers in poly (olefin monomer / olefin comonomer) blocks of the invention in which at least one of the polymeric blocks is amorphous (soft block) and at least one other polymeric block is crystallizable (hard block). Preferably the difference between the T _g (glass transition temperature, measured by differential scanning calorimetry (DSC) expected for the amorphous polymeric block and the T _m (melting transition temperature, measured by DSC) for the crystallizable polymeric block is at least 40 ° C, more preferably at least 80 ° C, and even more preferably at least 100 ° C. The crystalline melting point (T _m ) refers to the melting point
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Maximum 56/113 determined by DSC according to the ASTM D-3418 test method. Preferably, T _m for the crystallizable polymeric block is greater than the expected T _g for the amorphous polymeric block. More preferably, at least one block is crystalline or semi-crystalline, having a crystalline melting point of at least 100 ° C, more preferably at least 105 ° C, and even more preferably at least 120 ° C; and at least one block is amorphous or non-crystalline. Also preferably, the heat of melting associated with the melting point of any crystalline polymeric block is at least 20 Joule per gram (J / g), preferably at least 40 J / g, and more preferably at least 50 J / g g, determined by DSC analysis. DSC analysis is in accordance with the standard method described last. The invention also includes polymers in which crystallinity is induced or improved by the use of nucleating agents, thermal annealing, and / or deformation. When used here, the expected term (s) when used in reference to the properties of polymeric entities are those predicted by the method for calculating the infinite molecular weight, at room temperature (25 ° C), of infinite molecular weight, published in Jozef Bicerabo, Prediction of Polymer Properties, 2nd edition, Marcel Dekker, Inc., New York (Bicerano technique). The technique is also incorporated into software, including SYNTHIA ™, obtainable from Molecular Simulations Inc., a subsidiary of Pharmacopeia, Inc. The expected properties of certain representative polymers calculated according to the Bicerano technique are found in Table 1 in WO 2008 / 027283 and in the corresponding US patent application No. 12 / 377,034, filed on February 10, 2009. In some
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57/113 incorporations, the segments or hard blocks comprise all or at least 90 molar percent of an alpha-olefin. Such hard blocks can be referred to herein as blocks (segments) rich in poly (alpha-olefin). The alpha-olefin comprising the poly (alpha-olefin) rich hard block can be, for example, polypropylene, poly (1-butene), or poly (4methyl-1-pentene).
[0126] Preferred polyolefins include copolymers (e.g., ethylene / octene copolymers) bearing the trade names ATTANE ™ and AFFINITY ™, and ENGAGE ™ polyolefin elastomers, each obtainable from The Dow Chemical Company, Michigan, USA; and olefinic copolymers (e.g., ethylene / l-butene copolymers) prepared using INSITE® technology from The Dow Chemical Company.
[0127] Each of the multi-block copolymer compositions of poly (olefin monomer / olefin comonomer) telekelic, of copolymer in poly multi-blocks (olefin monomer / olefin comonomer), of poly interpolymer (olefin monomer / comonomer) olefin) / polyester, poly interpolymer (olefin monomer / olefin comonomer) / polyether, poly interpolymer (olefin monomer / olefin comonomer) / polyamide, and poly interpolymer (olefin monomer / comonomer) olefin) / polyisocyanate of formula (IVa) comprises at least a portion which is poly (olefin monomer / olefin comonomer). The poly (olefin monomer / olefin comonomer) comprises a plurality of repeat units, each repeat unit being, independently of a residue of the monomer or of the olefinic comonomer, or a derivative of the residue of the monomer or of the olefinic comonomer, the plurality
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58/113 repeat units of the poly (olefin monomer / olefin comonomer) comprising a segment rich in poly (olefin monomer) (i.e., comprising more residues of the olefin monomer than of the olefin comonomer, if any) and a different poly (olefin comonomer) segment (i.e., comprising a higher molar percentage of olefin comonomer residues than the molar percentage of olefin monomer residues, if any, in the poly (olefin monomer) segment).
[0128] The preferred inventive poly (olefin monomer / olefin comonomer) is characterized by having blocks or segments of two or more polymerized monomer units differing in chemical or physical properties, and characterized by being separated by mesophase. Sometimes, such polymers are referred to here as interpolymers in multiblock separated by mesophase. Preferably, each poly (olefin monomer / olefin comonomer) is independently characterized by being separated by mesophase and having a PDI greater than or equal to 1.4.
[0129] More preferably, each poly (olefin monomer / olefin comonomer) is, independently, a poly (ethylene / alpha-olefin). The poly (ethylene / alpha-olefin) comprises a hard segment derived from ethylene and a soft segment comprising residues of alpha-olefin and ethylene. Where the poly (ethylene / alpha-olefin) comprises a segment rich in polyethylene, the crystallization of such a segment rich in polyethylene is mainly restricted to the resulting mesodomains, and such poly (ethylene / alpha-olefin) can be referred to as separated by mesophase.
[0130] Preferably, poly (ethylene / alpha-olefin) is,
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59/113 independently, characterized by being separated by mesophase and having a PDI of 1.4 to 8. Preferably, each such PDI is characterized by fitting to a Schutz-Flory distribution instead of a Poisson distribution. Preferably, each poly (ethylene / alpha-olefin) is, independently, characterized by having both a polydispersed block distribution as well as a polydispersed distribution of block sizes, which gives improved characteristics and distinguishable physical properties to it. Preferably also, each poly (ethylene / alpha-olefin) is independently characterized by having a difference in molar percentage of alpha-olefin content between the polyethylene and other blocks. [0131] When used here, the term mesophase separation means a process in which polymeric blocks are locally segregated to form ordered domains. These mesodomains can take the form of spheres, cylinders, lamellae, or any other known morphology for block copolymers.
[0132] The domain sizes of the multi-block olefinic interpolymer separated by mesophase can be controlled by varying the molecular weight of the multi-block olefinic interpolymer separated by mesophase or by changing the difference in comonomer content of the multi-block olefinic interpolymer separated by mesophase. Domain sizes can also be modified by mixing a mixture component with multi-block olefinic interpolymer mass separated by mesophase. Examples of mixing components include homo polymer or copolymer with composition similar to that of the respective blocks or segments of the interpolymer
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60/113 multi-block olefin separated by mesophase, an oil such as a mineral oil, and a solvent (used as a diluent) such as toluene or hexane.
[0133] In some embodiments, the domains of the multi-block olefinic interpolymer separated by mesophase are characterized by having a size that is at least 50% larger than domain sizes in conventional monodispersed block copolymers (ie, PDI less than 2, for example). example, POI of about 1). Domain sizes can be controlled by varying the molecular weight of the olefinic interpolymers in multiblocks separated by mesophase or by changing the comonomer content of the same such that at least two blocks (i.e., the hard and soft segments) of the olefinic multiblock interpolymers separated by mesophase differ in this way. The desired amounts of comonomer can be measured in molar percent. The calculation can be done for any desired comonomer in order to determine the amount required to achieve mesophase separation.
[0134] Domain sizes of the multi-block olefinic interpolymer separated by mesophase are typically in the range of about 40 nm (nanometer) to about 300 nm. Those of the olefinic interpolymers in multiblock separated by mesophase comprise olefinic block copolymers in which the amount of comonomer in the soft segments compared to that in the hard segments is such that that of the olefinic interpolymer in multiblocks separated by mesophase undergoes mesophase separation in a melt of the same.
[0135] In some embodiments, the polyolefin comprises an ethylene / alpha-olefin interpolymer, such as those described in the international patent application publication
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PCT No. WO 2009/097560, which is incorporated by reference, preferably a block copolymer, comprising a hard segment and a soft segment, is characterized by M _w / M _n in the range of about 1.4 to about 2.8 e: (a) for having at least one melting point, T _m , in Celsius degree (° C) and a density, d, in gram / cubic centimeter (g / cm ³ ), with numerical values of the variables correspond to the relationship: Tm> -6553.3 + 13735 (d) -7051.7 (d) ² , or (b) is characterized by a fusion heat ΔΗ, in J / g, and by an amount of delta temperature, ΔΤ, in ° C, defined as the temperature difference between the highest peak of DSC and the highest peak of fractionation of CRYSTAF, with the numerical values of ΔΤ and ΔΗ satisfying the following relationships: Δτ> 0, 1299 (ΔΗ) +62.81 for ΔΗ greater than zero and up to 130 J / g, ΔΤ> 48 ° C for ΔΗ greater than 130 J / g, and the CRYSTAF peak is determined using at least 5 percent of cumulative polymer, and if less than 5 percent of the polymer has an identifiable CRYSTAF peak, then the CRYSTAF temperature will be 30 ° C; or (c) characterized by an elastic recovery, Re, in percentage at 300% deformation and 1 cycle measured in a film molded by compression of an ethylene / a-olefin interpolymer, and has a density, d, in g / cm ³ , with the numerical values of R _and ed satisfying the following relationship when the ethylene / aolefin interpolymer is substantially free of a crosslinked phase: R _e > 1481-1629 (d); or (d) have a molecular fraction that elutes between 40 ° C and 130 ° C when fractionated using TREF, characterized by the fact that the fraction has a comonomer molar content of at least 5 percent greater than that of an interpolimer fraction of comparable random ethylene
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62/113 eluting between the same temperatures, the said comparable random ethylene interpolymer having the same comonomers, and having a melting index, density, and molar content of comonomer (based on the whole polymer) within 10 percent limits those of the ethylene / α-olefin interpolymer; or (e) have a storage module at 25 ° C, G '(25 ° C), and a storage module at 100 ° C,
G '(100 ° C), the ratio of G' (25 ° C) to G '(100 ° C) is in the range of about 1: 1 to about 9: 1; or (f) is characterized by an average block index greater than zero and up to about 1.0; or (g) have a molecular fraction that elutes between 40 ° C and 130 ° C when fractionated using TREF, characterized by the fact that the fraction has a molar comonomer content greater than or equal to the amount (-0,2013) T + 20, 07, more preferably greater than or equal to the quantity (-0,2013) T + 21.07, where T is the numerical value of the maximum elution temperature of the TREF fraction, measured in ° C; and the ethylene / alpha-olefin interpolymer in blocks is separated by mesophase.
