Chain transfer agent, process for polymerizing at least one addition polymerizable monomer, multi-bl

专利摘要:
chain transfer agent, process for the polymerization of at least one addition polymerizable monomer, multi-block copolymer and catalyst composition using specific catalyst compositions, including or use of chain transfer agents in the olefin polymerization process. Specifically, this disclosure provides for double-headed and multi-headed chain transfer agents (csas or msas) and for their use in the preparation of block copolymers. By controlling the ratio of double-headed and multi-headed csa sites to single-headed csa sites, a block copolymer may be provided having properties such as a narrow molecular weight distribution and / or improved melting properties.
公开号:BR112012001948B1
申请号:R112012001948-1
申请日:2010-07-20
公开日:2019-08-20
发明作者:Daniel ARRIOLA；Thomas Clark；Kevin Frazier；Sara Klamo；Francis Timmers
申请人:Dow Global Technologies Llc；
IPC主号:

专利说明:

CHAIN TRANSFER AGENT, PROCESS FOR THE POLYMERIZATION OF AT LEAST ONE POLYMERIZABLE MONOMER BY ADDITION, MULTI-BLOCK COPOLYMER AND CATALYST COMPOSITION
Invention field [0001]
The disclosure relates to catalysts compositions for the polymerization of olefins, their manufacture, to the production of polyolefins using specific catalyst compositions, including the use of chain transfer agents in the olefin polymerization process.
Background of the invention [0002]
The properties and applications of polyolefins depend to varying degrees on the specific characteristics of the catalysts used in their preparation.
Specific catalyst compositions, activation conditions, steric and electronic characteristics, and the like, all can influence the characteristics of the resulting polymer product. In fact, a multitude of polymer characteristics, such as monomer co incorporation, molecular weight, polydispersity, and polymeric chain branching, and related physical properties, such as density, modulus, melting properties, tension characteristics, and optical properties , may be affected by the catalyst design.
[0003]
In recent years, the use of well-defined catalyst precursors has generally allowed for improved control over the properties of the polymer, including branching architecture, stereochemistry, and building block copolymers. This last aspect of the polymer design in which the hard (semi-crystalline or high glass transition temperature) and soft (amorphous or
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2/119 low temperature glass transition) are mounted on a polymeric chain, it has been especially challenging. Recent advances in the formation of block copolymers have been seen with the use of chain transfer agents (CSAs) that can exchange a growing polymer chain between several catalytic sites, in such a way that portions of a single polymer molecule are synthesized by at least two different catalysts. In this way, block copolymers can be prepared from a common monomer environment using a mixture of catalysts of different selectivities, such as different stereoselectivities or monomer selectivities. Under the right conditions, an efficient chain transfer can produce a multi-block copolymer that presents a random distribution of hard and soft blocks of random length.
[0004] Generally, the present collection of chain transfer agents (CSAs) typically contain a single effective site for chain growth along each polymeric chain.
[0005] Although these CSAs can be considered to contain multiple sites, for example, diethyl zinc contains two portions of ethyl zinc to which a polymer may be attached, the chain transfer between the CSA and the catalyst occurring in one direction in each polymeric chain. The use of dual headed CSAs containing an equal number of zinc-alkyl and alkaline zinc groups could potentially lead to reduced homogeneity in the polymer architecture. Such materials could also potentially lead to an extension of the product's molecular weight distribution.
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3/119 [0006] Even with the advent of dual CSA catalyst combinations in the preparation of block copolymers, challenges remain in creating especially the specific polymer properties that are desired using this approach. Hence, it is desirable to develop new chain transfer agents, methods for making chain transfer agents, as well as CSA-catalyst combinations, which may provide new methods for preparing block copolymers and copolymers with improved properties.
Summary of the invention [0007] In some embodiments, the present disclosure provides a chain transfer agent having the formula: R ¹ [M ^A -R ² -] _N M ^A R ¹
R ¹ [MBR ¹ -R ² -] nMB (R ¹ ) 2
M ^C [R ² ] 2M ^C , or M ^B [R ² ] 3M ^B ;
or an aggregate of these, a derivative of these containing Lewis base, or any combination thereof; Where
A z
M is Zn or Mg;
M ^B is B, Al, or Ga;
M ^C is Mg;
R ¹ in each occurrence is independently selected from hydrogen, halide, amide, hydrocarbyl, hydrocarbilamide, dihydrocarbilamide, hydrocarbyl oxide, hydrocarbyl sulfide, dihydrocarbyl phosphide, tri (hydrocarbil) silyl; any hydrocarbyl group being optionally substituted with at least one halide, amide, hydrocarbilamide, dihydrocarbilamide, or hydrocarbyl oxide; and each R ¹ containing carbon having from 1 to 20 carbon atoms, inclusive;
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4/119 λ ζ
R at each occurrence and independently selected from (CH2) m, O [CH2) nCH2CH2] 2, S [(CH2) nCH2CH2] 2, RANHC ^ nC ^ C ^] 2, (RB) 2Si [(CH2) nCH2CH2] 2 , (RB) 3SiOSiRB [(CH2) nCH2CH2] 2, or [Si (R ^B ) 2 (CH2CH2) nCH2CH2] 2O;
where n in each occurrence and independently an integer from 1 to 20, inclusive; n is an integer from 2 to 20, inclusive; R ^A and H or a hydrocarbyl having from 1 to 12 carbon atoms, inclusive; and R ^B at each occurrence is a hydrocarbyl having 1 to 12 carbon atoms, inclusive; and N, on average, in each occurrence is a number from 2 to 150, inclusive.
[0008] In practice, N is the average that describes a sample of molecules and will not necessarily be an integer. For example, N on average may be a number from 5 to 140, from 10 to 125, from 15 to 110, or from 20 to 100, inclusive. The N value of a sample can be determined by NMR spectroscopy or comparable methods.
[0009] In these transfer agent formulas, R ¹ can generally be selected from any monovalent portion that does not prevent chain transfer from occurring. For example, R ¹ is typically selected from a hydrocarbyl such as an alkyl having 1 to 20 carbon atoms. Also for example, R ² can be selected from ethanediyl,
1,3-propanediyl, 1,4-butanediyl, 1,5-pentanediyl, 1,6hexanediyl, 2,5-hexanediyl, 1,7-heptanediyl, 1,8octanodiyl, 1,9-nonanodiyl, 1,10-decanodiyl, and similar.
[0010] In some embodiments, the present disclosure provides for a process for making chain transfer agents having the formula R ¹ [M ^A -R ² -] _N M ^A R ¹ ,
R ¹ [MBR ¹ -R ² -] nMB (R ² ) 2,
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5/119
M ^c [R ² ] 2M ^c , or M ^b [R ² ] 3M ^b , as described above.
[0011] In some embodiments, the present disclosure provides for a catalyst composition comprising the contact product of at least one polymerization catalyst precursor, at least one cocatalyst, and at least one chain transfer agent as described above. In other embodiments, the present disclosure provides for a process for preparing a catalyst component, the process comprising contacting at least one polymerization catalyst precursor, at least one cocatalyst, and at least one chain transfer agent having the formula R ¹ [ M ^to -R ² ] nMAR ¹ ,
R ¹ [M ^b R ¹ -R ² -] nM ^b (r ¹ ) 2,
M ^c [R ² ] ₂ M ^c , or M ^b [R ² ] 3M ^b , as described above.
[0012]
In some embodiments, the present disclosure provides for a process for the polymerization of at least one addition-curable monomer to form a polymer composition, the process comprising:
contacting at least one polymerizable monomer by addition with a catalyst composition under polymerization conditions; the catalyst composition comprising the contact product of at least one polymerization catalyst precursor, at least one cocatalyst, and at least one chain transfer agent having the formula R ¹ [MA-R ² -] _n MAR ¹ ,
R ¹ [M ^b R ¹ -R ² -] nM ^b (r ¹ ) 2,
M ^c [R ² ] ₂ M ^c , or M ^b [R ² ] ₃ M ^b , as described above.
[0013] In one aspect, this disclosure provides a chain transfer agent represented by the following Newkome dendrimer nomenclature:
G [C] [(R) Nb (Z)] Nc, or an aggregate thereof, a derivative containing Lewis base
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6/119 thereof, or any combination thereof; being that:
C is a nucleus selected from a metal, di (metal) of alkydyl, tri (metal) of alkydryl, or tetra (metal of alkydraila, the metal being Zn, Mg, B, Al, or Ga, and any nucleus containing carbon having 2 to 20 carbon atoms;
R at each occurrence is a repetitive unit selected from an alkydyl metal, alkydyl di (metal), or alkydetrail tri (metal) having 2 to 20 carbon atoms and an average Nb branch multiplicity;
G is the generation of the dendrimer cascade;
Z is a terminal monovalent group having up to 20 carbon atoms;
NC is the multiplicity of branches of the nucleus; and the transfer agent comprises at least one generation of repetitive units of R, such that G, on average, is a number from 2 to 150 inclusive.
[0014] In practice, G is the generational description of a sample of molecules and will not necessarily be an integer. The G and N of a sample can be determined by NMR spectroscopy or comparable methods.
[0015] This disclosure also provides a process for the polymerization of at least one addition-curable monomer to form a polymer composition, the process comprising:
contacting at least one polymerizable monomer by addition with a catalyst composition under polymerization conditions; the catalyst composition comprising the contact product of at least one polymerization catalyst precursor, at least one cocatalyst, and at least one
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7/119 chain transfer agent as described above.
[0016] This disclosure also provides for a catalyst composition comprising the contact product of at least one polymerization catalyst precursor, at least one cocatalyst, and at least one chain transfer agent represented by the Newkome dendrimer nomenclature above. This disclosure also provides for a process for preparing such a catalyst component, the reaction comprising contacting at least one polymerization catalyst precursor, at least one cocatalyst, and at least one chain transfer agent of this Newkome dendrimer nomenclature.
[0017] In some embodiments, the present disclosure provides for a process for making chain transfer agents having the formulas
G [C] [(R) N _b (Z)] N _c , as described above.
[0018] While the Newkome nomenclature is not the molecular formula in the traditional sense, it constitutes a shorthand by which the one with a medium understanding of the subject will be able to understand the traditional molecular formula. According to Newkome's nomenclature parameters, because G is a number from 2 to 150, there is at least one repetitive unit in the dendritic chain transfer agent in this disclosure.
[0019] As understood by the one medically understood in the subject, the multiplicity of branching of the nucleus (N _c ) is two for zinc and one alkyl (di) metal, three for one alkyl (tri) metal, and four for an alkyl tetra (metal) tetra. However, the
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8/119 plurality of branching of the C _b is a repeating unit R for alcnodiila metal, di two to one (metal) of alcanotriila, and three for a tri (metal) of alcanotetraila.
[0020]
Another aspect of this disclosure is that chain transfer agents such as R ¹ [M ^to -R ² -] NM ^to R ¹ and R ¹ [M ^b R ¹ -R ² ] NM ^b (R ¹ ) ₂ disclosed here constitute CSAs that can typically be described by the dendrimer nomenclature of
Newkome
G [C] [(R) Nb (Z)] Nc.
[0021]
A further aspect of this disclosure relates to the preparation and utility of catalyst compositions having new structural entities containing repetitive units of metals of main groups and alkanodiyl groups, such as alkanediyl-zinc-alkanediyl-zinc-alkanediyl-zinc and so on. Such structures can function as two-headed CSAs and can be used in block-type polymerization reactions. For example, when the monomer feed or concentration is changed during the copolymerization process, symmetrical gradient triblock copolymers can be formed. The process may be extended to form a symmetrical block copolymer with an odd number of blocks, with those blocks having either a gradual or abrupt gradient of composition or crystallinity. In a further aspect, the disclosure provides for compositions comprising or selected from the polymeric and heteroatom-substituted CSAs disclosed herein, and processes for making and using them, and compositions of the product polymers.
[0022] Consequently, an aspect of the present disclosure provides an olefin polymer composition characterized by
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9/119 a narrow molecular weight distribution and a process for preparing the olefin polymer composition. The polymer composition is prepared in situ by the polymerization of one or more polymerisable monomers by addition, generally two or more polymerisable monomers by addition, particularly ethylene and at least one polymerizable comonomer, propylene and at least one copolymerizable comonomer having 4 or more carbons , or 4-methyl-1-pentene and at least one copolymerizable comonomer having 4 or more carbons, optionally comprising multiple blocks or segments of polymer composition or differentiated properties, especially blocks or segments comprising differentiated comonomer incorporation levels. In this regard, the present process includes contacting a monomer or a mixture of monomers polymerizable by addition, under conditions of polymerization by addition, with a composition comprising at least one polymerisation catalyst by addition, a cocatalyst, and a chain transfer agent. double heads or multiple heads as provided here.
[0023] Additionally, this disclosure provides a process for forming a n-block copolymer where n is an odd number greater than or equal to 3, the process comprising contacting at least one polymerizable monomer by addition with a catalyst composition under conditions of polymerization;
the catalyst composition comprising at least one catalyst precursor, at least one cocatalyst, and at least one chain transfer agent as disclosed herein; the process comprising a combination of (n + 1) / 2 transfer stages and chain growth.
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11/10
Detailed description of the invention [0024] The term "transfer agent" or "chain transfer agent" refers to a compound or mixture of compounds that is capable of causing polymeric transfer between various sites of active catalysts under polymerization conditions. That is, the transfer of a polymer segment occurs from, and to, an active catalyst site in an easy and reversible manner. In contrast to a transfer agent, an agent that acts merely as a chain transfer agent such as some alkyl chain compounds, may, for example, exchange an alkyl group on the chain transfer agent with the polymer chain in question. growth in the catalyst, which generally results in termination of the growth of the polymer chain. In this case, the core group center acts as a repository for a dead polymer chain, rather than engaging in reversible transfer with a catalyst site as the transfer agent acts. Desirably, the intermediate formed between the chain transfer agent and the polymeric chain is not sufficiently stable with respect to the exchange between this intermediate and any other growing polymeric chain, such that the chain termination is relatively rare.
[0025] Double or multiple headed transfer agents include species with metal-alkyl bonds that engage in chain transfer during a transition metal catalyzed polymerization. Because these chain transfer agents can be oligomeric, they can consist of mixtures of species, or both, it is difficult to
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11/119 describe precisely these agents since they are used in solution, the CSA solution typically comprising a complex mixture of different species. Hence, the useful CSAs disclosed here are typically described using average compositions, mean numbers of valences of multiple-headed sites, mean numbers of valences of single-headed sites, and reasons for those numbers. For example, in CSAs having the empirical formulas M [R] ₃ M or M [R] ₂ M as disclosed here (MB is B, Al, or Ga and MC is Mg), these products are typically non-discrete dimeric structures suggested by their empirical formulas, but in fact these formulas or descriptions are representative of the empirical formulas of the polymeric CSA structures.
The term double-headed or multiple-headed transfer agent (or chain transfer agent) refers to a compound or molecule containing more than one chain transfer portion linked by a polyvalent linking group. To illustrate, an example of a double-headed CSA is provided in the compounds of the general formula R ¹ - [Zn-R ² ] NZn-R ¹ or R ¹ [AlR ¹ R ² -] NAlR ¹ ₂ , where R ¹ is a monovalent hydrocarbon group ₂ and R is a divalent hydrocarbyl group. To further illustrate, an example of a triple-headed CSA is provided in the compounds of the general chemical formulas
3 1 1 (R Zn ₃ ) [(R (ZnR) ₂ ] ₃ , where R is a monovalent hydrocarbyl group ₃ such as ethyl, and R is a trivalent hydrocarbyl group. For a trivalent hydrocarbyl chain transfer agent, up to three polymer growth residues are possible, each connected to a trivalent residue. A single polymer growth residue can be comprised of concatenated segments of
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12/119 multiple catalysts. It is desirable to have all the valences of the R portion participating in this chain growth activity that will lead to the highest molecular weight polymer. In practice, suitable chain transfer plots typically include metal centers derived from a metal selected from Groups 2-14 of the Periodic Table of the Elements and having one or more available valences capable of reversibly linking a growing polymer chain prepared by a catalyst. polymerization by coordination. At the same time that the chain transfer portion attaches to the growing polymer chain, the remainder of the polyvalent linkage group remains after loss of the chain transfer portion or parcels is incorporated or otherwise linked to one or more sites of active catalyst, thus forming a catalyst composition containing an active coordination polymerization site capable of inserting polymer at least one end of what was originally the polyvalent linking group.
[0027] Many chain transfer agents in this disclosure could be considered dendritic, with double-headed CSAs constituting a type of dendritic CSA. A convenient and systematic nomenclature for describing cascading dendrimers or polymers or oligomers is reported in A Systematic Nomenclature for Cascade Polymers, Newkome, G.R .; Baker, G.R .; Young, J.K .; and Traynham, J.G., Journal of Polymer Science: Part A ”Polymer Chemistry, 1993, 312, 641-651, which is incorporated herein in its entirety by reference. The Newkome nomenclature may be adapted to describe a wide range of doubles CSAs
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13/119 and multiple heads having combinations of different sites of multiple- and single-heads. In some embodiments, the present disclosure provides for a series of double-headed and multiple-headed chain transfer agents that limit, reduce, or minimize the number of zinc-alkyl terminal groups of single-headed CSA sites R ¹ , compared to the double-headed R or multiple-headed R or R CSA sites, a feature that has been found to lead to a more homogeneous polymer. This aspect, in turn, may be reflected in more desirable polymer properties, such as a narrower molecular weight distribution, compared to polymers resulting from chain transfer agents without such limits. In one aspect, the chain transfer agent may be a double-headed CSA with the ratio of R ² sites to R ¹ sites being greater than 1. Therefore, controlling the ratio of valencies from multiple heads to single heads , Q, at values greater than one (Q> 1), this disclosure leads to polymeric materials with narrower molecular weight distributions than those obtained with diethylzinc or with double-headed CSAs having the ratio Q = 1.
[0028] The Q parameter is defined as the ratio of the number of valences of multiple head sites to the number of valences of single site in an empirical formula in the agent, or agents, of chain transfer. Therefore, each R ¹ group is considered as having a single site valence each _second R group is regarded as having two valencies heads ₃ double, i.e. valences of the folded type, each R is considered to have three valences of three heads or triple type, and each R ^{3 4} is considered as four
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14/119 valences of the quadruplicate type, and so on. Hence, if R1, R2, R3, R4, and so on through Rn, represent the number of plots or groups R ¹ , R ² , R ³ , R ⁴ and R ⁿ plots or groups respectively, in the empirical formula of an agent of chain transfer, then Q can be defined by the following formula:
Q = (2 »R2 + 3 * R3 + 4 * R4 + ... n * Rn) / R1 [0029] A similar series of aluminum chain transfer agents is also included in this disclosure, with corresponding characteristics that limit the ratio of R sites to R sites. Furthermore, in another aspect, the appropriate use of anionic heteroatom substitution, such as halide or alkoxide, in M can be used to reduce the value of R1 and thus increase Q to higher values approaching infinity.
[0030] An additional aspect of this disclosure is the use of double-headed CSAs as disclosed here for the preparation of symmetric multi-block copolymers with an odd number of blocks (n = 3.5.7, and so on), and a monomer gradient separating the blocks.