[0136] In some embodiments, the polyolefin comprises an ethylene / alpha-olefin interpolymer, such as that described in US Patent No. 7,355,089 and in US Patent Application Publication No. US 2006/0199930, where the interpolymer it is preferably a block copolymer, and comprises a hard segment and a soft segment, and the ethylene / alpha-olefin interpolymer: (a) has an M _w / M _n of about 1.7 to about 3.5, at least one melting point, T _m (° C) and density, d, in g / cm ³ , with the numerical values of Tm and d corresponding to the relationship: Tm> -2002.9 + 4538.5 (d) 2422 , 2 (d) ² ; or (b) has Mw / M _n of about 1.7 to about 3.5, and
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63/113 is distinguished by a heat of fusion, ΔΗ, in J / g, and a delta quantity, ΔΤ, in ° C, defined as the temperature difference between the maximum DSC peak and the maximum CRYSTAF peak, with the numerical values of ΔΤ and ΔΗ have the following relationships: ΔΤ> -0.1299 (ΔΗ) + 62.81 for ΔΗ greater than zero and up to 130 J / g; ΔΤ> 48 ° C for ΔΗ greater than 130 J / g, with the peak of CRYSTAF determined using at least 5 percent of the cumulative polymer, and if less than 5 percent of the polymer has an identifiable CRYSTAF peak, then the CRYSTAF temperature will be 30 ° C; or (c) distinguished by a percentage elastic recovery, R _e , in deformation of 300 percent, and 1 cycle, measured coated substrate molded by compression of the ethylene / a-olefin interpolymer, and has a density, d, in grams per cubic centimeter, with the numerical values of R _and ed satisfying the following relationship when the ethylene / α-olefin interpolymer is substantially free of a crosslinked phase: R _e > 1481 1629 (d); or (d) it has a molecular fraction that elutes between 40 ° C and 130 ° C when fractionated using TREF, characterized by having a comonomer molar content of at least 5 percent, greater than that of a comparable random ethylene interpolymer fraction eluting between the same temperatures, the said comparable random ethylene interpolymer having the same comonomers and having a melting index, density, and molar comonomer content (based on the entire polymer) within the 10 percent range of that of the interpolymer ethylene / α-olefin; or (e) having a storage module at 25 ° C, G '(25 ° C), and a storage module at 100 ° C, G' (100 ° C), the ratio being G '(25 ° C) ) for G '(100 ° C) is in the range of about 1: 1 to about 9: 1
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64/113 or (f) has a molecular fraction that elutes between 40 ° C and 130 ° C when fractioned using TREF, characterized by the fact that the fraction has a block index of at least 0.5 and up to about 1 and a molecular weight distribution, M _w / M _n , greater than about 1.3; or (g) have a block index greater than zero and up to about 1.0 and a molecular weight distribution, M _w / M _n , greater than about 1.3; or (h) has a molecular fraction that elutes between 40 ° C and 130 ° C when fractionated using TREF, characterized by the fact that the fraction has a molar comonomer content greater than or equal to the amount (-0,2013) T + 20, 07, more preferably greater than or equal to the quantity (-0,2013) T + 21.07, where T is the numerical value of the maximum elution temperature of the TREF fraction, measured in ° C.
[0137] Other embodiments comprise polymers and processes such as those described in US patent application publications WO 2005/090425 Al and their corresponding US 2007/0167315 Al, WO 2005/090426 Al and their corresponding US 2008/0311812 Al , and WO 2005/090427 A2 and its corresponding US 2007/0167578 A1.
[0138] In other embodiments, the present block interpolymers are copolymers of poly (ethylene / alpha-olefin) and related processes and methods described in PCT International Patent Application Publication No. WO 2009/097565, in which: (a) the poly (ethylene / alpha-olefin) copolymer comprises two or more substantially homogeneous intramolecular blocks comprising different chemical and physical properties and having a difference in percentage of molar percentage alpha-olefin, said intramolecular blocks characterized by having
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65/113 a very probable molecular weight distribution, in which at least one poly (ethylene / alpha-olefin) copolymer (i.e., ethylene / alpha-olefin interpolymer) is characterized by a molecular weight distribution, M _w / M _n , in the range of about 1.4 to about 2.8 and by an average block index greater than zero and up to about 1.0; and the ethylene / alpha-olefin block interpolymer being separated by mesophase; or the poly (ethylene / alpha-olefin) copolymer comprises two or more substantially homogeneous intramolecular blocks comprising different chemical and physical properties and having a difference in percentage of molar percentage alpha-olefin, said intramolecular blocks characterized by having a very probable distribution molecular weights, the block copolymer having a molecular weight of 1,000 g / mol to 1,000,000 g / mol and is separated by mesophase; or (c) the poly (ethylene / alpha-olefin) copolymer comprises two or more substantially homogeneous intramolecular blocks comprising different chemical and physical properties and having a difference in molar percentage alpha-olefin content, said intramolecular blocks characterized by having a very likely molecular weight distribution, with the copolymer being characterized by an average molecular weight greater than 40,000 g / mol, a molecular weight distribution, M _w / M _n , in the range of about 1.4 to about 2 , 8, and a difference in molar percentage alpha-olefin content between intramolecular blocks greater than about 20 molar percent.
[0139] Polyolefin monomer and comonomer content can be measured using any technique
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66/113 such as, for example, infrared (IR) spectroscopy and nuclear magnetic resonance (NMR) spectroscopy, with NMR-based techniques being preferred and ¹³ C NMR spectroscopy being more preferred. To use ¹³ C NMR spectroscopy, an analysis sample is prepared from a sample of high density polyethylene polymer or copolymer in poly (ethylene / alpha-olefin) blocks by adding approximately 3 g of a 50/50 mixture from tetrachloroethane-d ² / ortho-dichloro-benzene to 0.4 g of polymer sample by heating the tube and its contents to 150 ° C. ¹³ C NMR spectroscopy data is collected using a 400 MHz JEOL Eclipse ™ spectrometer or a 400 MHz Varian Unity Plus ™ spectrometer, corresponding to a carbon-13 resonance frequency of 100.5 MHz. carbon-13 data using 4000 transients per data file, adding multiple data files together. The spectral width is 25,000 Hz with a minimum file size of 32,000 data points. The analysis sample is analyzed at 130 ° C on a 10 mm wide band probe. Comonomer incorporation with carbon-13 data is determined using Randall's triad method (Randall, JC; JMS-Rev. Marcromol. Chem. Phys. C 29, 201-317 (1989), which is incorporated here entirely by reference.
[0140] In some incorporations, the amount of olefinic comonomer in the copolymer is characterized in poly blocks (olefin monomer / olefin comonomer) or segments thereof, by a comonomer incorporation index. When used here, the term comonomer incorporation index, refers to the molar percentage of comonomer residues
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67/113 olefin incorporated into the olefin monomer / comonomer copolymer, or segment thereof, prepared under representative olefin polymerization conditions. Preferably, the olefin monomer is ethylene or propylene and the comonomer is, respectively, a C3-C40 alpha-olefin, or a C4-C40 alpha-olefin, respectively. Ideally, olefin polymerization conditions are steady-state polymerization conditions in a hydrocarbon diluent at 100 ° C, ethylene (or propylene) pressure (reactor pressure) of 4.5 MPa (mega-Pascal), and conversion of olefin monomer greater than 92 percent (preferably greater than 95 percent), and conversion of olefin comonomer greater than 0.01 percent. The selection of catalyst compositions, which include the inventive multifunctional compositions, having the maximum difference in olefin comonomer incorporation indexes results in poly block copolymers (olefin monomer / olefin comonomer) having the maximum difference in block properties or segments, such as density.
[0141] In certain circumstances, the comonomer incorporation index can be directly determined, for example, by using the NMR spectroscopic techniques described above or by IR spectroscopy. If these techniques cannot be used, then any difference in monomer incorporation is indirectly determined. For polymers formed from multiple monomers, this indirect determination can be performed by various techniques based on reactivity of monomers.
[0142] For catalyst copolymers, the monomer amounts in the copolymer and hence produced by a relative comonomer data and the copolymer composition is
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68/113 determined by the relative rates of comonomer and monomer reaction. Mathematically, the molar ratio of comonomer to monomer is given by the equations described in US 2007/0167578 Al, in paragraphs numbers [0081] to [0090].
[0143] For this model the polymer composition is also only a function of temperature-dependent reactivity ratios and the comonomer molar fraction in the reactor. The same is also true when inverse insertion of a comonomer or monomer may occur or in the case of interpolymerization of more than two monomers.
[0144] Reactivity ratios for use in the previous models can be predicted using well-known theoretical techniques or empirically derived from actual polymerization data. Such theoretical techniques are disclosed, for example, in B.G. Kyle, Chemical and Process Thermodynamics, third edition, Prentice-Hall, 1999, and in the Redlich-Kwong-Soave Equation of State (RKS), Chemical Engineering Science, 1972, pp 1197-1203. Commercially obtainable computer programs can be used to assist in deriving reactivity ratios from experimentally derived data. An example of such software is Aspen Plus from Aspen Technology, Inc., Tem Canal Park, MA 02141-2201 USA.
[0145] It is sometimes convenient to incorporate the original olefin polymerization catalyst and the associated olefin polymerization catalyst by reference examples. For convenience and consistency, one of these catalysts is therefore sometimes referred to as a first olefinic polymerization catalyst and one as a second olefinic polymerization catalyst. This is, in some embodiments, the first polymerization catalyst
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69/113 olefinic is the same as the original olefinic polymerization catalyst and the second olefinic polymerization catalyst is the same as the associated olefinic polymerization catalyst; and vice versa in other incorporations. When used herein, the first olefinic polymerization catalyst is characterized by having a comonomer incorporation index that is less than 90 percent, more preferably less than 50 percent, even more preferably less than 25 percent, and even more preferably less than 10 percent of the high comonomer incorporation rate of the first olefinic polymerization catalyst.
[0146] In some embodiments, the inventive process employs a catalytic system comprising a mixture or reaction product of: (A) a first olefinic polymerization catalyst, the first olefinic polymerization catalyst characterized by having a high rate of incorporation of comonomer (for example, a comonomer incorporation index greater than or equal to 15 mol%); (B) a second olefinic polymerization catalyst, the second olefinic polymerization catalyst characterized by having a comonomer incorporation index less than 90 percent of the comonomer incorporation index of the first olefinic polymerization catalyst; and (C) the inventive multifunctional chain exchange agent.
[0147] In some embodiments, the original olefin polymerization catalyst is the second olefin polymerization catalyst and the associated olefin polymerization catalyst is the first polymerization catalyst
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70/113 olefinic.
[0148] The term catalyst as used herein generally refers to a deactivated form of a binder / metal complex (i.e., precursor) or, preferably, to the activated form of it (for example, after contact of the form deactivated with an activating co-catalyst to give a catalytically active mixture or product thereof). The metal of the metal / binder complex can be a Group 3 to 15, preferably Group $, metal from the Periodic Table of Elements. Examples of suitable types of metal / binder complexes are metallocene, semi-metallocene, constricted geometry and pyridimyl, polyether complexes or poly-based complexes. Such metal / binder complexes are described in WO 2008/027283 and in the corresponding U.S. patent application No. 12 / 377,034. Other suitable metal / binder complexes are those described
in US 5,064,802, US 5,153,157, US 5,296,433, US 5,321,106, USUS 5,350,723, US 5 .425,872, US 5,470,993, US 5,625,087, 5,721,185, US 5 .783,512, US 5,866,704, US 5,883,204, US 5,919,983, US 6 .015,868, US 6,034,022, US 6,103,657, US 6,150,297, US 6 .268,444, US 6,320,005, US 6,515,155, US 6,555,634, US 6. 696,379, US 7 .163,907, and US 7,355,089, good
as in patent applications WO 02/02577, WO 02/92610, WO 02/38628, WO 03/40195, WO 03/78480, WO 2009/012215 A2, US 2003/0004286, US 04/0220050, US 2006/0199930 Al, US 2007/0167578 Al, and US 2008/0311812 Al.
[0149] Also for convenience and consistency, the first olefinic polymerization catalyst is interchangeably referred to as Catalyst (A). The second olefinic polymerization catalyst is interchangeably referred to as
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Catalyst (A). The first and second olefinic polymerization catalysts preferably have different selectivities of ethylene and C3-C40 alpha-olefin · [0150] Preferably, the catalyst comonomer incorporation index (B) is less than 50 percent and more preferably less than 5 percent of the catalyst comonomer incorporation index (A). Preferably, the catalyst comonomer incorporation index (A) is greater than 20 mol%, more preferably greater than 30 mol%, and even more preferably greater than 40 mol% comonomer incorporation.
[0151] Preferably, Catalyst (A) of the catalytic system is, independently, a catalyst (A) described in US 2006/0199930 Al, US 2007/0167578 Al, US 2008/0311812 Al, US 7,355,089 B2, or WO 2009/012215 A2. Also preferably, the Catalyst (B) of the catalytic system is, independently, a catalyst (B) described in US 2006/0199930 Al, US 2007/0167578 Al, US 2008/0311812 Al, US 7,355,089 B2, or WO 2009 / 012215 A2. The most preferred catalysts are those described in US 2007/0167578 A1 in paragraphs numbers [0138] to [0476].
[0152] Representative catalysts (A) and (B) are the catalysts of formulas (Al) to (A5), (Bl), (B2), (Cl) to (C3), and (Dl):
[0153] Catalyst (Al) is dimethyl [N- (2,6-di (1-methyl ethyl) phenyl) starch) (2-isopropyl phenyl) (a-naphthalen-2-diyl (6pyridin-2-diyl) methane )] hafnium, prepared according to the teachings of WO 03/40195, 2003US0204017, USSN 10 / 429.024, deposited on May 2, 2003, and WO 04/24740, and having the structure:
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(Al) [0154] The catalyst (A2) is dimethyl [N- (2,6-di (1-methyl ethyl) phenyl) starch) (2-methylphenyl) (1,2-phenylene- (6-pyridin-2 diyl) methane)] hafnium, prepared according to the teachings of WO 03/40195, 2003US0204017, USSN 10 / 429.024, deposited in May 2003, and WO 04/24740, and having the structure:
(A2) [0155] The catalyst (A3) is dibenzyl bis [N, N '- (2,4,6 tri (methylphenyl) starch) ethylenediamine] hafnium, and having the structure:
[0156] The catalyst (A4) is dibenzyl bis ((2-oxoyl-3Petition 870190071820, from 07/26/2019, page 78/128
73/113 (dibenzo-1H-pyrrol-l-yl) -5- (methyl) phenyl) -2-phenoxy methyl) cyclohexane-1,2-diyl zirconium (IV), prepared substantially in accordance with the teachings of US-A2004 / 0010103. =, and having the structure:
(A4) [0157] The Catalyst (A5) is [T | ² -2,6-diisopropyl-N- (2methyl-3- (octyl imino) butan-2-yl) benzeneamide] trimethyl hafnium, prepared substantially in accordance with the teachings of WO 2003/051935, and having the structure:
(A5) [0158] The catalyst (Bl) is dibenzyl 1,2-bis- (3,5diterciobutyl phenylene) (1- (N- (1-methyl ethyl) imino) methyl) (2oxoyl) zirconium, and having the structure :
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C (CIIÚ3
(Bl) [0159] Catalyst (B2) is dibenzyl 1,2-bis- (3,5diterciobutyl phenylene) (1- (N- (2-methylcyclohexyl) imino) methyl) (2-oxoyl) zirconium, and having the structure:
(B2) [0160] The catalyst (Cl) is dimethyl (terciobutyl starch) dimethyl (3-N-pyrrolyl-1,2,3,3a, 7a-T | -inden-1yl) titanium silane prepared substantially in accordance with techniques of USP 6,268,444, and having the structure:
C (CH ₃ ) ₃ (Cl) [0161] (C2) dimethyl catalyst
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75/113 (terciobutylamido) di (4-methylphenyl) (2-methyl-1,2,3,3a, 7a-T | inden-1-yl) titanium silane prepared substantially in accordance with the teachings of US-A-2003 / 004286, and having the structure:
(C2) [0162] The catalyst (C3) is dimethyl (terciobutyl starch) di (4-methylphenyl) (2-methyl-1,2,3,3a, 8a-T | -sindacen-l-yl) titanium prepared substantially according to the teachings of US-A-2003/004286, and having the structure:
(C3); and [0163] The catalyst (Dl) is bis (dimethyl disyloxane) (inden-1-yl) zirconium dichloride obtainable from Sigma-Aldrich, and having the structure:
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(Dl) [0164] In some embodiments, the original and associated olefinic polymerization catalysts become catalytically active by contacting them or reacting them with the same co-catalyst (sometimes referred to as an activating cocatalyst or co-catalyst) or using a activation techniques such as those known in the art for use with olefin polymerization reactions with metal (eg, Group 4). For example, some embodiments using both the original and associated olefinic polymerization catalysts still employ only the original co-catalyst. In other embodiments, the original co-catalyst is used to activate the original olefinic polymerization catalyst and the associated co-catalyst is used to activate the associated olefinic polymerization catalyst.
[0165] Co-catalysts suitable for use here include alkyl aluminum; polymeric or oligomeric alumoxanes (also known as aluminoxanes); neutral Lewis acids; and ion-forming, non-coordinating, non-polymeric compounds (including the use of such compounds under oxidizing conditions). An appropriate activation technique is mass electrolysis (explained in more detail below). Combinations of one or more of the co
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77/113 prior catalysts and techniques. The term alkyl aluminum means a monoalkyl aluminum dihydride or monoalkyl aluminum dihalide, or dialkyl aluminum hydride or dialkyl aluminum halide, or trialkyl aluminum. Aluminoxanes and their preparations are known, for example, in U.S. Patent No. 6,103,657. Examples of preferred polymeric or oligomeric aluminoxanes are methyl aluminoxane, methyl aluminoxane modified with triisobutyl aluminum, and isobutyl aluminoxane.
[0166] Preferred Lewis acid co-catalysts are compounds of Group 13 metals containing from 1 to 3 hydrocarbyl substituents described herein. The most preferred Group 13 metal compounds include tri (hydrocarbyl) or tri (hydrocarbyl) boron substituted aluminum compounds, even more preferred are tri (C1 -C10 alkyl) aluminum or tri (Cg-aryl) compounds CisJboro and halogenated derivatives (including perhalogenates) thereof, even more especially tris (phenyl substituted by fluorine) boranes, even more especially tris (penta-fluorine phenyl) borane. In some embodiments, the co-catalyst is a tris borate (C1-C20 hydrocarbyl) (for example, trityl tetrafluoro borate) or a tetra (C1-C20 hydrocarbyl) tri (C1-C20 hydrocarbyl) ammonium (for example, tetrakis (phenyl penta-fluorine) borane bis (octadecyl) methyl ammonium. When used here, the term ammonium means a nitrogen cation which is one (C-C2o hydrocarbyl) 4N ⁺ , one (C1-C20 hydrocarbyl) 3N (H) ⁺ , one (hydrocarbyl of CiC2o) 2N (H) 2 ⁺ , one (C1-C20 hydrocarbyl) N (H) 3 ⁺ , or N (H) ₄ ⁺ , with ca of the C1-C20 hydrocarbyl can be the same or different.
[0167] Preferred combinations of co-catalysts of
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78/113 neutral Lewis acids include mixtures comprising a combination of tri (C1-C4 alkyl) aluminum or a compound of halogenated tri (Cg-CisJboro aryl), especially tris (pentafluor phenyl) borane. Also preferred are combinations of such mixtures of neutral Lewis acids with a polymeric or oligomeric aluminoxane, and combinations of a single neutral Lewis acid, especially neutral Lewis acids with a polymeric or oligomeric aluminoxane. Preferred mole numbers of (metal / binder complex) ratios: ( tris (pentafluor phenyl) borane) :( aluminoxane) [for example, (Group 4 metal complex / binder): (tris (pentafluor phenyl) borane) :( aluminoxane)] are from 1: 1: 1 to 1 : 10: 30, more preferably from 1: 1: 1.5 to 1: 5: 10.
[0168] Many co-catalysts and activation techniques have been taught previously with respect to different metal / binder complexes in: US 5,064,802, US 5,153,157, US 5,296,433, US 5,321,106, US 5,350,723, US 5,425,872, US 5,625,087, US 5,721,185, US 5,783,512, 5,883,204, US 5,919,983, US 6,696,379, and US 7,163,907. Examples of suitable hydrocarbyl oxides are disclosed in US 5,296,433. Examples of salts of Brõnsted acids suitable for addition polymerization catalysts are disclosed in US 5,064,802, US 5,919,983, US 5,783,512. Examples of appropriate salts of cationic oxidizing agent and a compatible non-coordinating anion as co-catalysts for addition polymerization catalysts are disclosed in US 5,321,106. Examples of suitable carbene salts as co-catalysts for addition polymerization catalysts are disclosed in US 5,350,723. Examples of suitable silyl salts as co-catalysts for catalysts
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79/113 addition polymerization is disclosed in US 5,625,087. Examples of suitable complexes of alcohols, mercaptan, silanols, and oxides with tris (penta-fluorine phenyl) borane are disclosed in US 5,296,433. Some of these catalysts are also described in a portion of US 6,515,155 BI starting at column 50, line 39, and going up to column 56, line 55, which portion is hereby incorporated by reference.
[0169] In some embodiments, one or more of the previous cocatalysts is used in combination with each other. An especially preferred combination is a mixture of tri (C1-C4 hydrocarbyl) aluminum, tri (C1 -C4 hydrocarbyl) borane, or an ammonium borate with an oligomeric or polymeric aluminoxane compound.
[0170] The ratio of the total number of moles of the original and associated olefin polymerization catalysts to the total number of moles of one or more of the co-catalysts is 1: 10,000 to 100: 1. Preferably, the ratio is at least 1: 5000, more preferably at least 1: 1000, and less than or equal to 10: 1, preferably less than or equal to 1: 1. When using an aluminoxane alone as a co-catalyst, preferably the number of moles of the aluminoxane used is at least 100 times the number of moles of the original and associated olefin polymerization catalysts. When using tris (penta-fluoro phenyl) borane alone as the co-catalyst, preferably the number of moles of tris (penta-fluoro phenyl) borane that is used for the total number of moles of one or more original olefinic polymerization catalysts and associated is 0.5: 1 to 10: 1, more preferably 1: 1 to 6: 1, even more preferably 1: 1 to 5: 1. The remaining co-catalysts
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80/113 are generally employed in approximately molar amounts equal to the total molar quantities of one or more original and associated olefinic polymerization catalysts.
[0171] The term catalyst preparation conditions refers, independently, to reaction conditions such as solvent (s), atmosphere (s), temperature (s), pressures, time (s), and the like that are preferred for give at least 10 percent (1%), more preferably at least 20%, and even more preferably at least 30% reaction yield of the relevant inventive process catalyst after a reaction time of 2 hours. Preferably, the relevant inventive process occurs independently in an inert atmosphere (for example, in an inert gas consisting essentially of, for example, nitrogen gas, argon gas, helium gas, or a mixture of any two or more of them). Preferably, the relevant inventive process takes place with an aprotic solvent or mixture of two or more aprotic solvents, for example, toluene. Preferably, the relevant inventive process takes place as a reagent mixture comprising the aprotic solvent. The reaction mixture can comprise additional ingredients such as those described above. Preferably, the relevant inventive process takes place at a temperature of the reaction mixture from -20 ° C to about 200 ° C. In some embodiments, the temperature is at least 0 ° C, and more preferably at least 20 ° C. In other embodiments, the temperature is less than or equal to 100 ° C, more preferably less than or equal to 50 ° C, and even more preferably less than or equal to 40 ° C. A convenient temperature is approximately the temperature
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81/113 environment, that is, from about 20 ° C to about 30 ° C. Preferably, the relevant inventive process occurs, independently, at ambient pressure, that is, from about 1 atm (for example, from about 95kPa to about 107 kPa, such as 101 kPa).
[0172] The term catalytic quantity means molar percentage (mol%) of the catalyst for a catalyzed reaction that is less than 100 mol% of a number of moles of a stoichiometric reagent limiting the product used in the catalyzed reaction and greater than or equal to a value minimum molar% required to form and detect (mp, by mass spectroscopy) at least some product of the catalyzed reaction, 100% molar equal to the number of moles of the stoichiometric reagent limiting the product used in the reaction catalyzed. The minimum catalytic amount is preferably 0.000001 mol%, and can be 0.00001 mol%, 0.0001 mol%, 0.001 mol%, or even 0.01 mol%. Preferably, the catalytic amount of each of the olefin polymerization catalysts is, independently, from 0.00001 mol% to 50 mol% of the olefin monomer or comonomer moles, whichever is less.