[0031] In one aspect, the present disclosure provides for double-headed and multi-headed chain transfer agents (CSAs) for their use to prepare block copolymers having desired properties. Among other things, the present disclosure provides for the design and CSA for use in a polymerization process of olefins in which the ratio (Q) of valences CSA sites dual heads (for example _2, alcadiila or R) or valences of multiple-headed sites (for example, rump (R) or rump (R) for R ¹ valences of single-headed CSA sites (for
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15/119 example, alkyl or any monovalent R ¹ ) is regulated. Controlling the ratio of double or multiple head CSA sites R, R or R to R sites (monovalent) or terminal valences, typically for values greater than 1, multi-block copolymers are provided having specially made properties, such as such as narrow molecular weight distributions or improved melting properties. For example, by controlling the ratio of double-headed and multiple-headed sites to single-headed sites (for example, R ¹ , such as alkyl) to values greater than 1, a more homogeneous CSA can be obtained resulting in more homogeneous polymers with properties improvements such as narrowing the molecular weight distribution or improved melting properties. This class of reagents provides a chemical alternative to control the process condition of homogeneity of the polymer.
[0032] In several respects, the following references are generally related to zinc and aluminum compounds, each of which is incorporated herein in its entirety by reference.
[0033] Preparation of Dizinc Compounds by a Boron-Zinc Exchange. Eick, H .; Knochel, P. Angew. Chem. Int. Ed. Engl. 1996, 35, 218-220; The Direct Formation of Functionalized Alkyl (aryl) zinc Halides by Oxidative Addition of Highly Reactive Zinc with Organic Halides and Their Reactions with Acid Chlorides, α, β-Unsaturated Ketones, and Allylic, Aryl, and Vinyl Halides, Zhu, L .; Wehmeyer, RM; Rieke, RDJ Org. Chem. 1991, 56, 1445-1453; Synthesis of New C ₂ Symmetrical Diphosphines Using Chiral Zinc Organometallics, Longeau, A .; Durand, S .; Spiegel, A .; Knochel, P.
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11/16
Tetrahedron; Asymmetry 1997, 8, 987-990; Control of Polymer Architecture and Molecular Weight Distribution Via MultiCentered Shuttling Agent, Carnahan, E .; Hustad, P .; Jazdzewski, B.A .; Kuhlman, R.L .; Wenzel, T .; WO 2007/035493 A2; and Catalytic Olefin Block Copolymers with Controlled Block Sequence Distribution. Wenzel, T .; Carnahan, E .; Kuhlman, R.L .; Hustad, P.D .; WO 2007/035485 A1.
[0034] The following references are also generally related to various aspects of this disclosure, for example, chain transfer agents, each of which is incorporated herein in its entirety by reference; Lieber and Brintzinger, Macromolecules 2000, 33, 9192-9199; Liu and Rytter, Macromolecular Rapid Comm. 2001, 22, 952-956; and Bruaseth and Rytter, Macromolecules 2003, 36, 3026-3034; Rytter et al., Polymer 2004, 45, 97853-7861; WO 07/35493; WO / 98/34970; Gibson et al., J. Am. Chem. Soc. 2004, 126, 10701-10712; and US Patent ^Nos 6,380,341; 6,169,151, 5,210,338; 5,276,220; and 6,444,867.
[0035] Another aspect of the present disclosure provides for the preparation of new structural entities containing repetitive units of metals of main groups such as zinc, aluminum, magnesium, boron, or gallium, and alkanodiyl groups (for example, containing repetitive plots such as -alkadiylazinc-alkadiyl-zinc). In this disclosure, the terms alkanediyl, alkadiyl, and alkdiyl are used interchangeably. These structures are considered double-headed CSASs and can be used in block polymerization reactions. For example, when the monomer feed or concentration is changed during copolymerization, triblock copolymers may be formed
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17/119 symmetrical gradient. The process can be extended to form a symmetrical multi-block copolymer with an odd number of blocks with those blocks having a gradual or abrupt gradient in composition or crystallinity. [0036] As disclosed here, one aspect provides for a batch reaction with ethylene and propylene and an activated catalyst using the double-headed CSAs disclosed here. Because ethylene generally has a substantially higher reactivity than propylene, propylene is added in excess since the reaction is carried out below the full consumption of the limiting ethylene reagent. The final polymer morphology may include an ethylene / propylene rubber segment with isotactic propylene at each end.
[0037] Yet an additional aspect of this disclosure provides for the use of double-headed CSAs as described here, along with the addition of diethyl zinc or other single-site CSA portions that may create inhomogeneity. The relative amount of inhomogeneity can be controlled by adding more or less diethyl zinc to the reactor. In addition, additional blocks can be added to the end of the polymer, for example, by adding another monomer or transferring the reaction mixture to another reactor.
[0038] In another aspect, the present disclosure provides for inventive polymer products that include combinations of two or more polymers comprising regions or segments (blocks) of different chemical composition or physical properties. Because the polymer composition may contain a binding group that is the remnant of a multi-centered chain transfer agent, the composition
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The resultant polymeric 18/119 may have unprecedented physical and chemical properties compared with random mixtures of polymers of the same crude chemical composition and comparatively with block copolymers prepared with a missing chain transfer agent from double or multiple chain chain transfer centers . Depending on the number of active centers in the double-stranded or multi-stranded transfer agent, that is, whether each chain-transfer agent molecule has two, three, or more active transfer sites, and the number of separate additions of that agent , the resulting polymer may be relatively monodispersed, form a controllable distribution of molecular weight polymers and / or branched or multi-branched polymers. In general, the resulting polymers contain a reduced incidence of cross-linked polymer formation, as evidenced by a reduced gel fraction. For example, typically the polymers produced according to this disclosure comprise less than 2 percent crosslinked gel fraction, more preferably less than 1 percent crosslinked gel fraction, and most preferably less than 0.5 percent fraction of crosslinked gel of cross-linked gel.
[0039] Therefore, in one aspect, a process for the polymerization of at least one addition-curable monomer is disclosed herein to form a polymer composition, the process comprising:
contacting at least one polymerizable monomer by addition with a catalyst composition under polymerization conditions; the catalyst composition comprising the contact product of at least one polymerization catalyst precursor, at least one cocatalyst, and at least one
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19/119 chain transfer agent represented by the following Newkome dendrimer nomenclature:
G [C] [(R) N _b (Z)] Nc, or an aggregate thereof, a derivative containing Lewis base thereof, or any combination thereof; being that:
C is a nucleus selected from a metal, di (metal) of alkydyl, tri (metal) of alkydryl, or tetra (metal of alkydraila, the metal being Zn, Mg, B, Al, or Ga, and any nucleus containing carbon having 2 to 50 carbon atoms;
R at each occurrence is a repetitive unit selected from an alkydyl metal, alkydyl di (metal), or alkydetrail tri (metal) having 2 to 20 carbon atoms and an average Nb branch multiplicity;
G is the generation of the dendrimer cascade;
Z is a terminal monovalent group having up to 20 carbon atoms;
NC is the multiplicity of branches of the nucleus; and the transfer agent comprises at least one generation of repetitive units of R, such that G, on average, is a number from 2 to 150 inclusive.
[0040] In practice, G is the average generative description of a sample of molecules and will not necessarily be an integer. The G and N of a sample can be determined by NMR spectroscopy or comparable methods.
[0041] Also provided is a catalyst composition comprising the contact product of at least one polymerization catalyst precursor, at least one cocatalyst, and at least one chain transfer agent represented by the Newkome dendrimer nomenclature immediately
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11/20 above.
[0042] Although the Newkome nomenclature is not the molecular formula in the traditional sense, it constitutes a shorthand by which the one with a medium understanding of the subject can understand the traditional molecular formula. According to Newkome's nomenclature parameters, because G is a number from 2 to 150, there is at least one repetitive unit in the dendritic chain transfer agent in this disclosure. In an additional aspect, G can be from 2 to 100, from 2 to 50, or from 2 to 25, as well as the intermediate bands and sub-bands.
[0043] The present disclosure also provides a polymerization process of at least one monomer polymerizable by addition to form a polymer composition, the process comprising:
contacting at least one polymerizable monomer by addition with a catalyst composition under polymerization conditions; the catalyst composition comprising at least one chain transfer agent having the formula: R ¹ [M ^A -R ² -] _N M ^A R ¹ , where M ^a is Zn or Mg;
R ¹ [MBR ¹ -R ² -] _n MB (R ¹ ) 2, where MB is B, Al, or Ga;
M ^C [R ² ] ₂ M ^C , where M ^C is Mg;
M ^B [R ² ] 3M ^B , where M ^B is B, Al, or Ga, as provided above;
or an aggregate of these, a derivative of these containing Lewis base, or any combination thereof; Where
R ¹ in each occurrence is independently selected from hydrogen, halide, amide, hydrocarbyl, hydrocarbilamide, dihydrocarbilamide, hydrocarbyl oxide, hydrocarbyl sulfide, dihydrocarbyl phosphide, tri (hydrocarbil) silyl; any hydrocarbyl group being
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21/119 optionally substituted with at least one halide, amide, hydrocarbilamide, dihydrocarbilamide, or hydrocarbyl oxide; and each R ¹ containing carbon having from 1 to 20 carbon atoms, inclusive;
λ z
R in each occurrence is independently selected from (CH2) m, O [CH2) nCH2CH2] 2, S [(CH2) nCH2CH2] 2, RAN [(CH2) nCH2CH2] 2, (RB) 2Si [(CH2) nCH2CH2] 2 , (RB ^ SÍOSÍRBHC ^^ C ^ C ^ L ·, or [Si (R ^B ) 2 (CH2) nCH2CH2] 2O;
where n in each occurrence is independently an integer from 1 to 20, inclusive; n is an integer from 2 to 20, inclusive; R ^A is H or a hydrocarbyl having from 1 to 12 carbon atoms, inclusive; and R ^B at each occurrence is independently a hydrocarbyl having from 1 to 12 carbon atoms, inclusive; and N, on average, in each occurrence is a number from 2 to 150, inclusive.
[0044] In these formulas of chain transfer agents,
R ¹ can be selected from any monovalent portion that does not prevent the chain transfer from occurring. Specific examples of R ¹ include, but are not limited to, CH3, CH2CH2, CH2CH2CH3, CH2CH2CH2CH3, CH (CH3) 2, CH2CH (CH3) 2, CF3, C6H5, C6H4CH3, Cl, Br, I, OCH3, OCH2CH2, OCF3 , OC6H5, OCH2CH2CH3, OCH (CH3) 2, OC6H5, OC6H4CH3, OC6H3 (CH3) 2, OC6H3 (CH3) 3, SCH3, SCH2CH2, SC6H5, NH2, NHCH3, NHCH2CH3, NHCH2CH2CH3, NHCH (CH3), NHCH (CH3) 2 N (CH3) 2, N (CH2 (CH2CH2) 2, Si (CH3) 3, Si (CH2CH3) 3, and the like, although typically R ¹ may be selected from a hydrocarbyl such as those specific portions exemplified here.
[0045] This disclosure also provides for a catalyst composition comprising the contact product of at least one catalyst precursor, at least one cocatalyst, and
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22/119 at least one chain transfer agent having the formulas shown immediately above. A number of multi-centered double-headed chain transfer agents have been described here that can generally be characterized either by the Newkome G [C] [(R) N _b (Z)] dendrimer nomenclature, or by the general formulas R ¹ [M ^to -R ² -] _n M ^to R ¹ ,
R ¹ [MBR ¹ -R ² -] nMB (R ¹ ) 2,
M ^c [R ² ] 2M ^c , or M ^b [R ² ] 3MB. When CSAs can be described using the Newkome G [C] [(R) Nb (Z)] Nc dendrimer nomenclature, such species are characterized by having a generation of the dendrimer cascade G> 1. When CSAs can be described using linear CSA formulas R ¹ [M ^to -R ² -] _n M ^to R ¹ and
B 1 2 B 1 '
R [MR-R-] _n M (R) ₂ , such species are characterized as having N> 1.
[0046] The CSAs in this disclosure have a generation of the cascade of dendrimers G greater than 1, or have an N in the formulas R ¹ [M ^to R ² -] nM ^to R ¹ , R ¹ [M ^b R ¹ -R ² - ] nM ^b (R ¹ ) ₂ greater than 1. Specific examples include compounds of the formulas Et [Zn (CH ₂ ) _n ] _x ZnEt, where n may be 2,3,4,5,6,7,8,9, 10,11,12,15,20, and similar, ex may be
2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19, 20,25,30,35,40,45,50, 55,60,65,70,75,80,85,90,95,100, or greater, or Et [AlEt (CH ₂ ) _m ] _y AlEt ₂ , where m can be
2,3,4,5,6,7,8,9,10,11,12,15,20, and similar, ex may be 2,3,4,5,6,7,8,9,10, 11,12,13,14,15,16,17,18,19,
20.25,30,35,40,45,50,55,60,65,70,75,80,85,90,95,100, or greater. Any particular sample of R [M -R] _n M ^to R ¹ , R ¹ [M ^b R ¹ -R ² -] nM ^b (R ¹ ) 2 is expected to contain mixtures or mixtures of different species, having a range of N values.
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11/23
Formulas such as R ¹ [M ^A -R ² -] _N M ^A R ¹ ,
R ¹ [MBR ¹ -R ² B1] _n M (R) ₂ , as used in this disclosure, reflect a population of molecules, characterized by a range or distribution of N values. Hence, unless otherwise provided, the values of N they are presented as mean values for the mixture of species in a particular sample, as evidenced by the ratio of R to R plots that can be determined, for example, by H ¹ NMR.
[0047] Additional examples of the chain transfer agents of this disclosure include compounds of the formulas X [ZnR ² ] xZnX or X [AlX (R ² )] yAlX2, where R ² is an alkali portion such as CH2CH2, and where x and y are numbers integers greater than 1 and where X is selected independently of CH3, CH2CH2,
CH2CH2CH3, CH2CH2CH2CH3, CH (CH3) 2, CH2CH (CH3) 2, C6H5, C6H4CH3, Cl, Br, I, OCH3, OCH2CH2, OC6H5, OCH2CH2CH3, OCH (CH3) 2, OC6H5, OC6H4CH3, OC6H3 OC6H3 (CH3) 3, SCH3, SCH2CH2, SC6H5, NH2, NHCH3, NHCH2CH3, NHCH2CH2CH3, NHCH (CH3) 2, NHC6H5 NHC6H4CH3, N (CH3) 2, N (CH2 (CH2CH2) 2, Si (CH3) 3, Si (CH2CH3) 3, and the like Monomers [0048] Monomers suitable for use in the preparation of the copolymers of the present disclosure include any polymerisable monomer by addition, generally any olefin or diolefin monomer. Suitable monomers may be linear, branched, acyclic, cyclic, substituted, or unsubstituted In one aspect, the olefin can be any α-olefin, including, for example, ethylene and at least one different copolymerizable comonomer, propylene and at least one different copolymerizable comonomer having 4 to 20 carbons, or 4 -methyl-1-pentene and at least one different copolymerizable comonomer, ranging from 4 to 20
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24/119 carbons. Examples of suitable monomers include, but are not limited to, α-olefins having 2 to 30 carbon atoms, 2 to 20 carbon atoms, or 2 to 12 carbon atoms. Specific examples of suitable monomers include, but are not limited to, ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1- octene, 1-decene, 1-dodecene, 1tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. Monomers suitable for use in the preparation of the copolymers disclosed herein also include cycloolefins having 3 to 30, 3 to 20 carbon atoms, or 3 to 12 carbon atoms. Examples of cycloolefins that may be used include, but are not limited to, cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclodecene, and 2methyl-1,4,5,8-dimethane-1,2,3, 4.4a, 5.8.8a-octahydronaphthalene. Suitable monomers to prepare the copolymers disclosed here also include di- and poly-olefins having from 3 to 30, from 3
to 20 atoms in carbon, or 3 to 12 atoms of carbon. Examples in di- and poly-olefins what may be used include, but no are limited to , butadiene, isoprene, 4-
methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5hexadiene, 1,4-hexadiene, 1,3-hexadiene, 1,3-octadiene, 1,4octadiene, 1,5- octadiene, 1,6-octadiene, 1,7-octadiene, ethylidene norbornene, vinyl norbornene, dicyclopentadiene, 7methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, and 5,9-dimethyl -1,4,8-decathriene. In a further aspect, aromatic vinyl compounds also constitute suitable monomers to prepare the copolymers disclosed herein, examples of which include, but are not limited to, mono or polyalkyl styrenes, (including styrene,
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25/119 methylstyrene, and p-methylstyrene, o, p-dimethylstyrene, oethylstyrene, m-ethyl styrene and p-ethyl styrene), and derivatives containing functional groups, such as methoxy styrene, ethoxy styrene, vinylbenzoic acid, methyl vinylbenzoate, vinyl benzene acetate, vinyl benzene acetate hydroxystyrene, o-chloro-styrene, p-chloro-styrene, divinylbenzene,
3-phenylpropene,
4phenylpropene, and α-methylstyrene, vinyl chloride,
1,2difluorethylene,
1,2-dichlorethylene, tetrafluoroethylene, and
3,3,3-trifluor-1-propene, with the exception that the monomer is polymerizable under the conditions employed.
[0049] In addition, in one aspect, monomers or mixtures of monomers suitable for use in combination with at least one double-stranded and multi-headed transfer agent disclosed herein include ethylene; propylene; ethylene mixtures; with one or more monomers selected from propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, and styrene; and mixtures of ethylene, propylene and a conjugated or unconjugated diene. In this regard, the copolymer or interpolymer may contain two or more intramolecular regions comprising differentiated chemical properties, especially regions of differentiated comonomer incorporation, assembled in a dimeric, linear, branched or poly-branched polymer structure. Such polymers may be prepared by alternating the polymerization conditions during a polymerization that includes a double-headed or multiple-headed chain transfer agent, for example, using two reactors with differentiated comonomer ratios, multiple catalysts with differentiated comonomer incorporation skills, or a combination of such process conditions, and optionally
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26/119 a polyfunctional coupling agent.
[0050] In one aspect of this polymerization system, while attached to the growing polymer chain, the chain transfer agent desirably does not alter the polymer structure or incorporate additional monomer. That is, the chain transfer agent typically also lacks significant catalytic properties for polymerization. Conversely, the chain transfer agent may form a metal-alkyl or other interaction with the polymer portion until the polymer portion is transferred again to an active polymerization catalyst site. The transfer of the same chain transfer agent site back to the original catalyst merely results in an increase in at least the polymer. In contrast, transferring to a different catalyst, if more than one type of catalyst is employed, results in the formation of a distinguishable type of polymer, due, for example, to a difference in monomer incorporation properties, tactility, or other property of the subsequent catalyst. Transferring through one of the remaining chain transfer agent sites results in growth from a different point on the polymer molecule. With a double-headed or multiple-headed chain transfer agent, at least some of the resulting polymer has at least twice the molecular weight of the remaining polymer segments. Under certain circumstances, the subsequently bonded polymer region also has a distinguishable physical or chemical property, such as a different monomer or comonomer identity, a difference in comonomer composition distribution, crystallinity,
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27/119 density, tacticity, regius-error, or other property, compared to the polymer formed at other times during polymerization. Subsequent repetitions of the above process may result in the formation of segments or blocks having a multiplicity of differentiated properties, or a repetition of a previously formed polymer composition, depending on the rates of polymer change, the number of reactors or zones within a reactor, the transport characteristics between the reactors or zones, the number of different catalysts, the monomer gradient
we) reactor (s), and so per against.[0051] The transfer of growing polymer may occur multiple times with continuous growth on one
polymer segment each time it is connected to an active catalyst. Under uniform polymerization conditions, the growing polymer blocks may be substantially homogeneous, although their size conforms to the distribution sizes, for example, a more likely size distribution. Under different polymerization conditions, such as in the presence of different monomers or monomer gradients, in a reactor, multiple reactors operating under different process conditions, and so on, the respective polymer segments can also be distinguished based on differences in chemical or physical properties. The chain transfer and additional growth may continue as described for any numbers or cycles.