[0173] A general process for preparing polyolefins that can be adapted to produce the polyolefins of the present invention (e.g., poly block copolymers (olefin monomer / olefin comonomer)) has been disclosed in PCT publication No. WO 2007/035485 Al. Preferably, such a method comprises a process for the polymerization of one or more addition-curable monomers, preferably two or more addition-curable monomers, especially of ethylene and at least one comonomer
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82/113 copolymerizable, of propylene and at least one copolymerizable comonomer having from 4 to 20 carbon atoms, or of 4methyl-1-pentene and at least one different copolymerizable comonomer having from 4 to 20 carbon atoms, to form a copolymer comprising two regions or segments of different polymeric properties and composition, especially regions comprising a different index of comonomer incorporation, said process comprising: (1) contacting a polymerizable monomer by adding or mixing monomers under addition polymerization conditions, preferably polymerization conditions uniform or homogeneous, in a reactor or reactor zone with a composition comprising at least one olefinic polymerization catalyst and at least one co-catalyst and characterized by the formation of polymeric segments of said monomer or monomers; (2) transfer the reaction mixture to a second reactor or reactor zone and optionally add one or more additional reagents, catalysts or other compounds before, simultaneously, or after said transfer: and (3) cause polymerization to occur in said second reactor or reactor zone to form polymeric segments that are different from the polymeric segments formed in step (1); said process being characterized by the addition of a chain exchange agent to the reagent mixture before, during, or subsequent to step (1) such that at least some polymer molecules resulting from step (3) comprise two or more blocks or segments chemically or physically distinguishable. As mentioned earlier, a feature of the inventive multifunctional chain exchange agent is that it comprises a single compound that is capable of functioning in such a way.
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83/113 so that at least one olefin-containing polymer chain can be exchanged between two or more olefinic polymerization catalysts. As a test, such a polymer chain exchange is characterized with a process to prepare a copolymer in poly (ethylene / octene) diblocks, the process comprising the steps listed above and operated under representative olefinic polymerization conditions, ideally under polymerization conditions in continuous and steady state solution in a hydrocarbon diluent at 100 ° C, in ethylene pressure (reactor pressure) of 4.5 MPa, with ethylene conversion greater than 92 percent (more preferably greater than 95 percent), and comonomer conversion (ie, 1octene) greater than 0.01 percent. Preferably, the process employs two olefinic polymerization catalysts, one of which being the Catalyst (Al). The entire process for producing block copolymers can also be carried out in a single reactor.
[0174] Although the foregoing process has been described for convenience to form a diblock version of the inventive poly (olefin monomer / olefin comonomer) block copolymer, it is an additional object of the invention to prepare copolymers in poly (monomer block) inventive olefin / olefin comonomer) having 3 or more blocks. The inventive poly (olefin monomer / olefin comonomer) block copolymers having 3 or more blocks also include hyper-branched and dendrimeric copolymers. Such copolymers having 3 or more blocks can be prepared by coupling the poly (olefin monomer / olefin comonomer) of the multifunctional chain exchange agent containing poly (olefin monomer / olefin comonomer) (for example, as in
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84/113 composition of formula (IVa)) leaving the second reactor or zone (or any subsequent reactor or zone) using a polyfunctional coupling agent (for example, difunctional), the coupling agent having functionality greater than or equal to three to prepare hyper-branched and dendrimeric copolymers. Additionally, if more than two reactors are employed, the inventive copolymer in poly (olefin monomer / olefin comonomer) blocks having three or more blocks is similar to what can be prepared by live polymerization in more than one reactor, with a difference being that each block of the copolymer in blocks of poly (olefin monomer / olefin comonomer) forming having three or more blocks has characteristics of a very probable distribution of molecular weights and composition whereas the blocks of the live polymerization product would not have such characteristics. In particular, the polydispersity of the inventive copolymer into poly (olefin monomer / olefin comonomer) blocks having three or more blocks is generally less than 2.4 and can approach 1.5 for product prepared in two reactors.
[0175] In general, the average number of blocks in the absence of polyfunctional coupling agent facilitated by copolymer polymers in poly blocks (olefin monomer / olefin comonomer) will be equal to the number of reactors employed. Poly-block copolymer products (olefin monomer / olefin comonomer) will normally include amounts of conventional polymer depending on the efficiency of the multifunctional chain exchange agent (and optionally additional chain exchange agents, if any) employed under the conditions gives
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85/113 polymerization.
[0176] The invention involves the concept of using multifunctional chain exchange agent as a way of prolonging (ie ensuring) the average life of a polymer chain such that a substantial fraction of the polymer chains come out of at least one first reactor. a series of multiple reactors or a first zone of a multizone reactor operating substantially in continuous conditions in the form of polymer chains terminated with the multifunctional chain exchange agent (for example, as in the composition of formula (IV) or (IVa )), and the polymer chains experience different polymerization conditions in the next reactor or polymerization zone. Different polymerization conditions in the respective reactors or zones include the use of different monomers, comonomers, or monomer / comonomer ratios, different polymerization temperatures, pressures or partial pressures of various monomers, different catalysts, different monomer gradients, or any other difference that leads to the formation of a distinguishable polymeric segment. Thus, at least a portion of the polymer resulting from the present process comprises two, three or more, preferably two or three differentiated polymer segments arranged in an intramolecular manner.
[0177] Since the various reactors or zones form a different polymer distribution than a single specific polymeric composition, the resulting product has improved properties over a random copolymer or monodispersed block copolymer.
[0178] As mentioned above, the
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86/113 copolymers in poly blocks (olefin monomer / olefin comonomer) under olefinic polymerization conditions. Olefinic polymerization conditions refer, independently, to reaction conditions such as solvents, atmospheres, temperatures, pressures, times, and the like that are preferred to give a reaction yield of at least 10%, more preferably at least 20% , and even more preferably at least 30% of the block copolymer of poly (olefin monomer / olefin comonomer) or polyolefin after 15 minutes of reaction time. Preferably, polymerization processes occur,
regardless, in inert atmosphere (per example, on one inert gas consisting essentially from, per example, gas nitrogen, gas argon, helium gas, or an mixture in
any two or more of them). However, other atmospheres are considered, and these include sacrificial olefin in the form of a gas and hydrogen gas (for example, as a polymerization terminating agent). In some respects, the polymerization processes occur, independently, without any solvent, that is, it is a pure polymerization process that occurs in a pure mixture of the aforementioned ingredients. In other respects, the pure mixture also contains additional ingredients (for example, catalyst stabilizer such as triphenyl phosphine) other than solvents. In still other aspects, the polymerization processes take place, independently, with a solvent or mixture of two or more solvents, that is, a solvent-based process that occurs as a solvent-containing mixture of the aforementioned ingredients, and at least one solvent, for example, an aprotic solvent. Preferably the process of
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87/113 pure polymerization or solvent-based polymerization process occurs in a pure mixture occurs at a temperature of the pure mixture or the mixture containing solvent from -20 ° C to about 200 ° C. In some embodiments, the temperature is at least 30 ° C, and more preferably at least 40 ° C. In other embodiments, the temperature is less than or equal to 175 ° C, more preferably less than or equal to 150 ° C, and even more preferably less than or equal to 140 ° C. A convenient temperature is about 60 ° C or about 70 ° C. In some embodiments, polymerization processes occur, independently, at a pressure less than or equal to about 1000 psi (pound per square inch), that is less than or equal to about 70 atm (atmosphere) or less than or equal to about 7000 kPa. Preferably, the polymerization processes occur independently at a pressure of about 0.9 atm to about 50 atm (i.e., from about 91 kPa to about 5000 kPa). A convenient pressure is 3000 kPa to 4900 kPa.
[0179] In some embodiments, the composition of formula (IV) is prepared at the site, and then used in a subsequent process step as described above; stored for future use; or isolated and stored for future use (for example, in a polyester, polyester, polyamide, or polyisocyanate forming process or as a chain exchange agent to prepare another composition of formula (IV) or (IVa)). Similarly, in some embodiments, the composition of formula (IVa) is prepared at the site, and then used in a subsequent process step as described above; stored for future use; or isolated and stored for future use (for example, in a polyester, polyester, polyamide forming process,
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88/113 or polyisocyanate).
[0180] In some embodiments, the inventive process comprises terminating the multifunctional chain exchange agent containing poly-radical / polyolefin (e.g., the composition of formula (IV)) to form the polyolefin. In this way, the polyolefin is released from the multifunctional chain exchange agent while leaving the terminal functional groups attached to the polyolefin. Such termination comprises, for example, contacting the multifunctional chain exchange agent containing polyradical / polyolefin with a terminating agent (i.e., quenching) for the polyolefin (for example, poly block copolymer (olefin monomer / comonomer) olefin)). The terminating agent preferably comprises a source of protons (for example, water, aqueous acid, or an alcohol such as 2-propanol). In some embodiments, the terminating agent further comprises a stabilizing agent such as, for example, an antioxidant (for example, a hindered phenol antioxidant (IRGANOX ™ 1010 from Ciba Geigy Corporation)), a phosphorus stabilizer (for example, IRGAFOS ™ 168 from Ciba Geigy Corporation), or both.
[0181] Preferably, the inventive telekelic polyolefin is characterized by having a non-statistical distribution of the first and second functional end groups.
[0182] In some embodiments, the inventive process comprises a step of terminally functionalizing the polyradical-polyolefin of the multifunctional chain exchange agent containing poly-radical-polyolefin to form the inventive telekeletal polyolefin (for example, the
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89/113 poly (olefin monomer / olefin comonomer) telekelic). Such terminal functionalization comprises conversion of an end (e.g., comprising a carbonanion) of the poly-radical-polyolefin to a vinyl, hydroxyl, silane, carboxylic acid, carboxylic acid, ionomeric ester, or other terminal functional group. Such terminal functionalization can be performed according to known and established techniques. Examples of appropriate chemistry to terminally functionalize the poly-radical-polyolefin of the multifunctional chain exchange agent containing polyradical-polyolefin include dehydrogenation, dehydration, hydrolysis, aminolysis, silylation, oxidation, oxidative esterification, and ion exchange (for example, to convert carboxylic acid groups in -COsNa plots).
[0183] Referring to formula (IV), the terminal functional groups derived from the termination of the X portions of formula (IV) linked to M ² are hydroxyl groups (i.e., -OH) when X is O; amino groups substituted by C1-C20 hydrocarbyl (i.e., C1-C20 -NH-hydrocarbyl) when X is N (C1-C20 hydrocarbyl); amino groups (-NH ₂ ) when X is N (H); -SH groups when X is S, -PH2 groups when X is P (H); and phosphorus groups substituted by C1-C20 hydrocarbyl (ie -PH-C1-C20 hydrocarbyl) when X is P (C1-C20 hydrocarbyl) · Each of the terminal functional groups derived from termination of poly-radical polyolefin portions Formula (IV) attached to M ¹ is, independently, the vinyl, hydroxyl, silane, carboxylic acid, carboxylic acid ester, ionomeric group, or other terminal functional group. Preferably, the inventive telekelic polyolefin comprises a telekelic polyolefin
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90/113 of formula (V):
T-polyolefin-CH ₂ -R ^L - (XH) _w (V) where w is an integer equal to 1 or 2; each RL is, independently, C1-C19 alkylene or C2C19 alkenylene; and each X is, independently as defined for formula (I). Consequently, termination of the composition of formula (IV) produces a telekelic polyolefin characterized by having at least one terminal functional group of formula -XH and at least one terminal functional group of formula T-, with T being vinyl, hydroxyl, silane, carboxylic acid, carboxylic acid ester, ionomeric, or other terminal functional group, thus establishing a preferred incorporation of the telekelic polyolefin characterized by having a non-statistical distribution of terminal functional groups -XH and T-.
[0184] In some embodiments, the inventive process comprises a step of terminating the poly-radical-polyolefin of the multifunctional chain exchange agent containing polyradical-polyolefin to form the polyolefin with inventive terminal functionality of formula (III). Again referring to formula (IV), terminally protonating the polyradical-polyolefin followed by termination of the X portions of formula (IV) gives the polyolefin with inventive terminal functionality of formula (III).
[0185] In the polyolefin with inventive terminal functionality of formula (III) and in the telehelic polyolefin of formula (V), w is preferably equal to 1.
[0186] In some embodiments, the poly-radical polyolefin of the multifunctional chain exchange agent
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91/113 containing poly-radical-polyolefin is coupled through the use of a polyfunctional coupling agent to form a new copolymer in diblocks, triblocks or more than three blocks, which includes hyper-branched derivatives and dendrimers.
[0187] Preferably, the multifunctional chain exchange agent containing poly-radical-polyolefin is employed with a polyester, polyether, polyamide or polyisocyanate-forming monomer to polymerize the polyester, polyether, polyamide or polyisocyanate-forming monomer, thereby producing the interpolymer in inventive polyolefin / polyester, polyether, polyamide or polyisocyanate multiblocks (for example, the poly multiblock interpolymers (olefin / olefin / polyester comonomer, polyether, polyamide or inventive polyisocyanate). Preferably, the polyester-forming monomer, polyether, polyamide or polyisocyanate comprises a hydroxy substituted carboxylic acid; a lactone; an oxetane; an oxirane (i.e. epoxide); a lactam; an isocyanate; a mixture comprising a diol and a dicarboxylic acid, dicarboxylic diester, dicarboxylic anhydride, or dicarboxylic dihalide, or a mixture comprising a dicarbox acid In some embodiments, the polyester-forming monomer comprises lactone, the polyester-forming conditions comprise polymerization by opening anionic ring opening, and the polyolefin / polyester block copolymer comprises a polyolefin / polyester block copolymer. open ring. In some embodiments, the lactone comprises ε-caprolactone or (D, L) lactide. In some embodiments, the polyether-forming monomer comprises epoxide (preferably oxide
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92/113 ethylene or propylene oxide), the polyether forming conditions comprise polymerization by living anionic ring opening, and the polyolefin / polyether block copolymer comprises an open ring polyolefin / polyether block copolymer. In some embodiments, the polyamide-forming monomer comprises the lactam (preferably 3-oxo-2-aziridinylidene, 1-methyl-2azetidinone, N-methyl-butyrolactam, N-methyl-valerolactam, or N-methyl-6-caprolactam) , the polyamide forming conditions comprise live anionic ring opening polymerization, and the polyolefin / polyamide block copolymer comprises an open ring polyolefin / polyamide block copolymer. In some embodiments, the polyisocyanate-forming monomer comprises the isocyanate (preferably, phenyl isocyanate, toluene diisocyanate or methylene diisocyanate), the polyisocyanate-forming conditions comprise live anionic polymerization, and the polyolefin / copolymer block copolymer comprises a copolymer / polyisolyanate in polyolefin / polyisocyanate blocks.
[0188] The present polymerization step by opening anionic ring alive to polymerize the polyester, polyether, or polyamide forming monomer to prepare the polyester, polyether, or polyamide portion of the interpolymer in polyolefin / polyester, polyether, or polyamide multiblocks inventive is an example of the aforementioned non-olefin polymerization reaction.
[0189] The present block interpolymers comprise two or more blocks or segments that come together to form a single interpolymer, and each block or segment is chemically or physically distinguishable (other than by molecular weight
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93/113 or molecular weight distribution) of contiguous blocks or segments, the resulting block interpolymer has unique physical and chemical properties compared to random interpolymers of the same crude chemical composition. In some embodiments, the poly (olefin monomer / olefin comonomer) comprises three or more blocks or segments and therefore the interpolymers in poly (olefin monomer / olefin comonomer) / polyester, poly (olefin monomer) / olefin comonomer) / polyether, poly (olefin monomer / olefin comonomer) / polyamide and poly (olefin monomer / olefin comonomer) / polyisocyanate comprise a total of four or more blocks or segments per polymer molecule. Preferably, the poly (olefin monomer / olefin comonomer) portions thereof comprise four or more blocks or segments, and therefore the respective block present, comprises a total of five or more blocks or segments per polymer molecule.
[0190] In some embodiments, interpolymers in poly (olefin monomer / olefin comonomer) / polyester, poly (olefin monomer / olefin comonomer) / polyether, poly (olefin monomer / olefin comonomer) / polyamide or poly (olefin monomer / olefin comonomer) / polyisocyanate are characterized by having a high degree of polydispersity (for example, PDI greater than 3). In some embodiments, the poly (olefin monomer / olefin comonomer) portion of the same is characterized by being derived from, and having mesophase separation characteristics of the interpolymer in olefin multi-block separated by mesophase.
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94/113 [0191] In some aspects of the thirteenth embodiment, the process comprises a step of: contacting the ingredients comprising the multi-functional chain exchange agent containing poly-radical-polyolefin comprising any of the chain exchange agent embodiments multifunctional (especially any of the embodiments indirectly incorporated later in claim 13 of any of claims 1 to 8) and, respectively, a polyester, polyether, polyamide or polyisocyanate forming monomer, the contact step being performed under polyester forming conditions, polyether, polyamide, or polyisocyanate, thus preparing a polyolefin / polyester multiblock interpolymer, a polyolefin / polyether multiblock interpolymer, a polyolefin / polyamide multiblock interpolymer, or a polyolefin / polyisocyanate multiblock interpolymer.
[0192] The articles of the invention include objects comprising at least one film layer, such as a monolayer film, or at least one layer in a multilayer film prepared by casting, blowing, calendering or extrusion coating processes; molded articles, such as blow-molded, injection-molded, or rotational molded articles; fibers; and woven or non-woven cloths. In some embodiments, the articles of the invention comprise or are formed by thermoplastic compositions comprising the inventive polymers including mixtures with other natural or synthetic polymers, additives, reinforcing agents, ignition resistant additives, antioxidants, stabilizers, colorants, extenders, crosslinking agents , agents
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95/113 expansion, and plasticizers.
[0193] Preferably, the article of the present invention comprises a natural or, preferably synthetic lubricant. More preferably, the article of the present invention comprises an elastic film for a hygiene application (for example, for a diaper cover); flexible molded article comprising an appliance, tool, or household article (for example, toothbrush handle), sporting article, building and construction component, automotive part, or measured component (for example, device); flexible gasket (for example, refrigerator door gasket); flexible profile; an adhesive (for example, for packaging, tape or label or tag); or a foam (for example, for a sporting goods, packaging, household product, automotive padding, or foam mat). Even more preferably, the article of the present invention comprises a photonic material, barrier film, separation membrane (also known as microporous film), compatibilizer, or battery separator.
[0194] The term photonic material means a substance characterized by having mesodomains separated by phase, journals alternating in refractive index, with the domains sized to provide a range of photonic band in the UV / visible spectrum, such as those disclosed in US patent n 6,433,931. Examples of photonic materials include photonic crystal, photonic band gap material, and elastomeric optical interference film. Photonic materials are useful in applications requiring reflectance, transmission, or both, of radiation
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96/113 electromagnetic, especially at wavelengths in the infrared, visible, or ultraviolet region. Examples of such applications include uses in anti-counterfeiting, and security films, micro-labels, display films, and light filtering (for example, backlit displays).
[0195] Examples of barrier films are bladders in shoes (for example, athletic shoes) and packaging (for example, food packaging). Examples of separation membranes are membrane filters, including gas separation membranes, dialysis / hemodialysis membranes, reverse osmosis membranes, ultrafiltration membranes, and microporous membranes. Areas in which these types of membranes may be applicable include analytical applications, beverages, chemicals, electronics, environmental applications, and pharmaceuticals.
[0196] In addition, microporous polymer films can be used as battery separators. Where the article comprises a battery separator, preferably the present block interpolymers comprising it is in the form of a microporous polymeric film. Advantageously, such microporous polymeric films can be used as battery separators because of their ease of manufacture, chemical inertness and thermal properties. The primary function of a battery separator is to allow ions to pass through the electrodes, but to prevent the electrodes from coming into contact. Hence, the microporous polymeric films comprised of the present block interpolymers inhibit or prevent it from puncturing. Likewise, for use in lithium-ion batteries the films
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97/113 microporous polymer would preferably shut down (interrupting ionic conduction) at certain temperatures to prevent thermal leakage from the battery. Preferably, the present block interpolymers used for the battery separator have high strength over a wide temperature window to allow for thinner or more porous battery separators, or a combination thereof. Also, in lithium-ion batteries, lower shutdown temperatures are preferable, and the microporous polymer film would maintain mechanical integrity after shutdown. In addition, it is preferable that the microporous polymer film maintains dimensional stability at high temperatures.
[0197] The microporous polymer films of the present invention can be used in any of the processes or applications described in, but not limited to, the following patents and patent publications: WO 2005/001956 A2, WO 2003/100954 A2; U.S. Patent No. 6,586,138; U.S. Patent No. 6,524,742; US 2006/0188786; US 2006/0177643; U.S. patent No. 6,749,961; U.S. Patent No. 6,372,379; and WO 2000/34384 A1.
[0198] Preferably, the photonic material, barrier film, separation membrane, compatibilizer, or battery separator comprises, or is prepared from, interpolymers in olefin multiblocks separated by mesophase, or from the interpolymers in poly ( olefin monomer / olefin comonomer / polyester, poly (olefin monomer / olefin comonomer / polyether, poly (olefin monomer / olefin comonomer / polyamide, or poly (olefin monomer / olefin comonomer / polyisocyanate having one portion characterized by being
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98/113 derived from, and have characteristics of mesophase separation of the interpolymer in olefin multiblocks separated by mesophase. Appropriate methods for making porous structures and methods for forming models using block copolymer patterns to form mesoporous materials are described in US 7,517,466 B2. For use or to prepare the photonic material or battery separator, preferably each of the interpolymers in olefinic blocks separated by mesophase or at least the portion of olefinic block interpolymers separated by mesophase of the poly (olefin monomer / olefin comonomer) / polyester, poly (olefin monomer / olefin comonomer) / polyether interpolymer / polyether, poly (olefin monomer / olefin comonomer) / polyamide or poly (olefin monomer / olefin comonomer) / polyisocyanate it is independently characterized by having at least two domain sizes greater than 100 nm; a weight average molecular weight of less than 500,000 g / mol, or more preferably both.
[0199] The mesophase-separated structure provided by the present block interpolymers provides several improvements over the prior art to form microporous polymeric films. The ordered morphologies result in a greater degree of control over pore size and channel structure. The melt morphology separated by mesophase also limits film shrinkage in the melt and, therefore, provides greater dimensional stability of the melt than in materials not separated by phases.
Materials and methods [0200] All solvents and reagents are obtained from
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99/113 commercial and used sources as received unless otherwise noted. Solvent hexanes are purified through an activated alumina column followed by a column of copper oxide Q5 in alumina (Cu-0226 S is obtained from Engelhard, a subsidiary of BASF Corporation). Tetrahydrofuran (THF) and diethyl ether are purified through activated alumina columns. All metal complexes are synthesized and stored in an inert atmosphere glove box of Vacuum Atmospheres in a dry nitrogen atmosphere. NMR spectra are recorded on a 300 MHz INOVA Varian spectrometer. Chemical shifts in parts per million (δ) are recorded against trimethyl silane with reference to residual protons in a deuterated solvent.