CSAs and their Preparation [0052] Examples of some chain transfer agents and their Newkome nomenclature are provided in table 1 below.
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11/28
These examples include general and core linker groups of the general type R ⁿ , where n is the valence of the particular group, examples of which include alkyl (R), alkadiyl (R), and alkatetrayl (R ⁴ ), although R ¹ - R ⁴ are not strictly limited to hydrocarbyl-like plots, for example, alkyl, halide, and alkoxy constitute R ¹ plots. As used throughout the text, the terms alkadyl or alkanodiyl can also be used to refer to a divalent alkadyl (R) portion ₂ , just as alcatriyl or alkanotriyl can be used to refer to a trivalent alkaline (R ³ ) portion, and alkatetrayl or alkanotetrayl may be used to refer to tetravalent alkatetraalkyl (R ⁴ ) plots, respectively. The CSA structures in Table 1 are not intended to be limiting, but illustrations of average stoichiometries or empirical formulas, as provided here.
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11/29
Table 1. Examples of Chain Transfer Agents and their
Newkome nomenclature,
G [C] [(R) Nb (Z)] NC
Chain Transfer Agent G [C] [(R) N _b (Z)] Nc - Zru R ³ H ^to / / Zn zn Zn ^Zn . / / / / T # ^R3 | _E / ^Zn f ⁿ z / zn Zn ^Et E / Et Et | Zn] [(R ³ Zn ₂ ) ^ (Et) | ₂ _ ^. R ³ Et- ^ Zn — R ³ -Zn / ^ zn to ³ ^ Zn / | Et Et 7n '/ Et Et | R ³ Zn ₃ ] KR-Znj. · (Ι · 1) | ₅ El · —r '' o ⁴ > - ^Zi1 Et ^- —Zn —— R ⁴ / / --Zn- Et / / Zn 7n Zn ^Η Ά / ηΑί ⁴ « ⁴ & / 'Í ^H z / l Z / / | / l n / AAa A ^z ' / 1 IN / I , Et nl.FtV, 1 l. ^H Fi IZnlKRVn,) (Et) b.| Zn | ((J 1 ₇ (J EZn)] ² (1 ^) 12 'ΆιΓ' '' ”zíA | Zn (CII _. ) Zn | [(Cn C) l./n: íl .i: | , „_. ·. - Δ L EUAI — R ² -AI R f Ff Ο _Λ | -Ά> AlEtp ^{Εΐί> ΑΙ R} ΔΙΓΙ / Albtp Et ^ AI | A1) [(R A1) ₂ (lil.) | ₃
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11/30
í í < | Λ11. · 1] | ((ΊΙ, (ΊΙ ₂ Λ111) ((] 't) | ₂ j _h << 11 ÍIAI (CI rgjAU -.t | | (CI Ι / Ί Ι, ΛΙΙ y) '· (I · 1) 1 ₂
[0053] An additional aspect of this disclosure provides for chain transfer agents that are not readily described by the Newkome nomenclature, as far as they are not formally dendritic species. Specifically,
M ^C [R ² ] ₂ M ^C , where M ^c is Mg, reagents from group 12 from group 13 MB [R ² ] ₃ MB, where
MB is B, Al, or Ga, chain transfer which are useful in and the reagents are disclosed polymerization agents, but are not classic dendrimers. Examples of these species include the following compounds:
similar.
The structures are representative of the polymeric species that make up the CSA compositions of this stoichiometry. Hence,
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11/31 chain transfer included in this disclosure include those with the formula:
R ¹ [MA-R ² -] _N MAR ¹ , where MA is Zn or Mg;
R ¹ [MBR ¹ -R ² -] nMB (R ¹ ) 2, where MB is B, Al, or Ga;
M ^C [R ² ] ₂ M ^C , where M ^C is Mg;
M ^B [R ² ] 3M ^B , where M ^B is B, Al, or Ga;
or an aggregate of these, a derivative of these containing Lewis base, or any combination thereof; Where
R ¹ in each occurrence is independently selected from hydrogen, halide, amide, hydrocarbyl, hydrocarbilamide, dihydrocarbilamide, hydrocarbyl oxide, hydrocarbyl sulfide, dihdrocarbyl phosphide, tri (hydrocarbil) silyl; any hydrocarbyl group being optionally substituted with at least one halide, amide, hydrocarbilamide, dihydrocarbilamide, or hydrocarbyl oxide; and each R ¹ containing carbon having from 1 to 20 carbon atoms, inclusive;
₂
R in each occurrence is independently selected from (CH2) m, O [CH2) nCH2CH2] 2, S [(CH2) nCH2CH2] 2, RAN [(CH2) nCH2CH2] 2, (R ^B ) 2Si [(CH2) nCH2CH2] 2, (R ^B ) 3SiOSiR ^B [(CH2) nCH2CH2] 2, or [Si (R ^B ) 2 (CH2) nCH2CH2] 2O;
where n in each occurrence is independently an integer from 1 to 20, inclusive; n is an integer from 2 to 20, inclusive; R ^A is H or a hydrocarbyl having from 1 to 12 carbon atoms, inclusive; and R ^B at each occurrence is a hydrocarbyl having 1 to 12 carbon atoms, inclusive; and N, on average, in each occurrence is a number from 2 to 150, inclusive.
₂
R in each occurrence is independently selected from (CH2) m, O [CH2) nCH2CH2] 2, S [(CH2) nCH2CH2] 2, R ^A N [(CH2) nCH2CH2] 2,
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32/119 (R ^B ) 2Si [(CH2) nCH2CH2] 2, (RBkSiOSiRBHCkínCkCkL ·, or [Sl (R ^B ) 2 (CH2) nCH2CH212O;
where n in each occurrence is independently an integer from 1 to 20, inclusive; n is an integer from 2 to 20, inclusive; RA is H or a hydrocarbyl having from 1 to 12 carbon atoms, inclusive; and R ^B at each occurrence is a hydrocarbyl having 1 to 12 carbon atoms, inclusive; and N, on average, in each occurrence is a number from 2 to 150, inclusive.
[0054] An additional aspect of the chain transfer agents of this disclosure considering the parameter Q, as defined above. When CSAs are used that have the ratio of multiple head site valences to single head site valences, Q, for values greater than one (Q> 1), then co-polymers or interpolymers can be prepared having more polymer properties desirable, such as a narrower molecular weight distribution compared to polymers resulting from chain transfer agents. Therefore, one aspect of this disclosure is the use of chain transfer agents with 2 or more metal atoms per CSA molecule having at least two reactive fragments with a valence of two or more, such as R2, R3, R4, and so on . Compositions, reagents, and methods that involve or comprise any aspect of chain transfer agents with Q> 1 are also included in this disclosure.
As used here, the definition of Q is not limited to R ¹ alkyl groups, but includes any of hydrogen, halide, amide, hydrocarbyl, hydrocarbilamide, hydrocarbyl oxide, and the like, each of which comprises a valence of
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33/119 single head site.
[0055] As an example, the following table includes a variety of double-headed and multiple-headed CSAs that are encompassed by this disclosure and are useful in polymerization chemistry here.
Table 2. Examples of Useful Chain Transfer Agents
Included in this Disclosure
CSA R3 R2 R1 Q (> 1) REfZn-R ^ lM ^ Zn-R ¹ 0 2N 2 N (> 1) R ¹ / Zn / R <-Zn “R ² -Zn-R ^s Zn V 3 2 3 5/3 R ¹ R ¹ / Zn Zn R'-Zn-R 'Zn Zn / R ¹ R ¹ 6 0 4 3/2 R ¹ R ⁽ / Zn Zn R ³ -Zn-R · '/ Zn Zn / R' Zn 'r- 6 2 4 2 AA Mg ^ Mg R ² 0 4 0 4/0 = “ ^ R ² Al> AI R ² 0 6 0 6/0 = “
[0056] While the CSAs in this disclosure typically have
Q> 1, a type of CSA that is included here has such a low Q
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34/119 and 4/5. Specifically, this exceptional CSA is the chain transfer agent of the linear group 13 (B, Al, Ga) having the formula R ¹ [M ^B R ¹ -R ² ] N> 1M ^B R ¹ 2, where MB is B, Al, or Ga. Referring to the disclosure CSAs as having Q> 1, it is intended to include this exception in the CSAs of group 13 of the form R ¹ [M ^B R ¹ -R ² ] N> 1M ^B R ¹ 2 that have a Q as low as 4 / 5. When these CSAs are linear reagents rather than branched reagents, _z 1 B 1
Useful CSAs in this disclosure include those R [MRR ² ] N> 1M ^B R ¹ 2 compounds having at least three atoms of group 13, that is,
R ¹ [M ^B R ¹ -R ² ] 2M ^B R ¹ 2.
[0057]
R ¹ [M ^B R ¹ -R ² ] 3M ^B R ¹ 2,
R ¹ [MBR ¹ -R ² ] 4MBR ¹ 2 and greater, despite the smaller molecule having N = 2, provide a calculated Q of less than 1. However, all linear group 13 reagents are included here, as long as N> 1. To illustrate group 13 CSAs in the form R ¹ [M ^B R ¹ -R ² ] N> 1M ^B R ¹ 2, and their Q values calculated, in the CSA R ¹ [M ^B R ¹ -R ² ] N> 1M ^B R ¹ 2, the value of R2 is 2N, and the value of R1 is 3 + N. Hence, when N is 2, for the smallest CSA of this formula with N> 1, then Q (= R2 / R1) is 4/5. Larger CSAs in this formula have calculated Q values>1; for example, when N = 3, Q = 8/7, and when N = 4, Q = 10/8.
[0058] An additional aspect of this disclosure provides for a catalyst composition comprising the contact product of at least one polymerization, at least one chain transfer agent R ¹ [M ^B R ¹ -R ² -] NM ^B (R ¹ ) 2, M ^C [R ² ] ₂ M ^C , precursor to cocatalyst catalyst, and at least one having the formula R ¹ [M ^A -R ² -] NM ^A R ¹ , or M ^B [R ² ] 3M ^B , or an aggregate of these, a derivative containing Lewis base of these, or any combination of these, where each variable M ^A , M ^B , M ^C , R ¹ , ₂
R, and N are defined here.
[0059] Considering the general formulas of the agents of
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35/119 transfer of chain R ¹ [M ^to -R ² -] _n M ^to R ¹ ,
R ¹ [MBR ¹ -R ² -] nMB (R ¹ ) 2,
M ^c [R ² ] 2M ^c , or M ^b [R ² ] 3MB, certain selections of R ¹ , R ² and N may be particularly useful. In this regard, for example, N values may be
2,3,4,5,6,7,8,9,10,11,12,13,
14,15,16,17,18,19, or values of about 20, 25, 30, 35, 40,
45, 50, 55, 60, 65, 70,
75, 80,
85, 90, 95, 100, 110, 120,
130, 140, or 150, or even greater, including any range or set of ranges between any of these values. It is expected that any particular sample of
R ¹ [M ^to -R ² -] _n M ^to R ¹ and R ¹ [M ^b R ¹ -R ² B1] _n M (R) ₂ contains a mixture of different species having different N values, hence any sample given of these
CSAs will be characterized by having a range of values
Formulas such as
R ¹ [MA-R ² -] _n MAR ¹
R ¹ [MBR ¹ -R ² -] nMB (R ¹ ) 2 as used in this disclosure are intended to reflect a population of molecules, characterized by a range of N value distribution.
Hence, unless otherwise stated, values of
N are given as mean values for the species mix in a particular sample, as
1 evidenced by the ratio of R to R plots that can, for example, be determined by H ¹ NMR. Within the general CSA formulas provided here, any number of useful R plots may be used. As used here, _z
R is any portion with two site valences, which does not prevent the formation and chain transfer activity of the chain transfer agent that contains the specific R.
✓ z
Desirably, the specific R does not contain a reactive functional group or reactive moiety that reacts substantially adversely with or interferes with a borohydride or alkylzinc reagent. The typical example _z of an R is a hydrocarbadiyl, such as alkadyl. For example, as
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36/119 illustrated in the diagrams and examples, R ² may be derived from a species containing α, ω-diene, including α, ω-dienes (also referred to as α, ω-diolefins) and, hence, R ² may be defined according to the precursor containing α, ω-diene used in the preparation. As used here, the term α, ω-diene is used interchangeably with molecules or species containing α, ωdiene to refer to any compound that contains at least two terminal olefin (-CH = CH ₂ ) portions, and is not intended for limiting strictly hydrocarbon species. The synthetic method for preparing the double-headed zinc reagents described in the examples is generally applicable to the synthesis of any chain transfer agent derived from any species containing α, ω-diene, or any molecule containing multiple olefin groups. These precursors are selected in such a way that the diene does not contain a reactive functional group that can react adversely or interfere with a borohydride or alkylzinc reagent. In appropriate cases, molecules containing multiple olefin groups and functional groups that have been adequately protected, as understood by those skilled in the art, may be used if it interferes with a borohydride reagent or alkylzinc reagent. Generally, suitable R ² groups may have 2 to 40 carbon atoms, inclusive. R ² groups can have up to 2 to 25 carbon atoms, 2 to 15 carbon atoms, or 2 to 12 carbon atoms.
[0060] Examples of suitable α, ω-diene-containing species include hydrocarbyl α, ω-dienes, hydrocarbyl α, functionalized ω-dienes, and other compounds containing α, ω-diene, such as 1,3-di (O) - alkenyl) tetramethyldisiloxanes, and di (O) Petition 870190033519, of 8/8/2019, p. 49/135
37/119 _ζ 2 alkenyl) ethers. The corresponding R plots that arise from the use of these compounds containing α, ω-diene include the corresponding alkali-like portion arising from the addition to the specific α, ω-diene compounds noted; however, this disclosure comprises _two such portions corresponding R, regardless of the particular synthetic method by which the linker R ₂ can be prepared.
[0061] Hydrocarbyl α, ω-dienes suitable as referred to here include α, ω-dienes having the formula CH ₂ = CH (CH + 2) _n CH ₂ , where n is an integer from 0 to 20, preferably n is an integer 1 to 20, including cyclic and bicyclic analogues thereof. Examples of such hydrocarbons α, ω-dienes include, but are not limited to, 1,3-butadiene, 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8 nonadiene, 1 , 9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene, 1,13-tetradecadiene, vinyl norbornene, norbornadiene, dicyclopentadiene, cyclooctadiene, vinyl cyclohexene, and the like; typically containing 5 to 40 carbon atoms. Consequently, the corresponding alkaliyl portion arising from the use of these precursors containing α, ωdiene includes the corresponding alkaliyl portion arising from the addition to the named diene, having the formula [-CH2CH2 (CH2) NCH2CH2-] where n and an integer from 1 to 20. For For example, the ₂ R plots that are derived from the dienes listed above could include 1,5-pentadiene (arising from 1,4-pentadiene) 1,6-hexadiene (arising from 1,5-hexadiene), 1,7-heptadiyl ( arising from 1,6-heptadiene), and so on. While the ethanediyl (or etadiyl) (C2) and 1,3-propadyl (C3) ligands are also useful in the chain transfer agents of this disclosure, CSAs containing these molecules are typically
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38/119 prepared by a different route from the scheme 3 method, as described in the examples section of the present disclosure, which is useful for these longer α, ω-diene precursors. Ethanediyl could be prepared by a known procedure (Eisch, JJ; Kotowicz, HWJ Inorg. Chem. 1998, 761-769). C3 ligands are prepared by a known route (Bhanu Prasad, AS; Eick, H .; Knochel, PJ Organomet. Chem. 1998, 562, 133-139). In addition, 1,4-butadryl (C ₄ ) CSA binders are generally prepared in a similar manner to that of propanodiyl.
[0062] α, ω-functionalized hydrocarbyl dienes as referred to herein include α, ω-dienes that are substituted with heteroatom by at least one atom of O, S, N, or Si, or a combination of atoms. Specific examples of α, ω-functionalized hydrocarbyl dienes include, but are not limited to, O [(CH2) nCH = CH2] 2, S [(CH2) nCH = CH2] 2, RAN [(CH2) nCH = CH2] 2, (RB) 2Si [(CH2) nCH = CH2] 2, (RB) 3SiOSiRB [(CH2) nCH = CH2] 2, and
[Si (RB) 2 (CH2) nCH = CH2] 2O; Where n in each occurrence is regardless a number all from 0 to 20 inclusive preferably 1 to 20 inclusive; FROG is H or a hydrocarbyl
having from 1 to 12 carbon atoms, inclusive; and R ^B at each occurrence is independently an integer from 0 to 20, inclusive, preferably 1 to 20 inclusive; R ^A is hydrogen or hydrocarbyl having 1 to 12 carbon atoms, inclusive, R ^B in each occurrence is independently a hydrocarbyl having 1 to 12 carbon atoms, inclusive. Consequently, the ₂ R plots that arise from the use of these compounds containing α, ωdieno include the corresponding alkali-like portion arising from the addition of the specific α, ω-diene compounds noted, and this disclosure encompasses such plots
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39/119 ''
R, regardless of any particular synthetic method ₂ by which they are prepared. For example, the R plots that are derived from O [(CH ₂ ) _n CH = CH ₂ ] ₂ and their corresponding O [(CH2) nCH2CH2-] 2 plots are included.
[0063] Examples of α, ω-functionalized hydrocarbons include, but are not limited to, divinyl ether, di (2-propenyl) ether, di (3-butenyl) ether, di (4 pentenyl) ether, ether di (5-hexenyl), divinyl amine ether, di (2-propenyl) amine ether, di (3-butenyl) amine ether, di (4-pentenyl) amine ether, divinyl methylamine, di (3 -butenyl) methylamine, di (5-hexenyl) methylamine ether, di (2-propenyl) methylamine ether, di (4-pentenyl) methylamine ether, di (5-hexenyl) methylamine ether, thioether divinyl, di (2-propenyl) thioether, di (3-butenyl) thioether, di (4-pentenyl) thioether di (5-hexenyl) thioether, divinyl dimethylsilane, di (2-propenyl) dimethylsilane, di ( 3-butenyl) dimethylsilane, di (4-pentenyl) dimethylsilane, di (5-hexenyl) dimethylsilane, similar, typically containing from 4 to 40 carbon atoms.