[0201] The percentage of incorporation of 1octene and polymer density is determined by spectroscopy in the infrared region: 140 gL of each polymeric solution are deposited in 1,2,4-trichlorobenzene (TCB) on a silica disk, heated run at 140 ° C until TCB evaporates, and analyzed using a Nicolet Nexus 670 FT-IR with software version 7.1 equipped with an AutoPro automatic sample collector.
[0202] Gel permeation chromatography (GPC):
[0203] The weight average molecular weight (M _w ) and the polydispersity index are determined. M _w and M _w / M _n ratio (polydispersity index or PDI) are determined using a PolymerLabs ™ 210 high temperature gel permeation chromatograph. Samples are prepared using 13 mg of polyethylene polymer that is diluted with 16 mL of 1,2,4-trichlorobenzene (stabilized with butylated hydroxy toluene (BHT)), heat and stir at 160 ° C for 2 hours.
[0204] Standardized DSC method: determined
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100/113 melting and crystallization temperatures and differential scanning calorimetry (DSC) melting heat using a DSC 2910 instrument (TA Instruments, Inc.): In purging nitrogen gas, samples are heated from room temperature to 180 ° C at a heating rate of 10 ° C / min. This temperature is maintained for 2 to 4 minutes, the samples are cooled to -40 ° C at a cooling rate of 10 ° C / min; the sample is kept in the cold temperature for 2 to 4 minutes, and then the sample is heated to 160 ° C.
[0205] Terminal groups are analyzed by proton nuclear magnetic resonance spectroscopy ( ¹ H NMR) using a 600 MHz NMR Varian instrument and deuterated tetrachloroethane.
[0206] Abbreviations (meanings): r.t. and RT (room temperature); g (gram); mL (milliliter); ° C (degree Celsius); mmol (millimol); MHz (mega-Hertz); Hz (Hertz).
Examples of the present invention [0207] The following examples are provided to further illustrate, but without limiting the scope of the present invention.
Example 1: Synthesis of multi-functional (difunctional) chain exchange agent (1)
-40 ° C to RT
HAI (iBu) ₂ AI (íBlj) ₂
OAI (íBu) ₂ (D [0208]
The reaction is arranged and executed in a glove box purged with nitrogen. Weigh triisobutyl aluminum (3.4 g, 17 mmol) in a glass jar loaded with a bar
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101/113 stirring coated with poly (ethylene tetrafluoro) (PTFE) and dissolving in 20 mL of hexanes. Weigh 5-hexen-1-ol (2.0 mL, 17 mmol) in a small glass vial and dissolve in 5 mL of hexanes. Both solutions are placed in a freezer at 40 ° C. The solutions are removed and half of the 5-hexen-1-ol solution is added in drops in the triisobutyl aluminum solution with stirring. After adding half of the 5-hexen-lol solution, the solutions are returned to the freezer to cool them again down to -40 ° C. The solutions are removed after about 10 minutes and the rest of the 5hexen-l-ol solution is added in drops to the reaction solution with stirring. The resulting combined solution is stirred for two hours at room temperature (RT). The combined solution is placed under vacuum to remove solvent. The resulting intermediate (3.68 g, 15 mmol) is analyzed by NMR spectroscopy of '' Η and NMR of ¹³ C (CgDg). The intermediate is dissolved in 10 ml of toluene. Diisobutyl aluminum hydride (2.18 g, 15.3 mmol) is added to the resulting toluene mixture. The resulting mixture is stirred overnight at 50 ° C in an aluminum heating block. The resulting colorless solution is placed under vacuum to remove toluene. The resulting viscous liquid product is not soluble in benzene-d6 (CgD ₆ ). An NMR spectrum of '' Η is measured in THF-d8: olefin peaks are observed in the spectrum; it is estimated by NMR that approximately 17% by weight of the sample is the olefin. Most of the product (4.23 g) is transferred to another glass jar and dissolved in toluene (10 ml). Diisobutyl aluminum hydride (0.47 g) is added. The resulting solution is stirred with a PTFE-coated stir bar overnight at 50 ° C. The solvent is removed in vacuo and the
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102/113 resulting final product into a separate jar. The final product is analyzed by NMR in THF-d8; the NMR spectrum is consistent with (1).
Example 2: Synthesis of multi-functional (difunctional) chain exchange agent (2) ₊ Ai ('Bu) ₃ _ _40% · ^^ ° -aicbu) ₂ ⁺ HAI (' Bu) ₂ ^at RT, 2h
---- CB _U ) ₂ AI ^^ O ° c ^ft l (bu) ₂
3 pm (2) [0209] The reaction is arranged and executed in a glove box purged with nitrogen. Weigh triisobutyl aluminum (3.47 g) in a glass jar loaded with a stirring bar coated with PTFE and dissolve in toluene (20 ml). Weigh allyl alcohol (1.0 g) in a small glass bottle and dissolve in toluene (10 ml). Both solutions are sealed with lids coated with PTFE and both solutions are placed in a freezer at -40 ° C for 10 minutes. The solutions are removed and the alcohol solution is slowly added to the triisobutyl aluminum solution with stirring. After adding about half of the alcohol solution, put the solutions back in the freezer to cool them down again to -40 ° C. Remove the solutions from the freezer and slowly add the rest of the alcohol solution. The resulting combined solution mixture is stirred for about two hours at room temperature (RT). The solution is placed under vacuum to remove solvent and produce a colorless liquid (3.18 g, FW 182.28). An NMR spectrum of ‘‘ Η of the liquid in benzene-d is measured: the spectrum
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103/113 indicates the presence of the desired intermediate. A molar equivalent (relative to the isolated product) of diisobutyl aluminum hydride is added to the liquid. The resulting solution is stirred and heated to 60 ° C. in an aluminum heating block and stir for a total of 8 hours. NMR spectra of 'Ή show that the reaction is not complete after 4 hours and 8 hours. The solution is stirred overnight at 75 ° C keeping it lightly capped (to allow loss of isobutylene). The liquid is placed under vacuum: a small amount of gas escapes from the solution, potentially due to a loss of isobutylene. Spectra of the remaining liquid are measured; very messy spectra, consistent with the formation of multiple bridging species, but most vinyl groups have been converted. Transfer the liquid to a small bottle: 3.48 g. A sample of the liquid is transferred to a small vial and dissolved in deuterated methylene chloride. Deuterated methanol is added: a vigorous reaction is observed and a significant white solid is formed. The solution is stirred for about 1 hour. Dilute the solution with more deuterated methylene chloride and filter through a 0.45 micron disposable syringe frit. 'Ή and ¹³ C NMR spectra are measured: the spectra are consistent with the presence of CH2DCH2CH2OD and CH2DCH (CH ₃ ) ₂ . This result is consistent with the liquid containing (2).
Example 3: Polymerization of 1-octene with the multi-functional chain exchange agent (1) to give the multi-functional chain exchange agent containing poly-radical-polyolefin (3)
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104/113 (excess)
Catalyst (Al) _n BOMÀTPB ⁺ ('bu) 2ak' - ^ ^{/ x} ^ 'ai ( ^í bu) 2 ^^ T _L) (1) 45-58 ° C
AIR ₂
R ₂ AI- ^Polycytene - (CH ₂ ) ₆ -O '(3) (each R is, independently n-octyl or isobutyl ( ^L Bu)) [0210] The reaction is arranged and carried out in a purged glove box with nitrogen. The multifunctional chain exchange agent (1) of Example 1 (0.31 g) is weighed in a glass jar loaded with a stirring bar coated with PTFE and 1-octene (22.4 g) is added. The multifunctional chain exchange agent (1) becomes a white solid in the 1octene. Toluene (40 ml) is added. The resulting mixture is heated to 45 ° C to dissolve most of the multifunctional chain exchange agent (1). A catalyst solution is formed by combining a Catalyst (Al) solution shown above (0.20 mL of a 0.005M solution in toluene) and a co-catalyst solution (co-catalyst = tetrakis (pentafluor phenyl) bis borate (octadecyl) methyl ammonium ([HNMe (Ci8H ₃₇ ) ₂ ] [B (CgF ₅ ) ₄ ], abbreviated as BOMATPB) (0.22 mL of a .005M solution) about 5 minutes before its addition to the polymerization. The catalytic solution is added to the polymerization reaction to give a reactive mixture. A thermocouple is placed in the reaction mixture to monitor the temperature. The temperature rises to about 58 ° C in 30 minutes before stabilizing. The solution becomes viscous. When the temperature rise ends, the reaction mixture is removed from the heating block of
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105/113 aluminum and placed in a freezer at -40 ° C.
The solvent is removed from the reaction mixture under vacuum and the resulting reaction product comprising (3) is kept under vacuum overnight at ° C. The NMR spectra of and ¹³ C of a sample of the reaction product are measured in toluene-d8:
it is observed that the spectra are consistent with (3).
Example 4: Polymerization of D, L-lactide with multifunctional chain transfer agent (1) (D, L) -lactida + _{{i Bu) aa |} (1) Toluene,
70 ° C Poly (D, Llactide) [0211] 'AI (' Bu) ₂ (2) 1 M HCI
Day 1. In a N ₂ glove box, add 5 ml of toluene in a small 20 ml bottle loaded with a stir bar and 0.249 g of initiator, the initiator being the multifunctional chain exchange agent (1) of the Example 1. The initiator does not dissolve completely at room temperature. 2.38 g of D, L-lactide is added to the small flask followed by an additional 11 ml of toluene. The reaction mixture is covered and heated to 70 ° C using a temperature-controlled glove box using a thermocouple. (Heating starts at 10:30 am and the temperature reaches 70 ° C at 10:40 am). The reaction is stirred overnight at 70 ° C.
[0212] Day 2. At 8:30 am, it is observed that the agitation was interrupted. The cap of the small vial is removed and replaced by a septum. The small vial is removed from the glove box and seasoned with about 3.0 mL of 1M HCI solution. The NMR spectrum of a sample is measured in CDCI3. Transfer the reaction mixture to a flask containing about 50 ml of methanol. The cloudy mixture is cooled using a dry ice / acetone bath. The viscous polymer is removed
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106/113 resulting from the cloudy solution and place it in a small bottle. N ₂ gas is blown over the sample overnight to remove solvent and give the final polymeric product.
[0213] Day 3. An NMR spectrum of ‘‘ Η of the final polymeric product is measured in CDCI3. The spectrum is consistent with the final polymeric product comprising poly (D, L-lactide).
Example 5: Preparation of copolymer in diblocks of poly (octene / D, L-lactide) (l) Toluene 70 ° C (D, L) -lactidat R ₂ AI- ^Polycytene - (CH ₂ ) ₆ -Ó —--- ------- (3) (2) 1 M HCI Polioctene- (CH ₂ ) 6 ^- 0-Poly (D, L-lactide [0214] The procedure of Example 4 is repeated except that instead of using the multifunctional chain exchange agent (1), use the multifunctional chain exchange agent containing poly-radical-polyolefin (3) to give the copolymer in poly diblocks (octene / D, L-lactide). in poly diblocks (octene / D, L-lactide) it is characterized by having a polyocene block and a poly ((D, L) -lactide) block, and an oxygen connecting the polyocene block to the poly block ( (D, L) -lactide).
Example 6a: Preparation of a telekelic polyoctene
AIRR ₂ AI- ^PolTOCten ° - (CH ₂ ) ₆ -O '(1) excess isobutylene (2) 1 M HCI
CH ₂ = C (H) Polyioctene (CH ₂ ) _and -OH (3) (4) [0215] The multifunctional chain exchange agent containing poly-radical-polyolefin (3) is contacted for dehydrogenation conditions (for example , displacement of
R ₂ A1 with excess of an alpha-olefin such as isobutylene in
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107/113
ISOPAR E), followed by acidulation to give the telekelic polyoctene (4), which is designed to illustrate vinyl and hydroxyl terminal functional groups.
Example 6b: Preparation of a telekelic polyoctene
Gas stream AIR ₂ oxygen R ₂ AI— Polycytene - (CH ₂ ) ₆ ~ O (2) 1 M HCI (3)
CH ₂ = C (H; ^Ρ ζ ^1ί _η °° e- (CH ₂ ) ₆ -OH (4) [0216] A suspension of the multifunctional chain exchange agent containing poly-radical-polyolefin (3) is contacted with a current of oxygen for 1.5 h at 60 ° C (see Burfield, Polymer 1984; 25; 1817-1822 for precedent). After completing the reaction, quench the reaction by adding HCI in methanol to give the telekelic polyoctene ( 4).
Example 7: Synthesis of multifunctional chain exchange agent (5) + AI (ÍBu), ------ ^^ ^^^^ OAI (ÍBu) ₂ '-40 ° c to RT (iBu) ₂ AI '^ ^xx - ^x ^^ ^{OAI (iBU} ' ²
HAI (ÍBu) ₂ ° C (5) [0217] The procedure of Example 1 is repeated except as noted here. Toluene (30 mL) is used to dissolve triisobutyl aluminum (10.9 g) instead of hexanes; 2,7octadien-1-ol (8.0 ml) instead of 5-hexen-1-ol; toluene (10 mL) to dissolve 2,7-octadien-1-ol instead of hexanes; to give the diisobutyl 2,7-octadien-l-oxide aluminum (14.3 g), and the intermediate is analyzed by NMR spectroscopy of 'ή (CgD ₆ ). (Note that gas evolves vigorously during the addition of the solution of 2,7-octadien-1-ol in toluene in the solution of triisobutyl aluminum in toluene). Hydride is added
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108/113 diisobutyl pure aluminum (3.8 g, 1.05 molar equivalents) in a portion (6.76 g) of the intermediate, and the resulting mixture is heated to 60 ° C for 6 hours. NMR spectroscopy of ‘‘ Η (THF-d8) shows incomplete conversion of the terminal olefin functional group. More pure aluminum diisobutyl hydride (0.4 mL) is added and stirred overnight at 60 ° C. Hexane is added to give a colorless solution. Hexane is removed in vacuo to give a colorless oil. A 1.1 g portion of the colorless oil is removed; mix; isolate a gel of funds of 0.3 g of solid; the remainder of the 1.1 g portion remains dissolved in hexane. The rest of the colorless oil is placed in a 150 ml glass jar, and 1octene (5 ml) is added to it to consume the excess aluminum hydride species. The jar is sealed, stirred in an aluminum heating block at 75 ° C for 3 hours, then at room temperature overnight.
[0218] Residual 1-octene is removed in vacuo for 24 hours to give the multifunctional chain exchange agent (5) as a colorless oil; the NMR spectroscopy of ‘‘ Η (THFd8) is consistent with (5).
Example 8: Polymerization of 1-octene with multifunctional chain exchange agent (5) to give the multifunctional chain exchange agent containing poly-radical-polyolefin (6)
(excess) (ÍBli) ₂ AI (5)
Catalyst (Al)BOMÁTPB .r ,. - Polythene. (R) ₂ AI- Tol (40 mL)45-58 ° C (6)
(each R is independently n-octyl or isobutyl ( ^L Bu)).
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109/113 [0219] The procedure of Example 3 is repeated except that the multifunctional chain exchange agent (5) of Example 7 is used instead of the multifunctional chain exchange agent (1) to give the exchange agent of multifunctional chain containing poly-radical-polyolefin (6).
Example 9: Synthesis of the multifunctional chain exchange agent (5a)
HAlfBuJa ---------- ► (iBu) (Octyl) AI ^U Ί 1) 6h at 60 ° C ^U Ί
2) 20 mL of (5a)
From example 7 octene 4 hours at 100 ° C [0220] In a procedure similar to that of Example 7, a reaction is arranged and carried out in a glove box purged with nitrogen. Weigh the intermediate diisobutyl aluminum 2,7-octadien-1-oxide (10.0 g, 37.5 mmol, prepared as in Example 7) in a glass jar loaded with a PTFE-coated stir bar. To this, diisobutyl aluminum hydride (5.4 g, 37.5 mmol) is added at room temperature (RT) with stirring. The glass jar is sealed, and the resulting mixture is stirred for 6 hours at 60 ° C. NMR spectroscopy of the stirred mixture shows that a significant amount of unreacted vinyl groups is still present. An additional 80 mg of diisobutyl aluminum hydride is added, and the new mixture is stirred overnight at 50 ° C. 1-octene (20 mL) is added to the new mixture, and the resulting solution is stirred for 4 hours at 100 ° C with a reflux condenser over the solution. The volatiles are removed in vacuo, and the residual product is analyzed by ‘‘ opia NMR spectroscopy (THF-d8). NMR data of ‘‘ Η are consistent with multifunctional chain exchange agent (5a) and show
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110/113 that approximately one isobutyl / Al group is converted by aluminum to the diisobutyl aluminum 2,7-octadien-1-oxide intermediate in n-octyl / Al group as shown in (5a). Example 10: Polymerization of 1-octene with multifunctional chain exchange agent (5a) to give the multifunctional chain exchange agent containing poly-radical-polyolefin (6a)
[0221] A reaction is arranged and executed in a glove box purged with nitrogen. The multifunctional chain exchange agent (5a) (1.5 g, about 3.0 mmol) is weighed in a glass jar loaded with a PTFE-coated stir bar. Diethyl zinc (0.10 g, 0.75 mmol) is added and the resulting mixture is diluted with 25 ml of toluene. The stirred solution is placed in an external aluminum heating block (in the glass jar) set at 60 ° C and the internal temperature of the solution is monitored with a thermocouple probe. Separately, the Catalyst (Al) (0.3 ml of a 0.005M solution in toluene) is combined with BOMATPB (0.36 ml of a 0.005M solution in toluene) in a small glass bottle. The contents of the small vial are added to the solution to give a reagent solution. Additional 1-octene is added to the reagent solution at a rate of 3 mL of it every 10 minutes. After 30 minutes, no
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111/113 significant heat release in order to prepare two separate additions of new solutions of Catalyst (Al) and BOMATPB (prepared as before) to the reagent solution. (Total amounts of catalyst added: 4.5 pmol of Catalyst (Al) and 5.4 μιηοΐ of BOMATPB). The temperature of the resulting reagent solution rises to 67 ° C. The temperature is kept below 67 ° C by lowering the temperature of the external aluminum heating block. Additional 1-octene is added at a rate of 3 ml every 10 minutes until an overall total of 27 ml (173 mmol) of 1octene is added. This prepares the multifunctional chain exchange agent containing poly-radical-polyolefin (6a) at the site. Quench the reaction by adding methanol to it. The resulting methanol-containing mixture is stirred for 4 hours at 60 ° C to completely quench any alkyl aluminum compounds. Solvent (toluene, methanol, excess 1octene) is removed. The molecular weight of the initial batch (6a) is analyzed on a Viscotek gel permeation chromatograph (GPC): M _n is equal to 2,446 g / mol and the PDI is equal to 3.63. From the molecular weight data it can be concluded that both Al and Zn are transferring chain in the above reaction with the catalyst (prepared from Catalyst (Al) and BOMATPB, when native polyocene M _n is greater than 141,000 g / mol under the same conditions of reaction except without a multifunctional chain exchange agent (5a) and diethyl zinc).
[0222] Initial batch solvent treatment (6a). The initial batch (6a) is dissolved in a small amount of toluene and 60 ml of methanol are added. The resulting mixture is stirred for 2 hours at 60 ° C. The resulting liquid from the solids is removed and the solids are washed with hot methanol. SecamPetição 870190071820, of 07/26/2019, p. 117/128
112/113 If the solids were vacuum washed overnight at 100 ° C to give the treated solvent (6a). The treated solvent (6a) is analyzed by NMR spectroscopy of (CDCI3). The alkoxy / Al end group is present at 4.1 ppm and is present in a ratio of 1 alkoxy / Al end group to 274 monomer units of octylene (determined from CH ₃ side chain integration. The treated solvent is analyzed (6a) by Viscotek GPC as before. M _n equal to 5,060 g / mol and PDIO equal to 1.86 is determined for the treated solvent (6a). The molecular weight distribution of the treated solvent (6a) shows a sharp cut below 1000 (10 ³ )
Daltons. Polymeric components of lower molecular weight in the initial batch (6a) appear to have been removed by solvent treatment. From the NMR spectrum of ‘‘ ’and molecular weight data, it can be estimated that 16 mol% of polymer chains in the treated solvent (6a) end with an alkoxy / Al group.
[0223] As the Examples have shown, inventive multifunctional chain exchange agents are characterized by having at least two different functional activities and yet mutually compatible. One of the activities comprises a chain swap function. Another of the functional activities comprises a protective / initiating polymerization function, which comprises a protective group function or, in some embodiments, a polymerization initiation function, or in some incorporations, both. Multifunctional chain exchange agents incorporate at least two portions of different functionalities containing metal in a single compound or molecule. The metal-containing functional portion used to exchange the chain successfully performs the
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113/113 functional activity of chain exchange in the presence of the functional group containing metal used to initiate polymerization or group protection. The invention provides for terminally functionalizing the poly-radical-polyolefin of the multifunctional chain exchange agent containing polyradical-polyolefin or a means for initiating functional polymerization activity in the presence of the metal-containing functional group to exchange the chain. Such mutual compatibility between what could have been considered conflicting activities and functional parcels until now, is particularly valuable for preparing copolymers in amphiphilic diblocks or multiblocks, especially in a continuous polymerization process.

权利要求:
Claims (15)
[1]
1. Multifunctional chain exchange agent, characterized by the fact that it comprises a single compound distinguishable by being able to function in such a way that at least one polymer chain containing olefin can be exchanged between two or more catalytic sites of a polymerization catalyst. olefin having two or more catalytic sites or between two or more olefin polymerization catalysts and independently: (a) a non-olefin polymerization reaction can be initiated by the multifunctional chain exchange agent; (b) a functional group of the multifunctional exchange agent can be distinguished as being protected with a protecting group during the chain exchange, and then incorporated into the olefin-containing polymer chain; or (c) a non-olefin polymerization reaction can be initiated by the functional group after it has been incorporated into the olefin-containing polymer chain.
[2]
2. Multifunctional chain exchange agent, characterized by the fact that it comprises a compound having one or more parcels capable of chain exchange, one or more parcels capable of protecting or initiating polymerization, and at least one polyvalent binding group; the chain exchange portions are different from the polymerization protective / initiator portions, each chain exchange portion and each polymerization initiator portion independently comprises a metal cation, each metal of the metal cations is independently tin or a metal from any of the Groups 2, 12, and 13 of the Periodic Table of the Elements; each polyvalent linker group independently comprises from 2 to 20 carbon atoms; 0, 1, or 2
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2/9 double carbon-carbon bonds; and from 1 to 4 hetero atoms, each hetero atom being independently an oxygen atom, a sulfur atom, hydrogen substituted nitrogen atom, hydrocarbyl substituted nitrogen atom, hydrogen substituted phosphorus atom, or hydrocarbyl substituted atom; each metal cation of a chain exchange portion is independently attached to a different carbon atom from the same polyvalent linker group or to a carbon atom of a different polyvalent linker group and each metal cation of a polymerization initiator portion is independently attached to a heteroatom other than the same polyvalent linker group or to a heteroatom of a different linker group, the metal cations are thus separated from each other by at least one polyvalent linker group.