[0064] Additional examples of suitable functionalized αω-dienes include, but are not limited to, disiloxane compounds, such as the divinyl tetramethyldisiloxane isomers 1,1- and 1,3- (also referred to herein as di (ethane-1, 2 diyl) tetramethyldisiloxane), di (2-propenyl) tetramethyldisiloxane, di (3-butenyl) tetramethyldisiloxane, di (4-pentenyl) tetramethyldisiloxane, di (5-hexenyl) tetramethyldisiloxane, di (6-heptenyl), di (6-heptenyl) 7-octenyl) tetramethyldisiloxane, di (8-nonenyl) tetramethyldisiloxane, di (9-decenyl) tetramethyldisiloxan-di, di (2-propenyl) tetraethyldisiloxane, di (3Petition 870190033519, from 4/8/2019, page 52/135
40/119 butenyl) tetramethyldisiloxane / di (4-pentenyl) tetraethyldisiloxane / di (5-hexenyl) tetramethyldisiloxane, di (6heptenyl) tetraethyldisiloxane / di (7-octenyl) tetraethyldisiloxane, di (8-nonenyl) tetraethyldethyldetylethylethyldetylethylethyldetyl) tetraethyl , and the like. The respective R plots that could arise from these precursors are the isomers 1 / 1- and 1,3- of di (ethan-1,2diyl) tetramethyldisiloxane / di (propan-1/3-diyl) tetramethyldisiloxane / di (butan-1 / 4-diyl) tetramethyldisiloxane / di (pentan-1,5-diyl) tetramethyldisiloxane / di (hexan-1,6diyl) tetramethyldisiloxane / di (heptan-1/7-diyl) tetramethyldisiloxane / di (octan-1/8-diyl) tetramethyldisiloxane / di (nonan-1/9-diyl) tetramethyldisiloxane / di (decan-1 / 10diyl) tetramethyldisiloxane / di (ethan-1/2-diyl) tetraethyldisiloxane / di (propan-1/3-diyl) tetraethyldisiloxane / di ( butan-1/4-diyl) tetraethyldisiloxane / di (pentan-1 / 5diyl) tetraethyldisiloxane / di (hexan-1/6-diyl) tetraethyldisiloxane / di (heptan-1/7-diyl) tetraethyldisiloxane / di (octan-1 / 8-diyl) tetraethyldisiloxane / di (nonan-1 / 9diyl) tetraethyldisiloxane / di (decan-1/10-diyl) tetraethyldisiloxane. Generally / the R ² type portions of 1 / 1- and 1 / 3di (ao-alkenyl) tetraalkyldisiloxane may have 8 to 40 carbon atoms / including / or 8 to 30 carbon atoms / or 8 to 20 atoms of carbon.
[0065] In this aspect / it is noted that asymmetric awdiene-containing molecules may be employed / examples of which include (3-butenyl) (5-hexenyl) / (2-propenyl) (4-pentenyl) ethylamine / ether and so on. These αω-diene hydrocarbon precursors also give rise to the corresponding alkali-like portion arising from the addition to the named diene.
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For example, the di (3-butenyl) ether could form the corresponding _z 2 di (butadlyl) ether of R illustrated below.
[0066]
here they provide the corresponding alkali-like plot, for example, the corresponding
1,3-dialcadiiltetraalkylsiloxane than the 1,3-di (ω-alkenyl) tetraalkylsilyoxane employed.
[0067]
This disclosure also provides for methods for making the new chain transfer agents. For example, a process is provided for preparing a chain transfer agent having the formula:
R ¹ [MA-R ² -] _n MAR ¹ , where MA is Zn or Mg;
R ¹ [MBR ¹ -R ² -] nMB (R ¹ ) 2, where MB is B, Al, or Ga;
or an aggregate of these, a derivative of these containing base
Lewis, or any combination thereof;
the process comprising:
provide an αω-diene having the formula CH ₂ = CH (CH ₂ ) n _N CH = CH ₂ , O [(CH3) nCH = CH2] 2, S [(CH2) nCH = CH2] 2, RAN [(CH2) nCH = CH2] 2, (R ^B ) 2Si [(CH2) nCH = CH2] 2, (R ^B ) 3SiOSiR ^B [(CH2) nCH = CH2] 2, or [Si (R ^B ) 2 (CH2) nCH = CH2] 2O; where n in each occurrence is independently an integer from 0 to 20, inclusive, R ^A is H or a hydrocarbyl having from 1 to 12 carbon atoms, inclusive; and R ^B at each occurrence is independently an integer from 1 to 12 carbon atoms, inclusive;
contact αω-diene with a borohydride compound having the
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42/119 formula (R ^C ) 2BH, where R ^C is a hydrocarbyl having from 1 to 20 carbon atoms, to form a first composition; and contacting the first composition with MA (R ^1A ) (R ¹ ) or M ^B (R ^1A ) (R ¹ ) 2 to form a second composition comprising the chain transfer agent;
where R ^1A at each occurrence is independently selected from hydrogen or a hydrocarbyl having from 1 to 20 carbon atoms, optionally substituted with at least one halide, amide, hydrocarbilamide, dihydrocarbilamide, or hydrocarbyl oxide;
R ¹ in each occurrence is independently selected from hydrogen, halide, amide, hydrocarbyl, hydrocarbilamide, dihydrocarbilamide, hydrocarbyl oxide, hydrocarbyl sulfide, dihydrocarbyl phosphide, tri (hydrocarbil) silyl; any hydrocarbyl group being optionally substituted with at least one halide, amide, hydrocarbilamide, dihydrocarbilamide, or hydrocarbyl oxide; and each R ¹ containing carbon having from 1 to 20 carbon atoms, inclusive;
₂
R in each occurrence is independently selected from (CH2) m, O [CH2) nCH2CH2] 2, S [(CH2) nCH2CH2] 2, RAN [(CH2) nCH2CH2] 2, (R ^B ) 2Si [(CH2) nCH2CH2] 2, (R ^B ) 3SiOSiR ^B [(CH2) nCH2CH2] 2, or [Si (R ^B ) 2 (CH2) nCH2CH2] 2O;
where n in each occurrence is independently an integer from 1 to 20, inclusive; m is an integer from 2 to 20, inclusive; R ^A is H or a hydrocarbyl having from 1 to 12 carbon atoms, inclusive; and R ^B at each occurrence is a hydrocarbyl having 1 to 12 carbon atoms, inclusive; and N, on average, in each occurrence is a number from 2 to 150, inclusive.
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43/119 [0068] The average value of N can be controlled by adjusting the relative amount of MA (R ^1A ) (R ¹ ) or MB (R ^1A ) (R ¹ ) 2 relative to the calculated amount of αω-diene or ( R ^C ) 2BH in the second composition.
[0069] Similarly, a process is also provided for preparing a chain transfer agent having the formula:
R ¹ [M ^to -R ² -] _n M ^to R ¹ , where MA is Zn or Mg; R ¹ [M ^B R ¹ -R ² -] NM ^B (R ¹ ) 2, where M ^B is B, Al, or Ga; or one aggregate of these, a derivative of these containing basis of Lewis, or any combination of these; O process
comprising contacting the CSAs of the formula: R ^1A [M ^A -R ² ] NM ^A R ^1A or R ^1A [M ^B -R ² ] NM ^B (R ^1A ) ₂ , where
R ^1A at each occurrence is independently selected from hydrogen or a hydrocarbyl having from 1 to 20 carbon atoms, including, optionally substituted with at least one halide, amide, hydrocarbilamide, dihydrocarbilamide, or 1B 1B A 2 hydrocarbyl oxide; and with HR to provide an R [M -R] _N M ^A R ^1B or R ^1B [M ^B -R ^1B -] _N M ^B (R ^1B );
Where
1B
R at each occurrence is independently selected from halide, amide, hydrocarbilamide, dihydrocarbilamide, hydrocarbyl oxide, hydrocarbyl sulfide, dihydrocarbyl phosphide, tri (hydrocarbil) silyl; any hydrocarbyl group being optionally substituted with at least one halide, amide, hydrocarbilamide, dihydrocarbilamide, or hydrocarbyl oxide; and each R ^1B containing carbon having from 1 to 20 carbon atoms, inclusive.
[0070] In this embodiment, R ² and N are provided above CSAs R ¹ [M ^A -R ² -] NM ^A R ¹ and R ¹ [M ^B -R ¹ -R ² -] NM ^B (R ¹ ) ₂ . The average value of N
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44/119 can also be controlled here by adjusting the relative amount of MA (R ^1A ) 2 or MB (R ^1A ) relative to the calculated amount of (RC) 2BH αω-diene in the second composition.
[0071] Mc [R ² ] Mc chain transfer agents, where MC is Mg and M ^b [R ² ] ₃ MB, where MB is B, Al, or Ga, can be prepared by providing an αω-diene with a composition that serves as a precursor to M ^C H2 or M ^B H3, an example of which is triisobutyl aluminum hydride or diisobutyl aluminum.
[0072] As illustrated in the examples, other methods for preparing CSAs are provided. For example, R ¹ [M ^A R ² -] NM ^A R ¹ , where M ^A is Zn or Mg, can be prepared by reacting a chain transfer agent of the formula M ^A [R ² ] 2M ^A with a reagent having the formula R ¹ [M ^A -R ² ] M ^A R ¹ .
This is the R ¹ [M ^A -R ² ] M ^A R ¹ is a double-headed CSA similar to those of the formula R ¹ [M ^to R ² ] NM ^A R ¹ provided here, except where the value of N is 1. Similarly, chain transfer agents having the formula R ¹ [M ^B R ¹ -R ² -] NM ^B (R ¹ ) 2, where M ^B is B, Al, or Ga, a transfer agent of chain having the formula M ^B [R ² ] 3M ^B with a reagent having the formula R ¹ [M ^B R ¹ -R ² -] M ^B (R ¹ ) 2, where R ¹ [M ^B R ¹ -R ² - ] M ^B (R ¹ ) ₂ is also similar to those of R ¹ [M ^B R ¹ 2 B 1
R -] _n M (R) ₂ disclosed here, except for the value of N equal to
1.
[0073] Methods for preparing a chain transfer agent represented by the following Newkome dendrimer nomenclature
G [c] [(R) Nb (Z)] NC, is also provided. For example, in one aspect, dendrimer CSAs may be prepared as follows, as shown in schemes 8 and 9.
[0074] Provide a polyene having the formula R ^A C [(CH ₂ ) _n CH = CH ₂ ] ₃
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45/119 or C [(CH ₂ ) _n CH = CH ₂ ] ₄ , where n in each occurrence is independently an integer from 0 to 2 0 and RA is H or a hydrocarbyl having from 1 to 12 carbon atoms, inclusive ; and [0075] contacting the polyene with a borohydride having the formula (R ^C ) ₂ BH, where R ^C is a hydrocarbyl having from 1 to 20 carbon atoms, to form a first composition comprising a partially hydrophobic polyene;
[0076] contacting the first composition with MA (R ^1A ) 2 or M ^b (R ^1a ) 3 to form a second composition comprising M ^A {CH2CH2 (CH2) nE [(CH2) nCH = CH2] m-1} 2 or
M ^B {CH2CH2 (CH2) nE [(CH2) nCH = CH2] m-1} 3, where R ^1A in each occurrence is independently a hydrocarbyl having from 1 to 20 carbon atoms, inclusive, optionally substituted with at least one halide , amide, hydrocarbilamide, dihydrocarbilamide, or hydrocarbyl oxide;
contacting the second composition with (R ^C ) 2BH, followed by contacting the resulting composition with M ^A (R ^1A ) 2 or M ^B (R ^1A ) 3 to form a third composition;
contacting the third composition with the partially hydrophobic polyene prepared according to step b); and repeating steps d) and e) any number of times to form the dendrimeric chain transfer agent.
[0077] In one aspect, the block copolymers provided by the methods and CSAs of this disclosure may be characterized by relatively narrow molecular weight distributions. For example, polymers having a narrow molecular weight distribution typically have a
index of polydispersity (PDI = Mw / Mn) of 1.0 The 4.0, more usually from 1.05 to 3.5, or 1.1 to 2.5. In contrast, polymers generally considered to be by having one PDI broad
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46/119 include those with POIs from 4.0 to 20 or from 4.0 to 10.
[0078] In one aspect, this disclosure encompasses double-headed chain transfer agents having the formulas
R ¹ [MA-R ² -] nMAR ¹ , R ¹ [MBR ¹ -R ² -] nMB (R ¹ ) 2, M ^c [R ² ] 2MC, or MB [R ² ]
2 ~
R and R are defined as disclosed here, and N occurrence may be an integer of 2
M ^B , Where in each The 150,
inclusive.
Therefore, examples of chain transfer agents encompassed by this disclosure include those with N> 1 in these formulas. The N values increase, the ratio (Q) of multiple-headed CSA sites (for example, alkali or ₂
R) for single-headed CSA sites (for example, alkyl or R ¹ ) also increases, and the properties of the resulting polymer composition may be altered, as provided in table 6. For example, it is shown that the polydispersity of the copolymers of Resulting ethylene prepared using increasingly long double-headed CSAs decreases as Q increases. Therefore, as the Q value increases, the overall molecular weight increases while the polydispersity decreases and approaches the values for the double-headed CSA, calculated to have a PDI of 1.5. The following structure illustrates the difference between a double-headed (D) CSA site that constitutes each zinc alkanodiyl bond and a single-headed (M) CSA site that constitutes each zinc alkyl bond. For form CSAs
R ¹ [M ^A -R ² -] _N M ^A R ¹ ,
R ¹ [M ^B R ¹ -R ² -] NM ^B (R ¹ ) 2,
M ^C [R ² ] ₂ M ^C , and MB [R ² ] ₃ MB, the multiple-headed CSA sites are all ₂ alkylidiyl or R sites, so Q is the ratio of double-headed (D) sites to sites single head (M).
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47/119
D D
R ^l - | Zn-R ² - | _N Zn-R 'tt
Μ M [0079] While not wishing to link to any theory, it is thought that the double-headed CSAs in this disclosure, for example, composed of the formulas R ¹ - [Zn-R ² -] NZn-R ¹ and R ¹ - [AlR ¹ R -] NAlR 2 where Q, the ratio of R sites (two per R) to sites (one per R ¹ ), is greater than 1, forming predominantly odd-numbered multi-block polymers. Again, while not binding to any theory, it is thought that this feature affects the polymer distribution in such a way that it is not multimodal, and that it will have a narrower molecular weight distribution than polymers using double-headed CSAs from formulas R ¹ [M ^A -R ² ] NM ^A R ¹ and R ¹ [M ^B -R ¹ -R ² ] NM ^B (R ¹ ) 2, where the ratio of R ² sites to R ¹ , Q sites is equal to 1.
[0080] As provided herein, double headed chain transfer agents of the formulas R ¹ [M ^A -R ² ] _N M ^A R ¹ and R ¹ [M ^B -R ¹ R ² ] NM ^B (R ¹ ) 2 are characterized by having values of N> 1. In one aspect, the rapid exchange at room temperature of zinc-hydrocarbyl groups between and across dihydrocarbyl zinc molecules can be used to adjust the value or range of N values in chain transfer agents when M is zinc. This quick and reversible equilibrium aspect is used as a synthetic advantage here, for example, as illustrated in scheme 1, where a solution of Et [ZnCH2CH2] 2ZnEt and ZnEt2. Similarly, scheme 2 illustrates how Et [ZnCH2CH2] 2ZnEt in solution can establish
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48/119 additional equilibria, for example, with another Et [ZnCH ₂ CH ₂ ] ₂ ZnEt to form Et [ZnCH ₂ CH ₂ ] ₂ ZnEt and ZnEt ₂ . These reactions are reversible; hence, the N value may be lowered by combining a known amount of ZnR ¹ , such as a dialkyl zinc, with a known amount of the double-headed CSA. Similarly, the value of N can be increased by dissolving the zinc double headed chain transfer agent in a solvent such as toluene and placing the solution under vacuum. In the latter case, the more volatile ZnR ¹ ₂ , for example, ZnEt ₂ , is removed by vacuum, shifting the balance from the lower N values towards higher N values.
[0081] The ratio of R ² to R ¹ plots can be measured by NMR spectroscopy of H and NMR of {H} C and used to determine the average value or range of N for
Et [ZnCH2CH2] 2ZnEt prepared in this way.
Layout 1
Layout 2
The double headed chain transfer agents [0082] of the formulas R ¹ [Zn-R ² -] NZnR ¹ , R ¹ [Mg-R ² -] NMgR ¹ , R ¹ [BR ¹ -R ² ] NB (R ¹ ) 2, R ¹ [AlR ¹ -R ² ] NAl (R ¹ ) 2, and R ¹ [GaR ¹ -R ² ] NGa (R ¹ ) 2, can be prepared according to examples 1 and 2. A selection of
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49/119 reagents allows adjustment of the approximate values of N in the formulas listed. For example, controlling the molar ratio of (R ¹ ) 2MA or (R ¹ ) 3MB to aw-Et ₂ B (CH ₂ ) _n BEt ₂ , in such a way that there is a less than 10-fold excess of any of the organometallic reagents (R ¹ ) 2M ^A or (R ¹ ) 3M ^B and less than a 10-fold excess of the reagent aw-Et2B (CH2) nBEt2 may provide the desired chain transfer agents having N values greater than 1. In another In this respect, control stoichiometry in such a way that there is a less than 5-fold excess of any of the organometallic reagents ((R ¹ ) 2M ^A or (R) 3M) and an excess of less than 5-fold aw-Et ₂ B ( CH ₂ ) _n BEt ₂ may provide double-headed CSAs (CD) with N values greater than 1. In addition, CD CSAs with N values greater than 1 may be prepared when the molar ratio of organometallic reagent ((R ¹ ) 2MA or (R ¹ ) 3M ^B ) for aw-Et ₂ B (CH ₂ ) _n BEt ₂ is from about 7: 1 to about 0.5: 1, from about 5: 1 to about 1: 1, or from about 4: 1 to about 2: 1.
[0083] The various stages of chain transfer and polymerization that may occur using such CSAs may be understood by reference to WO 2007/035493, which is incorporated herein in full by reference. Those skilled in the subject will understand that the various steps illustrated in WO 2007/035493 and as disclosed here may occur in any order. For example, by selecting different catalysts with respect to their ability or inability to incorporate comonomer, or otherwise produce distinguishable polymers, the polymer segments formed by the respective catalysts, will have different physical properties. In particular, in one embodiment, a block copolymer having at least one piece of an ethylene polymer
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50/119 or highly crystalline propylene characterized by little or no comonomer incorporation and at least one other block of an amorphous ethylene or propylene copolymer characterized by a greater amount of comonomer incorporation, can be readily prepared in this manner. One of skill in the art will appreciate that employing multiple catalysts, multiple monomers, multiple chain transfer agents (including both double and single head types), multiple reactors, or varying reactor conditions, a large number of product combinations of reaction is obtainable.
[0084] The polymer products provided here may be recovered by termination, such as by reaction with water or another source of protons, or functionalized, if desired, forming functional end groups vinyl, hydroxyl, silane, carboxylic acid, carboxylic acid ester , ionomeric, or other functional end groups, especially to replace the chain transfer agent. Alternatively, the polymer segments may be coupled with a polyfunctional coupling agent, especially a difunctional coupling agent, such as tolyl diisocyanate, dichlorodimethylsilane, or ethylene dichloride, and recovered.
[0085] Those skilled in the matter will readily appreciate that the above process may employ a multi-centered dendritic transfer agent initially containing 2,3,4 or even more active centers, resulting in the formation of polymer mixtures containing some amount of a polymer that approximately double, triple, quadruple, or other multiple of the molecular weight of the remaining polymer and one
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51/119 then star or branched morphology, before hydrolysis.
[0086] In one aspect of this disclosure, the chain transfer rate is equivalent to faster than the polymer termination rate, for example, up to 10 times faster, or up to 100 times faster or higher, than the rate of polymer termination. polymer termination and significant with respect to the polymerization rate. This allows the formation of significant amounts of polymer chains terminated with chain transfer agents and capable of continuous monomer insertion leading to significant amounts of polymer chains terminated with chain transfer agents and capable of insertion leading to significant amounts of the polymer higher molecular weight.