[3]
Multifunctional chain exchange agent according to either of claims 1 or 2, characterized in that it is a compound of formula (I):
{((RÕXH (-CH ₂ ) _r ) _t -R ^L - [(X-) s} q} mM ² (R ² ) _z ] _p ] _n (D or an exchange product thereof, in which:
m is an integer dei, 2, 3, or 4; aft an integer of 1 or 2; t is an integer of 1 or 2; each of n, p, q, es is an integer of 1; and when r is 1, then each R ¹ is independently a (C1-C19) alkylene or (C ₂ -Cig) alkenylene; or when (a) r is 1 and t is 2, or (b) r is 2 and t is 1, or (c) each of months is 2 and each of ret is 1, then each R ^L is independently one
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3/9 trivalent radical of an (C3-C19) alkane or (C3-C19) alkene; or n is an integer of 1, 2, or 3; is an integer of 1 or 2; p is an integer of 1 or 2; each of m, q, r, et is an integer of 1; and when each of sep is equal to 1, then each R ^L will independently be a (C1-C19) alkylene or (C2-C19) alkenylene; or when (a) s is 1 and p is 2, or (b) s is 2 and p is 1, then each R ^L is independently a trivalent radical of an (C3C19) alkane or (C3-C19) alkene; or q is an integer of 2 or 3; each of m, n, p, r, s, et is an integer of 1; and each R ^L is independently a (C1-C19) alkylene or (C2-C19) alkenylene; or each of m, n, eq is an integer of 1; each of p, r, s, et is an integer of 1 or 2; and R ^L is a tetravalent radical of an alkane of (C3-C19) or an alkene of (C3C19), where one of the other retes is 2 and one of feet is 1 and the other of feet is 2;
y is an integer of 0, 1, or 2e is chosen such that the sum of [y plus the multiplicative product of (n times q times
r] is equal to the formal oxidation state of M ¹ , that is, (the formal oxidation state of M ¹ ) = y + (n »q» r);
z is an integer of 0, 1, or 2 and is chosen such that the sum of [z plus the multiplicative product of (m times q times
s] is equal to the formal oxidation state of M ¹ , that is, (the formal oxidation state of M ¹ ) = z + (m * q * s);
each X is independently O, S, N (Η), N (C1 -C20 hydrocarbyl) _r P (Η), P (C1-C20 hydrocarbyl);
each M ¹ is a Group 2, 12, or 13 metal in the Periodic Table of the Elements, the Group 13 metal being in a state of
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[4]
4/9 formal oxidation equal to +3 and the Group 2 or 12 metal being in a state of formal oxidation equal to +2;
each M ² is tin or a Group 12 or 13 metal from the Periodic Table of Elements, the Group 12 metal being in a formal oxidation state equal to +2, the Group 13 metal being in a formal oxidation state equal to +3 , and the tin being in a state of formal oxidation equal to +2 or +4;
each R ¹ is independently a C1-C20 hydrocarbyl; or when y is 2, an R ¹ will be C1-C20 hydrocarbyl θ an R ¹ will be R ³ N (H) -, (R ³ ) 2N-, R ³ P (H) -, (R ³ ) 2P-, R ³ S-, or R ³ 0- or the two R ¹ come together to form a C2-C20 hydrocarbilene; and each R ² is independently a hydrogen, C1-C20 hydrocarbyl or C1-C20 -D-hydrocarbyl; or, when z is 2 or 3, two R ² come together to form a C2-C20 hydrocarbilene;
each D, as shown in C1-C20 -D-hydrocarbyl is independently -C (= 0) -, -C (= 0) -0-, -0-C (= 0) -, -C (= 0) N (Ci-Cg hydrocarbyl) -, -N (Ci-Cg hydrocarbyl) -C (= 0) -, -S (= 0) -, -S (= 0) ₂ -, or -Si (hydrocarbyl of Ci-C2o) 2 ^_;
each R ³ is independently a (C1-C20) hydrocarbyl or ((C1-C20) hydrocarbyl) 3S1-;
each of (C1-C19) alkylene, (C2-C19) alkenylene, (C3-C19) alkane, (C3-C19) alkene, (CiC20) hydrocarbyl, θ (C2-C20) hydrocarbene is the same or different and is independently unsubstituted or substituted with one or more substituents R ^s ; and each R ^s is independently halogen, polyfluor, perfluor, unsubstituted (C1-C1) alkyl, or unsubstituted (C1-C19) heteroaryl.
4. Multifunctional chain exchange agent, according to claim 3, characterized by the fact that it is a compound
Petition 870190071820, of 7/26/2019, p. 123/128
[5]
5/9 formula (IA):
{(R ¹ ) yM ¹ - [CH2-R ^l - [X-} mM ² (R ² ) _z ] _p ] _n (IA) or an exchange product thereof, in which:
m is an integer of 1, 2, 3, or 4, each of nep is an integer of 1, and each R ^L is independently one of the alkylene of (C1-C19) or an alkenylene of (C ₂ -Cig ); or n is an integer of 1, 2, or 3, each of mep is an integer of 1, and each R ^L is independently a (C1-C19) alkylene or (C ₂ -Cig) alkenylene; or p is an integer of 2, each of men is an integer of 1, and R ^L is a trivalent radical of an alkane of (C3-C19) or a trivalent radical of an alkene of (C3-C19);
y is one whole number in 0, 1, or 2 and is chosen such that sum in y + n is equal to state in oxidation formal in M ¹ ; z is one whole number in 0, 1, or 2 and is chosen such that sum in z + m is equal to state in oxidation formal in M ² ; and X,M ¹ , M ² , R ¹ , and R ²are tai s how were defined
previously for formula (I); or each of m, n, p is equal to 1, (R ¹ ) _and M ¹ are absent, and M ² , R ² and z are as defined above for formula (I).
5. Multifunctional chain exchange agent, according to claim 4, characterized in that each of m, n, and p is 1, (R ¹ ) ^ ¹ is absent and M ² joins with CH ₂ in the formula (IA) to form a multifunctional chain exchange agent of formula (II):
Petition 870190071820, of 7/26/2019, p. 124/128
[6]
6/9 or an exchange product thereof, where g is an integer of 0, 1, or 2e is chosen such that the sum of (g + 2q) is equal to the formal oxidation state of M; q is defined
T 2 as it was for the compound of formula (I), eR, X, M, and R are as defined above for the compound of formula (IA).
6. Multifunctional chain exchange agent according to claim 4, characterized by the fact that it is the compound of formula (Ia) in which yé2, zé2, XéO, and each of M ¹ and M and Al in an oxidized state formal equal to +3, the compound of formula (Ia) thus being a compound of formula (la-l):

(la-l)
12 in which R and R are as defined in claim 4.
[7]
7. Process for preparing a multifunctional chain exchange agent, as defined by either of claims 1 or 2, characterized in that it comprises the steps of: contacting a polyvalent group containing vinyl and hydroxy, thiol (ie, -SH) , hydrocarbilamino, amino, hydrocarbilfosfino, or phosphino (i.e., -PH ₂ ) to an alkylperhydrocarbon metal to prepare an organometallic intermediate, which is a vinyl alkoxide of
Petition 870190071820, of 7/26/2019, p. 125/128
7/9 hydrocarbyl metal, vinyl hydrocarbyl metal sulfide, vinyl (hydrocarbyl) metal hydrocarbyl amine, vinyl hydrocarbyl metal amine, vinyl hydrocarbyl (hydrocarbyl) metal, or vinyl hydrocarbyl metal; and contacting the organometallic intermediate with a hydrocarbyl metal monohydride, thereby preparing the multifunctional chain exchange agent, each metal being independently a tin or metal cation of any of Groups 2, 12, and 13 of the Periodic Table of the Elements.
[8]
8. Process for preparing a multifunctional composition, characterized in that it comprises the steps of: contacting the ingredients comprising the chain exchange agent, as defined by any one of claims 1 to 6, an original olefin polymerization catalyst, and a original cocatalyst, the contact being performed under catalyst preparation conditions, thus preparing the multifunctional composition, and the multifunctional composition being able to function as a multifunctional chain exchange agent and as an olefin polymerization catalyst.
[9]
9. Multifunctional composition, characterized by the fact that it is prepared by the process to prepare a multifunctional composition, as defined by claim 8.
[10]
10. Process for preparing a multifunctional chain exchange agent containing poly-radical-polyolefin, characterized in that it comprises a step of: contacting the reagents comprising one or more olefin polymerization catalysts and at least one olefin monomer, the one or more olefin polymerization catalysts comprising the multifunctional composition, as defined by claim 9, and the contact step being performed in
Petition 870190071820, of 7/26/2019, p. 126/128
8/9 olefin polymerization conditions, thereby preparing a multifunctional chain exchange agent containing poly-radical-polyolefin, the multifunctional chain exchange agent containing poly-radical-polyolefin being a reaction product of the reactants.
[11]
11. Multifunctional chain exchange agent containing polyradical-polyolefin, characterized by the fact that it comprises the multifunctional chain exchange agent containing poliradical-polyolefin prepared by the process, as defined by claim 10.
[12]
12. Process for preparing a telekeletal polyolefin, characterized by the fact that it comprises a step of terminally functionalizing the poly-radical-polyolefin of the multifunctional chain exchange agent containing poly-radical-polyolefin, as defined by claim 11, thus preparing a telekeletal polyolefin, the telekeletal polyolefin being distinguishable by having first and second spaced functional groups, the process deriving the first terminal functional group from a chain exchange portion and the second terminal functional group from a portion capable of protecting or initiating polymerization, each such portion being of the multifunctional chain exchange agent containing polyradical-polyolefin, the first and second terminal functional groups being structurally different from each other.
[13]
13. Telekeletal polyolefin, characterized by the fact that it comprises the telekeletal polyolefin prepared by the process, as defined by claim 12, and the telekeletal polyolefin has a non-statistical distribution of the first and second terminal functional groups.
Petition 870190071820, of 7/26/2019, p. 127/128
9/9
[14]
14. Process for preparing a polyolefin with terminal functionality, characterized in that it comprises a step of: terminating the poly-radical-polyolefin of the multifunctional chain exchange agent containing poly-radical-polyolefin, as defined by claim 11, thus preparing a polyolefin with terminal functionality of formula (III):
H-polyolefin-CH ₂ -RL- (XH) _w (III) in which w is an integer of 2; each RL is independently (C1-C19) alkylene or (C2-C19) alkenylene; and each X is independently 0, S, N (H),
N (((C1-C20) hydrocarbyl) r P (H), or P ((CiC20 hydrocarbyl)) ·
[15]
15. Battery separator, characterized by the fact that it comprises telekeletal polyolefin, as defined by claim 13.

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CA2768987A1|2011-02-03|

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US10703837B1|2019-05-01|2020-07-07|The Goodyear Tire & Rubber Company|Method of making a functionalized elastomer, elastomer, rubber composition and tire|

法律状态:
2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-02-05| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|

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2019-04-30| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2019-08-20| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2019-10-22| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 28/07/2010, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US22942509P| true| 2009-07-29|2009-07-29|

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PCT/US2010/043483|WO2011014533A1|2009-07-29|2010-07-28|Multifunctional chain shuttling agents|

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