[0087] Selecting different agents or mixture of transfer agents with a catalyst, changing the composition of comonomer, temperature, pressure, optional chain transfer agent, such as H ₂ , or other reaction conditions in reactors or zones separated from one reactor operating in reactors or zones separate from a reactor operating under piston flow conditions, polymer products may be prepared having segments of density or comonomer concentration, monomer content, and / or other properties, varied. For example, in a typical process employing two continuous solution polymerization reactors connected in series and operating under differentiated polymerization conditions, the resulting polymer segments will each have a more likely molecular weight distribution characteristic than typical polymerization catalysts. of olefin coordination. Additionally, certain amounts of random copolymer
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Conventional 52/119 may also be formed coincidentally with the formation of the present polymer composition, resulting in a mixture of resins. If a relatively fast chain transfer agent is used, a copolymer having shorter block lengths but a more uniform composition with little random copolymer formation is obtained. By the proper selection of both catalyst and multi-centered transfer agent, relatively pure mixtures of two polymers differing in molecular weight from a value of approximately a whole number, copolymers containing relatively large polymer segments or blocks approaching true block copolymers, or mixing these with more random copolymers.
[0088] In a further aspect of this disclosure, single-headed chain transfer agents may be used in combination with double-headed or multiple-headed transfer agents disclosed here. In this regard, suitable single head chain transfer agents include metal compounds or metal complexes of Groups 1-13, preferably Groups 1, 2, 12 or 13 of the Periodic Table of Elements. While not limited by the size of the hydrocarbyl, suitable single-headed CSAs generally include hydrocarbyl-substituted aluminum, gallium or zinc compounds containing 1 to 30 carbon atoms or 1 to 12 carbon atoms in each hydrocarbyl group, and reaction products thereof with a proton source. Typical hydrocarbyl groups include straight or branched C2-8 alkyl groups. In one respect, the single-headed CSA includes compounds of trialkyl aluminum, dialkyl zinc, or
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53/119 combinations of these, examples of which include triethyl aluminum, tri (i-propyl) aluminum, tri (i-butyl) aluminum, tri (n-hexyl) aluminum, tri (n-otyl) aluminum, triethyl aluminum, or diethyl zinc. Additional suitable transfer agents include the reaction product or mixture formed by combining at least one of the above organometallic compounds, for example, a trialkyl (C _1-8 ) aluminum or dialkyl (C _1-8 ) zinc such as triethyl aluminum, tri (i -propyl) aluminum, tri) ibutyl) aluminum, tri (n-hexyl) aluminum, tri (n-octyl) aluminum, or diethylzinc, with a less than stoichiometric amount (relative to the number of hydrocarbyl groups) of a secondary amine or a hydroxyl compound, such as bis (trimethylsilyl) amine, t-butyl (dimethyl) siloxane, 2-hydroxymethylpyridine, di (n-pentyl) amine, 2,6-di (tbutyl) phenol, ethyl (1-naphthyl) amine, bis ( 2,3,6,7-dibenzo-1azacycloheptanoamine), or 2,6-diphenylphenol. Desirably, sufficient amine or hydroxyl reagent is used in such a way that one hydrocarbyl group remains per metal atom. Examples of the primary reaction products of the above most desired combinations for use in the present disclosure as transfer agents are n-octylaluminium di (bis (trimethylsilyl) amide), i-propylaluminium bis (dimethyl) (t-butyl) siloxide), i- butylaluminum bis (dimethyl (t-butyl) siloxane), i-butylaluminum bis (di (trimethylsilyl) amide, n-octylaluminium di (iridine-2methoxide), i-butylaluminum bis (di (n-pentylamide), noctilaluminium bis [2, 6-di-t-butylphenoxide), n-octyl aluminum di (ethyl) (1-naphthyl) amide), ethyl aluminum bis (tbutyldimethyl) siloxide), ethyl aluminum bis (trimethylsilyl) amide), ethyl aluminum bis (2,3,6,7 -dibenzo
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1-azacycloheptanoamide), n-octyl aluminum bis (2,3,6,7-dibenzo1-azacycloheptanoamide), n-octyl aluminum bis (dmiethyl (tbutil) siloxide, ethylzinc (2,6-diphenylphenoxide), and ethylzinc (t-butoxide) .
[0089] The double-headed chain transfer agents provided in this disclosure, which include compounds of the general formula R ¹ [MA-R ² -] NMAR ¹ and R ¹ [MBR ¹ -R ² -] NMB (R ¹ ) ₂ , where MA is Zn or Mg and where M is B, Al, or Ga, may include a portion R
such divalent as a group hydrocarbadiyl or 1.3- dihydrocarbadiylteraalkylsiloxane. ₂ In this respect, R may be selected regardless of ethanediyl, 1.3- propanediila, 1,4-butanediyl, 1,5-pentanediyl, 1.6- hexanediyl, 2 , 5-hexanediyl, 1,7-heptanediyl, 1.8- octanodiyl, 1,9-nonanodiyl, 1,10-decanodiyl, and
₂ similar, including larger R plots. In addition, R ² can also be selected independently from 1,3ethanediyl-tetramethyldisiloxane, 1,3 (propan-1,3diyl) tetramethyldisiloxane, 1,3 (butan-1,4diyl) tetramethyldisiloxane, 1,3 (pentan-1,5- diyl) tetramethyldisiloxane, 1,3 (hexan-1,6-diyl) tetramethyldisiloxane,
1,3 (heptan-1,7-diyl) tetramethyldisiloxane, 1,3 (octan-1,8diyl) tetramethyldisiloxane, 1,3- (propan-1,3-diyl) tetramethyldisiloxane, 1,3- (butan-1, 4-diyl) tetramethyldisiloxane, 1,3- (pentan-1,5-diyl) tetramethyldisiloxane, 1,3- (hexan-1,6diyl) tetramethyldisiloxane, 1,3- (heptan-1,7-diyl) tetramethyldisiloxane , 1,3- (octan-1,8-diyl) tetramethyldisiloxane, or ₂ similar R plots.
[0090] Double-headed chain transfer agents provided in this disclosure such as compounds of the general formula M ^C [R ² ] 2M ^C or M ^B [R ² ] 3M ^B , where M ^B is B, Al, or Ga , and where M ^C
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55/119 _{ζ ζ} 2 and Mg also include divalent R portions such as a hydrocarbadiyl group or a 1,3 dihydrocarbadiyltetraalkylsilyoxane such as those disclosed for the CSAs of the formulas R ¹ [M ^A -R ² -] NM ^A R ¹ and R ¹ [MBR ¹ R ² -] NM ^B (R ¹ ) 2. In one aspect, CSAs of formulas M ^C [R ² ] 2M ^C and M ^B [R ² ] 3M ^B typically have R ² portions selected from alkali groups such as ethanediyl, 1,3-propanediyl, 1,4butanediyl, 1,5 -pentanodiyl, 1,6-hexanediyl, 1,7heptanediyl, 1,8-octanodiyl, 1,9-nonanodiyl, 1,10 ₂ decanodiyl, and the like, or even R portions of larger alkadiles.
[0091] Transition Metal Catalyst Precursors [0092] Among other things, this disclosure provides a catalyst composition and several methods that include at least one polymerization catalyst precursor, at least one cocatalyst, and at least one transfer agent. dendritic chain as disclosed here. Catalysts suitable for use in the methods and compositions disclosed herein include any compound or combination of compounds that is adapted to prepare polymers of the desired type or composition. Both heterogeneous and homogeneous catalysts can be used. Examples of heterogeneous catalysts include the well-known Ziegler-Natta compositions including Group 4 metal halides and their derivatives, and including Group 4 metal halides supported on Group 2 metal halides or mixed halides and alkoxides, including the well-known chromium or vanadium based catalysts. However, for ease of use and for the production of polymer segments with narrow molecular weight distribution in solution,
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56/119 Especially useful catalysts include homogeneous catalysts including a relatively pure organometallic compound or metal complex, especially compounds or complexes based on metals selected from Groups 3-15 or the Lanthanide series of the Periodic Table of Elements. [0093] Catalysts and catalyst processes suitable for use in the present invention include those disclosed in WO2005 / 090427, in particular those disclosed starting on page 25, line 19 through page 55, line 10. Suitable catalysts and catalyst precursors are also disclosed in US2006 / 0199930; US2007 / 0167578; US2008 / 0311812; US 7,355,089 B2; or WO
2009/012215.
[0094] One aspect of this disclosure provided for particularly useful polymerization catalyst precursors, including, but not limited to, those listed as Catalysts A1-A10 in the examples section of this disclosure as well as any combination of these.
[0095] Catalysts having high comonomer incorporation properties are also known to reincorporate long chain olefins prepared in situ incidentally resulting during polymerization by β-hydride elimination and growing polymer chain termination or other process. The concentration of such long-chain olefins is particularly improved by the use of continuous solution and high conversion polymerization conditions, especially conversions of ethylene of 95 percent or higher, and more particularly to ethylene conversions of 97 percent or higher. Under such conditions, a small but detectable amount of finished polymer
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57/119 in vinyl group may be reincorporated into the growing polymer chain, resulting in the formation of long chain branches, that is, branches with a longer carbon length than could result from another deliberately added monomer. In addition, such chains reflect the presence of other comonomers in the reaction mixture. That is, the chains may include short- or long-chain branches as well, depending on the composition of the comonomer in the reaction mixture. However, the presence of a chain transfer agent during polymerization may seriously limit the incidence of long chain branches as the vast majority of polymer chains are linked to CSA species and are prevented from experiencing β- hydride.
Cocatalysts [0096] Each of the metal complexes (also referred to interchangeably herein as procatalysts or catalyst precursors) may be activated to form the active catalyst composition in combination with a cocatalyst, preferably a cation-forming cocatalyst, a strong Lewis acid, or a combination of these. Therefore, this disclosure also provides for the use of at least one cocatalyst in a catalyst composition and various methods, together with at least one polymerization catalyst precursor, and at least one chain transfer agent as disclosed herein.
Suitable cation-forming cocatalysts include those previously known in the art for metal olefin polymerization complexes. Examples include neutral Lewis acids, such as compounds from the
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58/119 substituted with C _1-30 hydrocarbyl, especially compounds of tri (hydrocarbyl) aluminum or tri (hydrocarbyl) boron and halogenated derivatives (including perhalogenated thereof), having from 1 to 1 carbons in each hydrocarbyl or halogenated hydrocarbyl group, more especially perfluorinated tri (aryl) boron compounds, and most especially tris (pentafluorophenyl) borane; ion-forming compounds, non-polymeric, compatible, non-coordinating (including the use of such compounds under oxidizing conditions), especially the use of ammonium, phosphonium, oxon, carbonium, silyl, or sulfonium salts, of compatible non-coordinating anions; and combinations of the above cation-forming cocatalysts and techniques. Cocatalysts and activation techniques were previously taught with respect to different metal complexes for the polymerization of olefins previously taught in the following references: EP-A277.003; US 5,153,157; US 5,064,802; US 5,321,106; US 5,721,185; US 5.35o.723; US 5,425,872; US 5,625.o87; US 5,883,204; US 5,919,983; US 5,783,512; WO 99/15534; and WO 99/42467.
[0098] Combinations of neutral Lewis acids, especially the combination of a trialkyl aluminum compound having 1 to 4 carbons in each alkyl group and a halogenated tri (hydrocarbyl) boron compound having 1 to 20 carbons in each hydrocarbyl group, especially tris (penta-fluorphenyl) borane, additional combinations of such mixtures of neutral Lewis acids with an oligomeric alumoxane, and combinations of a single neutral Lewis acid, especially tris (pentafluorfenyl) borane with a polymeric or oligomeric alumoxane may be used as
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59/119 activating cocatalysts. Preferred molar ratios of metal complex: tris (pentafluorfenyl) borane: alumoxane are from 1: 1: 1 to 1: 5: 20, more preferably from 1: 1: 5 to 1: 5: 1.
[0099] Ion-forming compounds useful as cocatalysts in one embodiment of the present disclosure comprise a cation that is a Bronsted acid capable of donating a proton, and a non-coordinating, compatible anion, A ^- . As used here, the term non-coordinating refers to an anion or substance that either does not coordinate with the precursor complex containing Group 4 metal and the catalytic derivative derived from them, or that coordinates only weakly with such complexes and thus remains sufficiently labile to be displaced by a neutral Lewis base. A non-coordinating anion refers specifically to an anion that, when functioning as a charge-balancing anion in a cationic metal complex, does not transfer any anionic substituent or fragment thereof to said cation, thus forming neutral complexes.
Compatible anions are anions that are not degraded to neutrality when the complex initially formed decomposes, and are non-interfering with the desired subsequent polymerization or other uses of the complex.
[0100] Preferred anions are those containing a single coordination complex comprising a charge-bearing metal or metalloid core whose anion is capable of balancing the charge of the active catalyst species (the metal cation) that may be formed when the two components are combined. Also, said anion must be sufficiently labile to be displaced by olefinic, diolefinic, and acetylenically unsaturated or
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60/119 other neutral Lewis bases such as ethers and nitriles. Suitable metals include, but are not limited to, aluminum, gold and platinum. Suitable metalloids include, but are not limited to, boron, phosphorus, and silicon. Anion-containing compounds comprising coordination complexes containing a single metal or metalloid atom are, of course, well known, and many, particularly such compounds with a single boron atom in the anion portion, are commercially available.
[0101] In one aspect, suitable cocatalysts can be represented by the following general formula:
(L * -H) g ⁺ (A) ^g- , where:
L * is a neutral Lewis base;
(L * -H) ⁺ is a non-coordinating, compatible anion having a charge of g-, eg it is an integer from 1 to 3.
[0102] More particularly, A ^g- corresponds to the formula: [MiQ ₄ ]; Where:
Mi is boron or aluminum in the +3 formal oxidation state; and [0103] Q independently in each occurrence is selected from radicals hydride, dialkyl starch, halide, hydrocarbyl, hydrocarbyl oxide, halosubstituted hydrocarbyl, halo-substituted hydrocarbyloxy and halo-substituted silylhydrocarbyl (including pre-halogenated, hydrocarbyl, pre-halogenated, hydrocarbyloxy radicals pre-halogenated silylhydrocarbyl), each Q having up to 20 carbons with the proviso that in no more than one occurrence Q is halide. Examples of suitable hydrocarbyl oxide groups Q are disclosed in US-A-5,296,433.
[0104] In a more preferred embodiment, d is one, that is, the counter ion has a single negative charge A ^- .
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61/119
Activating cocatalysts comprising boron which are particularly useful in the preparation of catalysts for this disclosure may be represented by the formula:
(L * -H) ⁺ (BQ4) ^- ; Where
L * is as previously defined;
B is boron in a formal oxidation state of 3; and
Q is a hydrocarbyl, hydrocarbyloxy, fluorinated hydrocarbyl, fluorinated hydrocarbyloxide, fluorinated hydrocarbyloxy group of up to 20 different hydrogen atoms, with the proviso that in no more than one occurrence Q is hydrocarbyl.
[0105] Especially useful Lewis base salts are ammonium salts, more preferably trialkylammonium salts containing one or more C13-30 alkyl groups. In this respect, for example, Q in each occurrence may be a fluorinated aryl group, especially a pentafluorfenyl group.
[0106] Illustrative, but not limiting, examples of boron compounds that could be used as an activating cocatalyst in the preparation of the improved catalysts in this disclosure include the tri-substituted ammonium salts, such as:
tetrakis (pentafluorfenil) trimethylammonium borate;
tetrakis (pentafluorfenyl) triethylammonium borate;
tetrakis (pentafluorfenyl) tri (n-butyl) ammonium borate;
tetrakis (pentafluorfenyl) tri (sec-butyl) ammonium borate;
tetrakis borate (pentafluorfenil)
N, N-dimethylanilinium;
n-butyltris (pentafluorfenyl) N, N-dimethylanilinium borate;
benzyltris (pentafluorfenyl) N, N-dimethylanilinium borate;
tetrakis borate (4- (t-butyltris (pentafluorfenyl) N, N dimethylanilinium;
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62/119 tetrakis borate (4- (triisopropylsilyl) -2,3,5,6tetrafluorfenyl) N, N-dimethylanilinium;
tetrakis borate (pentafluorfenyl) N, N-diethylanilinium;
benzyltris (pentafluorfenyl) N, N-dimethyl-2,4,6trimethylanilinium borate;
benzyltris (pentafluorfenyl) dimethyloctadecyl ammonium borate;
benzyltris (pentafluorfenyl) methyldioctadecyl-ammonium borate;
a number of dialkyl ammonium salts, such as:
tetrakis borate (pentafluorfenil) tetrakis borate (pentafluorfenil) tetrakis borate (pentafluorfenil) tetrakis borate (pentafluorfenil) di (i-propyl) ammonium;
methyloctadecylammonium;
methyloctadodecylammonium;
dioctadecylammonium;
various tri-substituted phosphonium salts, such as tetrakis (pentafluorfenyl) triphenylphosphonium borate;
tetrakis borate (pentafluorfenyl) methyldioctadecyl phosphonium; and tetrakis (pentafluorfenyl) tri (2,6-dimethylphenyl) phosphonium borate;
di-substituted oxonium salts, such as:
tetrakis borate (pentafluorfenil) diphenyloxonium;
tetrakis (pentafluorfenyl) di (o-tolyl) oxonium borate; and tetrakis (pentafluorfenyl) di (octadecyl) oxonium borate; and di-substituted sulfonium salts, such as:
tetrakis borate (pentafluorfenyl) di (o-tolyl) sulfonium, and tetrakis borate (pentafluorfenyl) methyloctadecyl) sulfonium.
[0107] In addition to this aspect of the disclosure, examples of useful (L * -H) ⁺ cations include, but are not limited to, methyldioctadecylammonium cations, dimethyloctadecyl-ammonium cations, and ammonium cations derived from
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63/119 trialkyl amine mixtures containing one or more C14-18 alkyl groups · [0108] Another suitable ion-forming activator cocatalyst comprises a salt of a cationic oxidizing agent and a compatible, non-coordinating anion represented by the formula:
(Ox ^{h +} ) g (A ^g- ) _h , where:
Ox ^{h +} is a cationic oxidizing agent having a charge of h +;
H is an integer from 1 to 3; and
A ^g- eg are as previously defined · [0109] Examples of cationic oxidizing agents include: ferrocene, ferrocene substituted with hydrocarbyl, Ag ⁺ , or Pb ⁺² · Particularly useful examples of A ^g- are those anions previously defined with respect to cocatalysts Bronsted acid-containing activators containing activating cocatalysts, especially tetrakis borate (pentafluorfenyl) · Another suitable ion-forming activating cocatalyst may be a compound that is a carbenium ion salt and a non-coordinating, compatible anion represented by the following formula:
[C] ⁺ A ^- where:
[C] ⁺ is a C1-20 carbenium ion; and
A- is a non-coordinating, compatible anion having a charge of -1 · For example, a carbene ion that works well like the trityl cation, which is triphenylmethyl · [0110] A suitable ion-forming activator cocatalyst comprises a compound that is a salt of a silyl ion and a non-coordinating, compatible anion represented by the following
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64/119 formula:
(Q ¹ 3Si) ⁺ A where:
Q ¹ is a C ₁ - ₁₀ hydrocarbyl, and A ^- is as previously defined.
[0111] Suitable silicon salt activating cocatalysts include trimethylsilyl tetraquispentafluorphenylborate, triethylsilyl tetraquispentafluorphenylborate, and ether-substituted adducts. Silyl salts have previously been generally disclosed in J.Chem. Soc. Chem Comm. 1993, 383-384, as well as in Lambert, JB et al., Organometallics 1994, 13, 2430-2443. The use of the above silylium salts for polymerization catalysts is also described in U.S. Patent No. 5,625,087.
[0112] Certain complexes of alcohols, mercaptan, silanols, and oximes with tris (pentafluorfenyl) borane are also effective catalyst activators and may be used in accordance with the present disclosure. Such cocatalysts are disclosed in US Patent No. 5,296,433.
[0113] Activating cocatalysts suitable for use here also include polymeric or oligomeric alumoxanes (also called aluminoxanes), especially methylalumoxane (MAO), modified methylalumoxane (MMAO) with triisobutyl aluminum, or isobutylalumoxane; alumoxanes modified with Lewis acids, especially alumoxanes modified with perhalogenated tri (hydrocarbyl) aluminum or perhalogenated tri (hydrocarbyl) boron, having from 1 to 10 carbons in each hydrocarbyl or halogenated hydrocarbyl group, and most especially alumoxanes modified with tris (pentafluorfenil) borane. Such cocatalysts were previously
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65/119 disclosed in US Patents ^Nos 6,214,760, 6,160,146, 6,140,521, and 6,696,379.
[0114] A class of cocatalysts comprising non - coordinative anions generally referred to as expanded anions, further disclosed in US Patent No. 6,395,671, may be suitably employed to activate the metal complexes of the present disclosure for olefin polymerization. Generally, these cocatalysts (illustrated as those having imidazolid, substituted imidazolide, imidazolinide, substituted imidazolinide, benzimidazolid, or substituted benzimidazolid) anions may be
A ^{* +} is a cation, especially a proton-containing cation, and could be a trihydrocarbyl ammonium cation containing one or two C10-40 alkyl groups, especially a methyldi ((C _14-20 ) ammonium) cation,
Q, independently at each occurrence, is hydrogen, or a halo, hydrocarbyl, halocarbyl, halohydrocarbyl, silyl hydrocarbyl, or silyl group (including, for example, mono-, di- and tri (hydrocarbil) silyl) of up to 30 atoms not containing hydrogen , such as C1-20 alkyl, and
Q is tris (pentafluorfenil) borane or aluminum tris (pentafluorfenil).
[0115] Examples of these catalyst activators include
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66/119 trihydrocarbylammonium salts, especially methyldi (C _14-20 alkyl) ammonium salts of:
bis (tris (pentafluorfenil) borane) imidazolid, bis (tris (pentafluorfenyl) borane) -2-undecylimidazolid, bis (tris (pentafluorfenyl) borane) -2-heptadecylimidazolid, bis (tris (pentafluorfenil) borane) -4,5 (undecyl) imidazolid, bis (tris (pentafluorfenyl) borane) -4,5-bis (heptadecyl) imidazolid, bis (tris (pentafluorfenyl) borane) -2-undecylimidazolinide, bis (tris (pentafluorfenil) borane) -2-heptadecylimidaz da, bis (tris (pentafluorfenil) borane) -4,5-bis (undecyl) imidazolinide, bis (tris (pentafluorfenyl) borane) -4,5-bis (heptadecyl) imidazolinide, bis (tris (pentafluorfenil) borane) -5 , 6-dimethylbenzimidazo-lida, bis (tris (pentafluorfenil) aano) -5,6-bis (undecyl) benzimidazolid, bis (tris (pentafluorfenil) alumano) imidazolid, bis (tris (pentafluorfenil) alumano) -2-undecilimidazole (tris (pentafluorfenil) alumano) -2-heptadecilimidazoli-da, bis (tris (pentafluorfenil) alumano) -4,5-bis (undecil) imidazolid, bis (tris (pentafluorfenil) alumano) -4,5-bis (heptadecil) imidazolid, bis (tris (pentafluorfenil) alumano) -2-undecilim idazolinide, bis (tris (pentafluorfenil) alumano) -2-heptadecilimidazoli-nida, bis (tris (pentafluorfenil) alumano) -4,5-bis (undecyl) imidazolinide, bis (tris (pentafluorfenil) alumano) -4,5-bis (heptadecyl)
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67/119 imidazolinide, bis (tris (pentafluorfenil) alumano) -5,6-dimethylbenzimidazolid, bis (tris (pentafluorfenil) alumano) -5,6-bis (undecyl) benzimidazolid.
[0116] Other activators include those described in PCT publication WO 98/07515, such as tris fluoraluminate (2,2 ', 2-nonafluorbiphenyl). Combinations of activators are also contemplated by the disclosure, for example, alumoxanes and ionizing activators in combinations, see for example EP-A-0573120, WO 94/07928 and PCT publications WO 95/14044 and US patents ^Nos 5,153,157 and 5,453,410. For example, and in general terms, WO 98/09996 describes activating catalyst compounds with perchlorates, periodates and iodates, including their hydrates. WO 99/18135 describes the use of organoboroaluminators. WO 03/10171 discloses catalyst activators which are adducts of Bronsted acids with Lewis acids. Other activators or methods for activating a catalyst compound are described, for example, in US Patents ^Nos 5,849,852, 5,859,653, and
5,869,723, in EP-A-615981, and in PCT publication WO 98/32775. All of the above catalyst activators as well as any other known activator for transition metal complex catalysts may be employed separately or in combination in accordance with the present disclosure. However, in one aspect, the cocatalyst may be free of alumoxane. In another aspect, for example, the cocatalyst may be free of any activator or class of activators specifically cited as disclosed here.
[0117] In an additional aspect, the molar ratio of
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68/119 catalyst / cocatalyst employed generally ranges from 1: 10,000 to 100: 1, for example, from 1: 5000 to 10: 1, or from 1: 1000 to 1: 1. Alumoxane, when used alone as an activating cocatalyst, can be used in large quantities, usually at least 100 times the amount of metal complex on a molar basis.
[0118] Tris (pentafluorfenil) borane, when used as an activating cocatalyst, can generally be used at a molar to metal complex ratio of 0.5: 1 to 10: 1, more preferably from 1: 1 to 6: 1, the more preferably from 1: 1 to 5: 1. The remaining activating cocatalysts are generally used in equimolar amounts with the metal complex. [0119] In another aspect, the polymer products may contain at least an amount of a polymer containing two or more blocks of segments connected by means of a remainder of a double-headed or multiple-headed transfer agent.
Generally the product comprises distinct polymer species having different molecular weights, ideally the largest molecular weights being multiple integers of the smallest. As a general rule, the product comprises a first polymer having a first molecular weight and at least some quantity of a second polymer having a molecular weight that is approximately an integer multiple of the molecular weight of the first polymer, the whole number being equal to number of transfer centers in the transfer agent. The polymer recovered from the present process can be terminated to form polymers of conventional type, coupled through the use of a polyfunctional coupling agent in order to form multi-block copolymers, including
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69/119 hyper-branched or dendrimeric copolymers, or functionalized by converting remnants of double-headed or multiple-headed transfer agents into vinyl, hydroxyl, amine, silane, carboxylic acid, carboxylic acid ester, ionomeric, or other functional groups according to known techniques.
Polymerization Methods [0120] In one aspect of this disclosure, a process is provided and the resulting polymer, the process comprising polymerizing one or more olefin monomers in the presence of an olefin polymerization catalyst and a double headed or headed transfer agent (CSA or MSA) in a reactor or polymerization zone thus causing the formation of at least some amount of a polymer bound with the remainder of the double-headed or multiple-headed transfer agent.
[0121] In yet another aspect, a process is provided and the resulting polymer, the process comprising polymerizing one or more olefin monomers in the presence of an olefin polymerization catalyst and a double-headed or multiple-headed transfer agent (MSA) in a reactor or polymerization zone thus causing the formation of at least some amount of an initial polymer bound with the remainder of the double-headed or multiple-headed transfer agent within the reactor or zone; discharge the reaction product from the first reactor or zone to a second reactor or zone operating under polymerization conditions that are distinguishable from those of the first reactor or zone; transfer at least some of the initial polymer bound with the remainder of the double headed transfer agent or
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70/119 multiple heads for an active catalyst site in the second reactor or zone by means of at least one remaining transfer site of the double-headed or multiple-headed transfer agent; and conducting polymerization in the second reactor or polymerization zone so as to form a second polymer segment bound to some or all of the initial polymer by means of the remainder of the double-headed or multiple-headed transfer agent, the second polymer segment having polymer properties distinguishable from the initial polymer segment.
[0122]
During polymerization, the reaction mixture is contacted with the activated catalyst composition according to any suitable polymerization conditions.
The process can generally be characterized by the use of high temperatures and pressures. Hydrogen can be used as a chain transfer agent to control molecular weight according to known techniques, if desired. As with other similar polymerizations, it is generally desirable that the monomers and solvents employed are of sufficiently high purity so that catalyst deactivation or premature chain termination does not occur. Any suitable technique for the purification of monomers such as devolatilization under reduced pressures, contact with molecular sieves or high surface area alumina, or a combination of these processes can be employed.
[0123]
Supports can be used in the present methods, especially in polymerizations in paste or gas phase.
Suitable supports include metal oxides, metalloid oxides, solids, particulates, high area
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71/119 surface, or mixtures of these (interchangeably referred to here as an inorganic oxide). Examples include, but are not limited to, talc, silica, alumina, magnesia, titania, zirconia, Sn ₂ O ₃ , aluminosilicates, borosilicates, clays, and any combination or mixture thereof. Suitable supports preferably have a surface area as determined by nitrogen porosimetry using the BET method from 10 to 1000 m ² / g, and preferably from 100 to 600 m ² / g. The average particle size is typically 0.10 to 500 mm, preferably 1 to 200 mm, more preferably 10 to 100 mm.
[0124] In one aspect of the present disclosure, the catalyst and optional support composition may be dried or otherwise recovered in a solid, particulate form, to provide a composition that is readily transported and handled. Suitable methods of spray drying a liquid containing paste are well known in the art and usefully employed here. Preferred techniques for spray drying catalyst compositions for use herein are described in US Patents ^Nos 5,648,310 and 5,672,669.
[0125] The polymerization is desirably carried out as a continuous polymerization, for example, a continuous solution polymerization, in which the catalyst components, monomers, and optionally solvent, adjuvants, purgers, and polymerization auxiliaries are continuously supplied to one or more more reactors or zones and polymer product is continuously removed from them.
Within the scope of the terms continuously and continuously as used in this context include those processes in which there are intermittent reagent additions and product removal
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72/119 at small regular or irregular intervals, in such a way that, over time, the overall process is substantially continuous. While the multi-centered transfer agent and chain transfer agent (s) (if used) can be added at any point during polymerization including in the first reactor or zone, at the outlet or slightly before exit from the first reactor, between the first reactor or zone and any subsequent reactor or zone, or even just to the second reactor or zone, if present, both are typically added in the initial stages of polymerization. If there is any difference in monomers, temperatures, pressures or other polymerization conditions within the reactor or between two or more reactors or zones connected in series, polymer segments of differentiated compositions such as comonomer content, crystallinity, density, tactility, regency- regularity, or other chemical or physical differences within the same molecule, may be formed in the polymers of this disclosure. In such a case, the size of each segment or block is determined by the reaction conditions of the polymer, and is typically a more likely distribution of polymer sizes.
[0126] If multiple reactors are used, each one can be independently operated under conditions of high pressure polymerization, in solution, paste, or in gas phase. In a multiple zone polymerization, all zones operate under the same type of polymerization, such as solution, paste, or gas phase, but, optionally, under different process conditions. For a solution polymerization process, it is desirable to use dispersions
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73/119 homogeneous components of the catalyst in a liquid diluent in which the polymer is soluble under the polymerization conditions employed. One such process utilizing an extremely fine silica or similar dispersing agent to produce such a homogeneous catalyst dispersion where normally either the metal complex or the cocatalyst is only poorly soluble is disclosed in US Patent No 5,783,512 ^it. A high pressure process is generally carried out at temperatures of 100 ° C to 400 ° C and the pressure above 50 MPa (500 bar). A paste process typically uses an inert hydrocarbon diluent and temperatures from 0 ° C to a temperature just below the temperature at which the resulting polymer becomes substantially soluble in the inert polymerization medium. For example, typical temperatures in a paste polymerization are 30 ° C, generally from 60 ° C to 115 ° C, including up to 100 ° C, depending on the polymer being prepared. Pressures typically in the atmospheric range at 3.4 MPa (500 psi).
[0127] In all of the above processes, continuous or substantially continuous polymerization conditions are generally employed. The use of such polymerization conditions, especially continuous solution polymerization processes, allows the use of high reactor temperatures which result in the economical production of the present block copolymers at high yields and efficiencies. [0128] The catalyst can be prepared as a homogeneous composition by adding the necessary metal complex or multiple complexes to a solvent in which the polymerization is carried out or in a diluent compatible with the final reaction mixture. The cocatalyst or activator
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74/119 and, optionally, a transfer agent may be combined with the catalyst composition either before, or after combining the catalyst with the monomers to be polymerized and any additional reaction diluent. Desirably, the MSA is added at the same time.
[0129] At all times, the individual ingredients, as well as any active catalyst composition, are protected from oxygen, moisture, and other catalyst poisons. Hence, the components of the catalyst, multi-center transfer agent, and activated catalysts are repaired and stored in a moisture-free atmosphere, usually under an inert, dry gas such as nitrogen.
[0130] Without limiting in any way the scope of the disclosure, a means to carry out such a polymerization process is as follows. In one or more well-stirred tanks or loop reactors operating under solution polymerization conditions, the monomers to be polymerized are introduced continuously together with any solvent or diluent in a part of the reactor. The reactor contains a relatively homogeneous liquid phase composed substantially of monomers together with any solvent or diluent and dissolved polymer. Preferred solvents include C4-10 hydrocarbons or mixtures thereof, especially alkanes, such as hexane or mixtures of alkanes, as well as one or more monomers employed in polymerization. Examples of suitable loop reactors and a variety of suitable operating conditions for use therewith, including the use of multiple reactor loops, operating in series, are found in ^the US patent No 5,977,251, and 6,319,989 6.683.14 .
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75/119 [0131] Catalyst together with cocatalyst and multi-centered transfer agent are continuously or intermittently introduced into the liquid phase of the reactor or any recycled portion of these in at least one location. The reactor temperature and pressure can be controlled, for example, by adjusting the solvent / monomer ratio or the catalyst addition rate, as well as by using coils, liners, or both, for cooling or heating. The rate of polymerization can be controlled by the rate of addition of the catalyst. The content of a given monomer in the polymer product is influenced by the ratio of monomers in the reactor, which is controlled by manipulating the respective feed rates of these components to the reactor. The molecular weight of the polymer product is optionally controlled by controlling other variables such as temperature, monomer concentration, or by the multi-centered transfer agent mentioned above, or by a chain terminating agent such as hydrogen, as is known in the technical.
[0132] In one aspect of the disclosure, a second reactor is connected to the discharge of a first reactor, optionally via a conduit or other transfer medium, in such a way that the reaction mixture prepared in the first reactor is discharged into the second reactor without substantial termination of polymer growth. Between the first and the second reactors, a differential of at least one process condition can be established. Generally for use in forming a copolymer of two or more monomers, the difference is the presence or absence of one or more comonomers or a difference in the comonomer concentration. Reactors
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Additional 76/119, each arranged similarly to the second reactor in the series may also be provided. Additional polymerization is terminated by contacting the reactor effluent with a catalyst exterminating agent such as water, water vapor, or an alcohol or with a coupling agent if a coupled reaction product is desired. [0133] The resulting polymer product is recovered by flashing out volatile components from the reaction mixture such as monomer (s) or residual diluent (s) under reduced pressure and, if necessary, leading to further devolatilization in equipment such as devolatilizing extruder. In a continuous process, the average residence time of the catalyst and polymer in the reactor is generally 5 minutes to 8 hours, for example, 10 minutes to 6 hours.
[0134] In a further aspect of this disclosure, alternatively, the above polymerization may be carried out in a flow reactor optionally pistoned with a monomer, catalyst, multi-centered transfer agent, temperature or other gradient established between different zones or regions thereof, still optionally accompanied by separate addition of catalysts and / or transfer agent, and operating under adiabatic or non-adiabatic polymerization conditions.
[0135] In yet another aspect, the catalyst composition may also be prepared and employed as a heterogeneous catalyst by absorbing the necessary components in an organic or inorganic particulate solid, as previously disclosed. For example, a heterogeneous catalyst may be prepared by co-precipitating the complex
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77/119 metal and the reaction product of an inorganic compound and an active hydrogen containing activator, especially the reaction product of a tri (Ci _-4 alkyl) aluminum in a salt of an ammonium borate hidroxiariltris (pentafluorfenila) , such as a borate ammonium salt of (4-hydroxy-3,5diterciariobutylphenyl) tris (pentafluorfenyl). When prepared in a homogeneous or supported form, the catalyst composition can be used in a paste or gas phase polymerization. As a practical limitation, paste polymerization occurs in liquid diluents in which the polymer product is substantially insoluble. Generally, the diluent for slurry polymerization is one or more hydrocarbons with less than 5 carbon atoms. If desired, saturated hydrocarbons, such as ethane, propane, or butane can be used as a whole or in part as a diluent. As with solution polymerization, the a-olefin comonomer or a combination of different a-olefin monomers can be used as a whole or part as a diluent. More preferably, at least a major part of the diluent comprises the monomer or monomers of α-olefin to be (in) polymerized (s).
[0136] In this regard, for use in gas phase polymerization processes, the resulting support material and catalyst may typically have a median particle diameter of 20 pm to 200 pm, generally from 30 pm to 150 pm, and typically 50 pm to 100 pm. For use in paste polymerization processes, the support may have a median particle diameter of 1 pm to 200 pm, generally from 5 pm to 100 pm, and typically from 10 pm to 80 pm.
[0137] Suitable gas phase polymerization processes
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78/119 for use here are substantially similar to known processes used commercially on a large scale for the manufacture of polypropylene, ethylene / aolefin copolymers, and other olefin polymers. The gas phase process employed may be, for example, the type that uses a mechanically agitated or fluidized gas bed as the polymerization reaction zone. Preferred is the process where the polymerization reaction is carried out in a vertical cylindrical polymerization reactor containing a fluidized bed of polymer particles supported or suspended above a perforated plate or fluidization grid, for a
flow of gas in fluidization. Law Suit in phase gaseous suitable what are adaptable for use in process this disclosure are disclosed by example, in U patents .S. n ^the
4,588,790; 4,543,399; 5,352,749; 5,436,304; 5,405,922;
4,462,999; 4,461,123; 5,453,471; 5,032,562; 5,028,670;
5,473,028; 5,106,804; 5,556,238; 5,541,270; 5,608,019; and
5,616,661.
[0138] The use of functionalized polymer derivatives is also included in the present disclosure. Examples include metallized polymers where the metal is the remainder of the catalyst or chain transfer agent employed, as well as additional derivatives thereof. Since a substantial fraction of the polymer product exiting the reactor is terminated with the multi-centered transfer agent, any further functionalization is relatively easy. The metallized polymer species can be used in well-known chemical reactions such as those suitable for other alkyl aluminum compounds, alkyl gallium, alkyl zinc, or Group 1 alkyl compounds to form polymer products
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79/119 functionalized with amine, hydroxy, epoxy, silane, vinyl, and others. Examples of suitable reaction techniques that are acceptable for use here are described in Negishi, Organometallics in Organic Synthesis ”, Vols. 1 and 2, (1980), and other standard texts on organometallic and organic syntheses.
Polymer Products [0139] Using the polymerization processes disclosed here, new polymer compositions, including block copolymers of one or more olefin monomers having the present molecular weight distribution, are readily prepared. Desirable polymers comprise, in polymerized form, at least one monomer selected from ethylene, propylene, and 4methyl-1-pentene. In a highly desirable manner, the polymers give interpolymers comprising in the polymerized form ethylene, propylene, and 4-methyl-1-pentene and at least one different C2-20 α-olefin comonomer, and optionally one or more copolymerizable comonomers.
Suitable comonomers are selected from diolefins, cyclic olefins, cyclic diolefins, halogenated vinyl compounds, aromatic vinylidene compounds, and combinations of these.
Generally preferred polymers are ethylene interpolymers with 1-butene, 1-hexene, or 1-octene. Desirably, the polymer compositions disclosed herein have an ethylene content of 1 to 99 percent, a diene content of 0 to 10 percent, and a C _3-8 styrene and / or a-olefin content of 99 to 1 percent, based on the total weight of the polymer. Typically, the polymers of this disclosure have an average molecular weight (M _w ) of 10,000 to 2,500,000.
[0140] Polymers prepared according to this
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80/119 disclosures may have a melt index typically from 0.01 to 500 g / 10 minutes, and especially from 0.01 to 100/10 minutes. Desirably, the disclosed polymers may have molecular weights, Mw, from 1,000 g / mol to 5,000,000 g / mol, typically from 1000 g / mol to 1,000,000 g / mol, more patent from 1000 g / mol to 500,000 g / mol mol, and especially from 1,000 g / mol to 300,000 g / mol. The density of polymers in this disclosure can be from 0.80 to 0.99 g / cm ³ and, typically, for polymers containing ethylene, from 0.85 g / cm ³ to 0.97 g / cm ³ .
[0141] The polymers according to this disclosure may be differentiated from random, conventional copolymers, physical mixtures of polymers, and block copolymers prepared by sequential addition of monomer, fluxional catalysts, or by live anionic or cationic polymerization techniques due, among other things, to their narrow molecular weight distributions. In this regard, for example, the polymer composition prepared in accordance with this disclosure may be characterized by a polydispersity index (PDI) of the polymer composition may be 1.5 to 2.8, 1.5 to 2, 5, or 1.5 to 2.3.
[0142] If present, the regions or separate blocks within each polymer are relatively uniform, depending on the uniformity of reactor conditions, and chemically distinct from each other. That is, the comonomer distribution, tacticity, or other property of segments within the polymer are relatively uniform within the same block or segment. However, the average block length may be a narrow distribution, but it is not necessarily so. The average block length may also be a more likely distribution.
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81/119 [0143]
In an additional aspect, the resulting polymer may be linear or contain one or more branching centers, depending on whether a transfer agent of two centers, three centers, or more has been employed.
Desirably, these interpolymers may be characterized by terminal blocks or segments of polymer having higher tactility or crystallinity than at least some of the remaining segments or blocks. Even more desirably, the polymer may be a triblock copolymer containing a central block or segment that is relatively amorphous or even elastomeric.
[0144]
In yet another aspect, the
MSA may be a three-center transfer agent if the resulting polymers are characterized by the presence of long chain branches. In this regard, a method is provided for generating long chain branches in olefin polymers without the use of a polymerizable functional group, such as a vinyl group. Instead, the long chain branching point (LCB) may be the remainder of such a three-center MSA. Because the degree of LCB in the polymer can be controlled by adding the three-center MSA to a polymerization reaction at the desired rate, the process is advantageous over prior art processes.
[0145] In a further aspect of this disclosure, a polymer composition is provided comprising: (1) an organic or inorganic polymer, preferably an ethylene or propylene homopolymer and / or an ethylene or propylene copolymer with one or more comonomers copolymerisables, and (2) a polymer or combination of polymers according to the present disclosure or prepared
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82/119 according to the process disclosed here.
[0146] The inventive polymer products include combinations of two or more polymers comprising regions or segments (blocks) of differentiated polymer compositions. Additionally, at least one of the constituents of the polymer combination may contain a linking group that is the remainder of a two-center or multiple-center transfer agent, causing the polymer to have certain physical properties.
[0147] Several additives may usefully be incorporated into the present compositions in amounts that do not deviate from the properties of the resulting composition. Such additives include, for example, reinforcing agents, fillers including conductive and non-conductive materials, ignition resistant additives, antioxidants, thermal and light stabilizers, colorants, extenders, crosslinkers, blowing agents, plasticizers, flame retardants, anti-dripping agents. , lubricants, slip additives, anti-blocking aids, anti-degraders, softeners, waxes, pigments, and the like, including combinations of these.
Applications and Final Uses [0148] These polymeric products and mixtures comprising these polymeric products are usefully used in the preparation of solid articles, such as moldings, films, sheets, and foamed objects by molding, extrusion, or other processes, and are useful as components or ingredients in adhesives, laminates, polymeric mixtures, and other end uses. The resulting products can also be used in the manufacture of automotive components, such as profiles,
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83/119 bumpers and trim parts; packaging materials; electrical cable insulation, and numerous other applications. The polymer composition of this disclosure may also be used in a variety of conventional thermoplastic fabrication processes to produce useful articles, including objects containing at least one layer of film, such as a monolayer film, prepared by casting, blowing, calendering, or extrusion coating; molded articles, such as blow molded, injection molded, or rotational molded articles; extrusions; fibers; and woven or non-woven cloths. Thermoplastic compositions containing the present polymers include mixtures with other natural or synthetic polymers and additives, including reinforcing agents, fillers, ignition resistant additives, antioxidants, thermal and light stabilizers, colorants, extenders, crosslinkers, blowing agents, plasticizers, flame retardants, anti-dripping agents, lubricants, slip additives, anti-blocking aids, anti-degraders, softeners, waxes, pigments mentioned above.
[0149] Fibers that can be prepared from the present polymers or mixtures include filamentary fibers, tow, multicomponents, wrap / core, twisted, and monofilaments. Suitable processes for forming fibers include spinbonded, melt blowing techniques, as disclosed in U.S. patents
^Nos 4,430,563,
4,663,220,
4,668,566, and 4,322,027, spun gel fibers as disclosed in U.S. patent
No. 4,413,110, woven and nonwoven fabrics, as disclosed in ^the US patent No 3,485,706, or structures made from such fibers, including blends with
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84/119 other fibers, such as polyester, nylon or cotton, thermoformed articles, extruded shapes, including extrusions and co-extrusions of profiles, calendered articles, and stretched, twisted or crimped yarns or filaments. The new polymers described here are also useful for wire and cable coating operations, as well as sheet extrusion for vacuum forming operations, and forming molded articles, including the use of injection molding, blow molding processes, or rotomoulding processes. Compositions containing the olefin polymers may also be shaped into manufactured articles, such as those previously mentioned using conventional polyolefin processing techniques which are well known to those skilled in the art of polyolefin processing.
[0150] Dispersions (both aqueous and non-aqueous) can also be formed using the present polymers or formulations containing them. Foamed skams containing the polymers disclosed herein may also be formed using, for example, the process disclosed in WO 04/021622. Polymers can also be cross-linked by any known means, such as using peroxide, electron beam, silane, azide, or another cross-linking technique. Polymers may also be chemically modified, such as by grafting (for example, by using maleic anhydride (MAH), silanes, or other grafting agent), halogenation, amination, sulfonation, or other chemical modification.
[0151] Polymers suitable for mixing with polymers prepared in accordance with this disclosure include thermoplastic and non-thermoplastic polymers including natural and synthetic polymers. Exemplary polymers for
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85/119 mixtures include polypropylene (both impact-modified polypropylene, isotactic polypropylene, atactic polypropylene, and random ethylene / propylene copolymers), several types of polyethylene, including high pressure, LDPE via free radical, LLDPE via Ziegler-Natta, PE via metallocene, such as products disclosed in ^the US patent No 6,545,088, 6,538,070, 6,566,446, 5,844,045, 5,869,575, and 6,448,341, ethylene-vinyl acetate (EVA), ethylene / vinyl alcohol, polystyrene, impact-modified polystyrene, ABS, styrene / butadiene block copolymers and hydrogenated derivatives thereof (SBS and SEBS), and thermoplastic polyurethanes. Homogeneous polymers, such as olefin plastomers and elastomers, ethylene and propylene-based copolymers (for example, commercially available polymers under the trade names VERSIFY ^MR commercially available from The Dow Chemical Company and VISTAMAXX ^mr commercially available from ExxonMobil) are also useful components in mixtures containing the present polymer composition.
[0152] Mixtures can be prepared by mixing or kneading the respective components at a temperature of approximately or above the melting temperature of one or both components. For most of the present compositions, this temperature can be above 130 ° C, 145 ° C, or even above 150 ° C. Equipment for mixing or kneading polymers that is capable of reaching the desired temperatures and plasticizing under melting the mixture can be used. These include mills, kneaders, extruders (both single and double screw),
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86/119 Banbury mixers, and calenders. The sequence and method of mixing may depend on the final composition. A combination of Banbury batch mixers and continuous mixers can also be employed, such as a Banbury mixer followed by a mill mixer followed by an extruder.
[0153] Mixture compositions may also contain processing oils, plasticizers, and processing aids. Some rubber processing oils and paraffinic, naphthenic or aromatic processing oils are all suitable for use. Generally from 0 to 150 parts are used, more typically from 0 to 100 parts, and most typically from 0 to 50 parts of oil per 100 parts of total polymer composition. Larger quantities of oil may tend to improve the processing of the resulting product at the expense of some physical properties. Additional processing aids include conventional waxes, fatty acid salts, such as calcium stearate or zinc stearate, (poly) alcohols, including glycols, ethers of (poly) alcohols, including glycol ethers, (poly) esters, including poly (glycol) esters, and metal salts, especially those derived from Group 1 and 2 metal salts or zinc, and derivatives thereof.
[0154] Compositions according to this disclosure may also contain antiozonants and antioxidants, which are known to those skilled in the art. Antiozonants may be physical protectors such as brain materials that migrate to the surface and protect the piece from oxygen or ozone, or they may be chemical protectors that react with oxygen or ozone. Suitable chemical protectors include
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87/119 styrenated phenols, butylated octylated phenol, butylated di (dimethylbenzyl) phenol, p-phenylenediamines, butylated reaction products of p-cresol and dicyclopentadiene (DCPD), polyphenolic antioxidants, hydroquinone derivatives, quinoline, diphenylene antioxidants thioester, and mixtures thereof. Some representative trade names of such products are Wingstay ^MR S antioxidant, Polystay ^MR 100 antioxidant, Polystay ^MR 100 AZ antioxidant, Polystay ^MR 200 antioxidant, Wingstay ^MR L antioxidant, Wingstay ^MR LHLS antioxidant, Wingstay ^MR K antioxidant, Wingstay ^MR 29 antioxidant, Antioxidant Wingstay ^MR SN-1, and antioxidants Irganox ^MR . In some applications, the antioxidants and anti-zonants used typically do not stain and migrate.
[0155] To provide additional stability against UV radiation, hindered amine UV light stabilizers (HALS) and UV absorbers may also be used. Suitable examples include Tinuvin ^MR 123, Tinuvin ^MR 144, Tinuvin ^MR 622, Tinuvin ^MR 765, Tinuvin ^MR 770, and Tinuvin ^MR 780, commercially available from Ciba Specialty Chemicals, and Chemisorb ^MR T944, commercially available from Cytex Plastics, Houston, TX, USA. A Lewis acid may be additionally included with a HALS compound in order to achieve superior surface quality, as disclosed in ^the US patent No 6,051,681.
[0156] For some compositions, additional mixing processes may be employed to pre-disperse antioxidants, antiozonants, pigment, UV absorbers, and / or light stabilizers to form a base mixture, and subsequently to form polymer mixtures from
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88/119 of these.
[0157] Certain compositions according to the disclosure, especially those containing the remainder of the conjugated diene comonomer, may subsequently be cross-linked in order to form cured compositions. Suitable crosslinking agents (also referred to as curing agents or vulcanizing agents) for use herein include sulfur-based, peroxide-based, or phenolic-based compounds. Examples of the foregoing materials are found in the art, including in U.S. Patents No 3,758,643 ^to, 3806558, 5051478, 4104210, 4130535, 4202801, 4271049, 4340684, 4250273 , 4,927,882, 4,311,628, and 5,248,729.
[0158] When sulfur-based curing agents are employed, accelerators and curing activators may also be used. Accelerators are used to control the time and / or temperature required for dynamic vulcanization and to improve the properties of the resulting crosslinked article. In one embodiment, a single accelerator or primary accelerator is used. The primary accelerator (s) may be used in total amounts ranging from 0.5 to 4, typically 0.8 to 1.5, phr (parts per 100 parts of resin ), based on the weight of the total composition. In another embodiment, combinations of a primary and a secondary accelerator may be used with the secondary accelerator being used in smaller amounts, such as from 0.05 to 3 phr, in order to activate and to improve the properties of the cured article. Combinations of accelerators generally produce articles having properties that are somewhat better than those produced using a single accelerator.
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In addition, delayed action accelerators may be used that are not affected by normal processing temperatures and still produce satisfactory curing at common vulcanization temperatures. Vulcanization retardants may also be used. Types of suitable accelerators that may be used as disclosed herein are amines, disulfides, guanidines, thiourea, thiazoles, thiomes, sulfenamides, dithiocarbamates, and xanthates. In one aspect, typically, the primary accelerator is a sulfenamide. If a second accelerator is used, the secondary accelerator will typically be a compound of guanidine, dithiocarbamate or thiurama. Certain processing aids and curing activators such as stearic acid and ZnO may also be used. When peroxide-based curing agents are used, co-activators or co-agents may be used with them. Suitable co-agents include trimethylolpropane triacrylate (TMPTMA), trialyl cyanurate (TAC), trialyl isocyanurate (TAIC), among others. The use of crosslinking peroxide and co-agent option used for partial dynamic or full vulcanization is known in the art and disclosed for example in publication Peroxide Vulcanization of Elastomers ", Vol. 74, No 3, July-August 2001.
[0159] The degree of crosslinking in a composition cured according to the disclosure can be measured by dissolving the composition in a solvent for a specified duration, and by calculating the percentage of extractable gel or rubber. The percentage of gel normally increases with increasing levels of crosslinking. For articles cured in accordance with this disclosure, the percentage gel content is desirably in the
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90/119 range from 5 to 100 percent.
[0160] The present compositions and mixtures of these may also have unprecedentedly improved melt strength properties due to the presence of the high molecular weight component and unprecedented molecular weight distribution, thus allowing the present compositions and mixtures of these to be usefully used in applications of foams and thermoforming where high melt strength is desired.
[0161] Thermoplastic compositions in accordance with this disclosure may also contain organic or inorganic fillers, or other additives such as starch, talc, calcium carbonate, glass fibers, polymeric fibers (including nylon, rayon, cotton, polyester, and polyamides) , metal fibers, wires, wefts, flakes or particles, expandable stratified silicates, phosphates or carbonates, such as clays, mica, silica, alumina, aluminosilicates or aluminophosphates, capillary carbon crystals, carbon fibers, nanoparticles, including nanotubes and nanofibers, wollastonite, graphite, zeolites, and ceramics, such as silicon carbide, silicon nitride, or titaniums. Oils based on silanes or other coupling agents can also be used to better bond loads. Additional suitable additives include drying, oils, including paraffinic and naphthenic oils; and other natural and synthetic polymers, including other polymers in accordance with this disclosure.
[0162] The polymer compositions of this disclosure, including the blends above, may be processed by conventional molding techniques such as molding by
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91/119 injection, extrusion molding, thermoforming, slush molding, over molding, insertion molding, blow molding, and other techniques. Films, including multilayer films, may be produced by casting or ramping processes, including blown film processes. Additional Aspects [0163] Several additional elements, aspects, characteristics and / or embodiments are described. For polymerization reactions that employ a two- or multiple-head CSA as disclosed here, reactions may be conducted in a batch reactor with ethylene and propylene, for example, together with an activated catalyst. Ethylene has a substantially higher reactivity than propylene in such polymerizations; hence, propylene is typically added in excess and the reaction is carried out beyond the full consumption of ethylene. In this respect, the final morphology of the polymer is characterized as containing a segment of ethylene / propylene rubber with isotactic propylene at each end.
[0164] Additionally, reagents such as diethyl zinc or other single-site CSA plots may be used in varying amounts in the methods and processes of this disclosure to create non-homogeneity in the polymer. In this respect, the relative amount of inhomogeneity can be controlled by adding more or less diethyl zinc to the reactor. Additional blocks can be added to the end of the polymer, for example, by adding another monomer or transferring the reaction mixture to another reactor.
[0165] Generally, and in additional aspects, double-headed zinc or aluminum CSAs may be prepared at
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92/119 from any precursor structure containing two terminal vinyl groups, and can be used for polymerization as long as the binder does not prevent the olefin polymerization process. For example, the linker may be the product derived from 1,3-divinyl tetramethyldisiloxane.
[0166]
Double-headed zinc CSAs may also be prepared from any precursor structures containing two halide groups. While many of the
Dual-head CSAs disclosed here are either polymeric, a polymeric or oligomeric CSA is not required, as shown.
For example, adding sulfur, phosphorus, nitrogen, or an oxygen-containing layer to the CSA could also lead to the desired polymer architecture. For example, a
CSA containing Aryl-O-Zn-alkanediyl-Zn-O-Arila, where Arila is any substituted or unsubstituted aryl group that is compatible with the olefin polymerization process, may also work in the same way as
Double-headed CSA and may be especially useful in process conditions that are not ideal for the polymeric or oligomeric CSAs disclosed here.
[0167]
Another aspect of the disclosure provides for a catalyst and an activator (or activating catalyst) and a CSA to be fed to a continuous reactor containing excess ethylene and propylene, which are polymerized to form a rubber. The continuous reactor can feed into a tube where either ethylene is removed or consumed, and crystalline polypropylene is formed. This propylene polymerization proceeds to form a tri-block comprised of intermediate rubber block, capped in
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93/119 each end with a crystalline polypropylene terminal block. The process can also be carried out in multiple batch reactors to form multiple blocks. For example, operating the process in two reactors, one would expect to lead to a symmetrical tri-block. The process can also be operated in a single reactor where the reactor environment can be changed during or throughout the polymerization, allowing the formation of different types of olefin polymers. Generally, the processes, methods, and CSAs disclosed herein can be extended to a variety of monomers to produce multi-block copolymers encompassing a wide distribution of properties of polymer compositions.
Assay Methods [0168] In one aspect of the above disclosure and the following examples, the following analytical techniques may be employed to characterize the resulting polymer.
Molecular Weight Determination [0169] Molecular weights are determined by optical analysis techniques including deconvoluted gel permeation chromatography coupled with a laser light scattering detector (GPC-LALLS) as described by Rudin, A., Modern Methods of Polymer Characterization ”, John Wiley & Sons, New York (1991), p. 103-122.
CRYSTAF Standard Method [0170] Branch distributions are determined by Crystallization Fractionation Analysis (CRYSTAF) using a commercially available CRYSTAF 200 unit from PolymerChar, Valencia, Spain. The samples are dissolved in 1,2,4-trichlorobenzene at 160 ° C (0.66 mg / ml) for 1 h and stabilized at 95 ° C for 45 minutes. The temperatures of
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94/119 sampling ranges from 95 to 30 ° C at a cooling rate of 0.2 ° C / min. An infrared detector is used to measure the concentrations of the polymer solution. The cumulative soluble concentration is measured as the polymer crystallizes while the temperature is reduced.
[0171] The analytical derivative of the cumulative profile reflects the short chain branch distribution of the polymer. The peak temperature of CRYSTAF and the area are identified by the peak analysis module included in the CRYSTAF software (Version 2001.b, PolymerChar, Valencia, Spain). The CRYSTAF peak search routine identifies a peak temperature as
a maximum at dW / dT curve and The area among the biggest inflections positive in each side of peak identified on the curve derived. Standard Method from DSC [0172] The results in Scanning Calorimetry
Differentials are determined using a DSC TAI model Q1000 equipped with an RCS cooling accessory and a self-sampler. A flow of nitrogen purge gas of 50 mL / min is used. The sample is pressed into a thin film and melted in the press at about 175 ° C and then cooled in air to room temperature (25 ° C). About 10 mg of material in the form of discs 5-6 mm in diameter are precisely weighed and placed in a light aluminum pan (about 50 mg), then closed and seamed. The thermal behavior of the sample is investigated with the following temperature profile. The sample is quickly heated to 180 ° C and kept isothermal for 3 minutes to remove any previous thermal history. The sample is then cooled to -40 ° C at a cooling rate of
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10 ° C / min and maintained at -40 ° C for 3 minutes. The sample is then heated to 150 ° C at a heating rate of 10 ° C / min. The cooling and second heating curves are recorded.
[0173] The DSC melting peak is measured as the maximum in heat flow rate (W / g) with respect to the linear baseline drawn between -30 ° C and the end of the melt. The heat of fusion is measured as the area under the melting curve between -30 ° C and the end of fusion using a linear baseline.
GPC method [0174] The gel permeation chromatographic system consists of a Polymer Laboratories Model PL-210 or Polymer Laboratories Model PL-220 instrument. The carousel column and compartments are operated at 140 ° C. Three 10-micron Mixed-B columns from Polymer Laboratories are used. The solvent is 1,2,4-trichlorobenzene. The samples are prepared at a concentration of 0.1 gram of polymer in 50 milliliters of solvent containing 200 ppm of butylated hydroxytoluene (BHT). The samples are prepared by gently shaking for 2 hours at 160 ° C. The injection volume used is 100 microliters and the flow rate is 1.0 mL / minute.
[0175] The calibration of the GPC column set is performed with 21 polystyrene standards with narrow molecular weight distribution with molecular weights ranging from 580 to 8,400,000, arranged in 6 cocktail mixes with at least a decade of separation between weights individual molecules. The standards are purchased from Polymer Laboratories (Shropshire, UK). Polystyrene standards are prepared with 0.025 grams in 50 milliliters of solvent for molecular weights equal to or greater than 1,000,000, and with
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0.05 grams in 50 milliliters of solvent for molecular weights less than 1,000,000. The polystyrene standards are dissolved at 80 ° C with gentle agitation for 30 minutes. Mixtures with narrow patterns are processed first and in order to reduce the component with the highest molecular weight to minimize degradation. The peak molecular weights of polystyrene standards are converted to molecular weights of polyethylene using the following equation (as described by Williams and Ward, J. Poly, Sci., Polym. Let., 6, 621 (1968): Mpol iethylene 0, 431 (Mpol isstyrene ⁾ [0176] Calculations of equivalent molecular weight of polyethylene are performed using the Viscotek TriSec Version 3.0 software.
Density [0177] Density measurements are conducted according to ASTM D 1928. Measurements are made within one hour of pressing the sample using ASTM D792, Method B.
Flexional / Secant Modules [0178] The samples are molded by compression using ASTM D 1928. The flexional and secant modules at 2 percent are measured according to ASTM D-790.
Dynamic Mechanical Analysis (DMA) [0179] Dynamic Mechanical Analysis (DMA) is measured on compression-shaped discs formed in a press heated to 180 ° C at a pressure of 10 MPa for 5 minutes and then cooled in the press at 90 ° C / min The tests are conducted using an ARES controlled strain rheometer (TA Instruments) equipped with dual overhang adapters for torsion tests.
[0180] A 1.5 mm plate is pressed and cut like a
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97/119 bar with dimensions of 32x12 mm. The sample is fixed at both ends by claws separated by 10 mm (claw separation (DL) and subjected to successive temperature steps from -100 ° C to + 200 ° C (5 ° C per step). torsion module G 'is measured at an angular frequency of 10 rad / s, the strain range being maintained between 0.1 percent and 4 percent to ensure that the torque is sufficient and that the measurement remains in the linear regime.
[0181] An initial static force of 10 g is maintained (self-tensioning module) to prevent loosening of the sample when thermal expansion occurs. As a consequence, the separation of AL clamps increases with temperature, particularly above the melting or softening point of the polymer sample. The test stops at maximum temperature or when the space between the claws reaches 65 mm.
Fusion Properties [0182] The Melt Flow Rate (MFR) and the Melt Index (MI or I2) are measured according to ASTM D1238, Condition 190 ° C / 2.16 kg.
Fractionation by Analytical Temperature Rising Elution in (ATREF) [0183] The elution fractionation analysis by analytical temperature rising in (ATREF) is conducted using the method described in U.S. Patent No. 4,798,081, the relevant portion of which being hereby incorporated by reference. The composition to be analyzed is dissolved in trichlorobenzene and allowed to crystallize in a column containing an inert support (stainless steel shot) slowly reducing the temperature to 20 ° C at a cooling rate of 0.1 ° C / min. The column is equipped with a
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98/119 infrared. An ATREF chromatogram curve is then generated by eluting the crystallized polymer sample from the column by slowly increasing the temperature of the solvent (trichlorobenzene) eluting from
0 to 120 ° C at a rate of
1.5 ° C / min.
[0184]
All publications and patents mentioned in this disclosure are fully incorporated by reference, for the purpose of describing and disclosing, for example, the constructs and methodologies that are described in the publications, which may be used in connection with the methods, compositions, articles and processes presently described. The publications discussed throughout the text are provided solely for their disclosure before the filing date of this application. Nothing here should be understood as an admission that inventors do not deserve to predate such disclosure by virtue of a previous invention. If the use of terminology used in any reference that is incorporated by reference conflicts with the use or terminology used in this disclosure, the use or terminology used in this disclosure will prevail.
[0185] Unless otherwise specified, when a range of any kind is disclosed or claimed, for example, a range of molecular weights or values of a parameter such as N, and the like, it is intended to individually disclose or claim each possible number that such a range could reasonably encompass, including any sub-ranges encompassed by it. For example, when Depositors 'intention is to disclose that a value of N may be 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 60 or greater, the depositors' intention is to disclose or claim individually
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99/119 any possible number that such a range could encompass, consistent with the disclosure here, including any range, sub-range, or combinations of ranges encompassed here. Consequently, depositors reserve the right to reserve or exclude any members or sub-bands within such a group, which may be claimed according to a band or in any similar way, if for any reason the depositors choose to claim less than the full measure of disclosure, for example, to justify an unknown reference from depositors when filing the patent application.
[0186] The summary of this disclosure is provided to meet the requirements of 37 C.F.R. § 1.72 and the purpose established in 37 C.F.R. § 1.72 (b) to allow the United States Patent and Trademark Office and the general public to quickly determine from a quick inspection of the nature and essence of technical disclosure. The summary is not intended to be used to interpret the scope of the attached claims or to limit the scope of the matter disclosed here. Furthermore, it is not intended to use any headings to establish the scope of the attached claims or to limit the material disclosed here. Any use of the perfect past tense to describe an example otherwise indicated as constructive or prophetic is not intended to reflect that the constructive or prophetic example has in fact been realized.
EXAMPLES [0187] The following examples are provided as a further illustration of the invention and are not intended to be limiting. The term overnight, if used, refers to a
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100/119 time of approximately 16-18 hours, the term room temperature refers to a temperature of 20-25 ° C, and the term mixed alkanes refers to a commercially available mixture of commercially available C _6-9 aliphatic hydrocarbons under the trade name Isopar E®, by ExxonMobil Chemicals, Inc. If the name of a compound here is at variance with its structural representation, the structural representation will prevail. The synthesis of all metal complexes and the preparation of all classification experiments are carried out in a dry nitrogen atmosphere using desiccator techniques (glove box),
including reactions occurring fully inside of one desiccator under an nitrogen atmosphere.[0188] MMAO if refers to methylalumoxane modified, one methylalumoxanemodified with triisobutylaluminum,
commercially available from AkzoNobel Corporation.
[0189] The following catalysts and cocatalysts may be used in accordance with this disclosure.
[0190] Catalyst (A1) is [N- (2,6-di (1-methylethyl) phenyl) starch) (2-isopropylphenyl) (α-naphthalen-2-diyl (6-pyridin2-diyl)] dimethyl hafnium, prepared according to the teachings of WO 03/40195, 2003US0204017, US patent application serial No. 10 / 429,024, filed on May 2 , 2003 and WO 04/24740.
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101/119 [0191]
Catalyst (A2) [N- (2,6-di (1methylethyl) phenyl) starch) (2-methylphenyl) (1,2-phenylen-2-diyl (6pyridin-2-diyl) methane)] dimethyl hafnium, prepared from according to the teachings of WO 03/40195,
2003US0204017, patent application
US n ^the number 10 / 429,024, filed in May 2003, and WO 04/24740.
[0192]
Catalyst (A3) bis [N, N '- (2,4, 6tri (methylphenyl) starch) -ethylenediamine] hafnium dibenzyl.
[0193]
(A4) is
Bis (2-oxoyl-3- (dibenzo-1Hpirrol-1-yl) -5- (methyl) phenyl) -2-phenoxymethyl) cyclohexane-1,2diyl zirconium (IV) dibenzyl catalyst, prepared substantially in accordance with the teachings of U.S. patent No. 6,897,276.
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102/119 [0194]
Catalyst (A5) is (bis (1-methylethyl) (2-oxoyl-3,5di (t-butyl) phenyl) imino) zirconium dibenzyl.
[0195]
is here entirely with
WO 2007/035493, which agreement is incorporated by reference.
[0196]
(A6) bis- (1- (2methylcyclohexyl) ethyl) (2-oxoyl-3,5-di (t-
The preparation of the catalyst (A5) is carried out according to WO 2007/035493, which is incorporated here in full by
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103/119 reference.
[0197]
Catalyst (A7) is (t-butylamido) dimethyl (3-Npirrolil-1,2,3,3a-7a-p-inden-1-yl) silanetitanium dimethyl prepared substantially according to the techniques of U.S. Patent No. 6,268. 444.
[0198]
is (A8)
Catalyst (t-butylamido) di (4metilfenil) (2-methyl-1,2,3,3a, 7a-p-inden-1-yl) silanetitanium dimethyl prepared substantially according to US Patent No US-ensionamentos The -2003/004286.
[0199]
Catalyst (A9) is (t-butylamido) di (4-methylphenyl) (2-methyl-1,2,3,3a, 8a-p-indacen-1-yl) silanotitanium dimethyl prepared substantially in accordance with the teachings of US patent no. US-a-2003/004286.
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104/119 [0200]
Catalyst (A10) is bis (dimethyldisiloxane) (inden-1-yl) zirconium dichloride commercially available from
Sigma-Aldrich.
[0201]
Co-catalyst 1 A mixture of methyl salts (alkyl
C _14-18 ) tetrakis borate ammonium (pentafluorfenyl) (hereinafter armenian borate), prepared by the reaction of a trialkylamine (Armeen ^MR
M2HT, commercially available from Akzo-Nobel,
Inc.), HCl and Li [B (C ₆ F ₅ ) ₄ ], substantially as disclosed in the patent
US No 5.919.9883, ex.
2.
[0202]
2 alkyl cocatalyst salt (C14-18) dimethyl, bis (tris (pentafluorophenyl) -alumano) -2-undecilimidazolida mixed, prepared according to US Patent No. 6,395,671,
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105/119 ex. 16.
EXAMPLES
Example 1
Preparation and Characterization of a Double Headed Zinc Chain Transfer Agent Et [Zn (CH ₂ ) ₁₀ ] _N ZnEt [0203] With reference to scheme 3, a sample of triethylborane (6.2 g, 63 mmoles) is weighed into a 4-ounce glass jar. A PTFE-coated stir bar is added and stirring is started. Borane (3.0 mL of pure dimethyl sulfide complex, 32 mmoles) is added slowly to the liquid. The resulting colorless liquid is stirred for 2 hours at room temperature, after which time the liquid is cooled to -40 ° C, and 1,9-decadiene (2.9 ml, 16 mmol) is added slowly. The temperature of the solution is allowed to rise slowly to room temperature, and stirring is continued for 1 hour. NMR spectra are taken from the crude material, demonstrating complete consumption of the olefin. Excess diethylbotane is removed in vacuo in order to leave a colorless oil behind. The mixture is cooled to -40 ° C in a freezer. The mixture is then removed and diethyl zinc (5.8 g, 47 mmoles) that has been pre-cooled to -40 ° C is added dropwise to the mixture. The formation of a significant amount of white solid is observed as diethyl zinc is added. The mixture is stirred overnight at room temperature, after which time a gray solid is observed in the reaction mixture. Toluene (about 30 ml) is added and the mixture is stirred while heating to 55 ° C to dissolve the product. The mixture is decanted and the solution filtered through a 0.45 micron frit. The solution is placed in a
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106/119 freezer at -40 ° C. The white solid is isolated and dried under vacuum. The solid is redissolved in 20 ml of toluene at 60 ° C and the solvent removed in vacuo at 35 ° C to remove excess diethyl zinc. After drying in vacuo for 2 hours at 40 ° C, the product mass is 1.3 g.
[0204] The molar ratio of Zn: B is preferably greater than 1, to reduce or minimize any excess of Et2B (CH2) nBEt2 present in the mixture. The N value is controlled either by vacuuming the double-headed chain transfer agent to remove ZnR ^{1 2} 2 (to increase N) or by adding more ZnR ¹ 2 to the double-headed chain transfer agent (to increase N) .
[0205] Both H ¹ and C ^{1 3} NMR spectra are recorded in d _g -THF and are consistent with a polymer or oligomer containing Zn-octyl-Zn units. NMR data shows that the zinc-ethyl groups are present at a level of 2% of the zinc-decyl-zinc groups. These data indicate that the N value for Et [Zn (CH2) 10] NZnEt prepared in this way ranges from about 20 to about 150.
Layout 3
TEMPERATURE
BEt ₃ + BHj * SMc ₂ AMBIENTE, „| ij, _B | 11 + 0.25
Zn [0206]
Εΐ, Β
The results and conditions used for the polymerization of ethylene (E) and propylene (P) are provided in table 3. The double-headed CSA (abbreviated from DH CSA) was loaded as a toluene slurry in the Parr reactor for the
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107/119 matches. Both T _m and T _g were determined by DSC (Differential Scanning Calorimetry). Common conditions for matches 1-5 are as follows: Temperature, 60 ° C; IPE, 600 grams; P, 169 grams; E, 15 grams; catalyst precursor [N- (2,6-di (1-methylethyl) phenyl) starch) (2-isopropylphenyl) (anaftalen-2-diyl) (6-pyridin-2-diyl) methane) hafnium dimethyl (catalyst A1) . As these data illustrate, very low polydispersities can be performed on the resulting polymers using the CSAs as disclosed here.
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Table 3. Polymer properties and conditions for the polymerization of ethylene (E) and propylene (P) .A
Departure ^B P DP Departure Time Catalyst Activ. CSA AT Yield Efficiency Tg Tm Ah Mn Mw Mw / M _n n ^o (psi) (psi) min. pmoles Metal pmoles Name pmoles (° C) (g) (g in / g Metal) (° C)(° C) (J / g) (g / mol)1 187.8 37.7 11 5 Hf 6 DioctZinc 750 4.51 68.5 76,755 -45, 8 146.5 23, 6 14,385 104,869 7.29 2 222.9 16, 4 5 5 Hf 6 DH CSA 750 7.78 24.4 27,340 -53, 1 none28,939 94,630 3.27 3 221, 3 52.4 30 2.5 Hf 3 DH CSA 750 9, 37 42.7 95,692 -47, 3 none71,482 158,689 2.22 4 221, 8 66.6 30 2.5 Hf 3 DHCSA / 15% TEN 625 6, 57 53, 6 120,119 -47, 8 122.4 16, 0 124,614 267,921 2.15 5 218, 3 87.5 102 2 Hf 2.4 DH CSA 917 10.79 63, 1 176,761 -53, 3 139.7 28, 9 303,501 905/043 2.98
A Abbreviations: Dioct Zinc Zn (C ₈ H ₁₇ ) ₂ ; DH CSA, Head Chain Transfer Agent
108/119
Doubles Et [Zn (CH2) 10] NZnEt, shown in scheme 3 of example 1; catalyst Hf, catalyst precursor [N- (2,6-di (1-methylethyl) phenyl) starch (2-isopropylphenyl) (α-naphthalen-2-diyl (6-pyridin2-diyl) methane)] hafnium dimethyl (A1 ), (CAS # 52196-95-4); Activator, R ₂ N (H) MeB (C ₆ F ₅ ) ₄ , R = hydrogenated seboalkyl (C14-18 alkyl) (CAS # 200644-82-2).
[0207] ^B Common conditions for matches 1-5: Temperature, 60 ° C; IPE, 600 grams; P, 169 grams; And, 15 grams.
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Example 2
Control N values in Chain Transfer Agents
Double Heads [0208] As provided here, double head chain transfer agents
R ¹ [M ^A -R ² -] _N -M ^A R ¹ and R ¹ [MBR ¹ -R ² ] nMB (R ¹ ) 2 are characterized by having values of N> 1. As illustrated in schemes 1 and 2, the rapid exchange at room temperature of zinc-hydrocarbyl groups between and in the midst of zinc dihydrocarbyl molecules is used to adjust the value or range of N values in the chain transfer agents.
This fast and reversible equilibrium point allows the value of N may be lowered by combining a known amount of 2 ZNR ¹ as a zinc dialkyl, with a known amount of CSA dual heads. Similarly, the N value can be increased by dissolving the double headed chain transfer agent in a solvent such as toluene and placing the solution under vacuum. In the latter case, the more volatile ZnR ¹ 2, for example, ZnEt2, is removed by vacuum, shifting the balance from the lowest N values to the highest N values.
[0209] The ratio of R ² to R ¹ plots can be measured by NMR spectroscopy of H and NMR of C [H] and used to determine the average value or range of N values for double-headed CSAs such as Et [ZnCH2CH2] NZnEt prepared this way.
Example 3
Preparation and Usefulness of Other Airport Transfer Agents
Double Head Chain [0210] With reference to scheme 3 and example 1, a large number of double head chain transfer agents
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110/119 (DHCSAs) having the formulas iNMgR ¹ , R ¹ [BR ¹ -R ² ] _n B (R ¹ ) 2,
R] _N Ga (R) ₂ , are prepared described in example 1, and if general polymerization results R ¹ [Zn-R ² -] NZnR ¹ , R ¹ [Mg-R ² R ¹ [AlR ¹ -R ² ] NAl (R ¹ ) 2, and R ¹ [GaR ¹ using methods analogous to those expected to provide polymers and similar to those described in table 3. Examples of DH CSAs are shown in table 4.
Table 4. Examples of possible double-headed chain transfer agents
General Formula R ¹ R ² N Average R ¹ [Zn-R ² ] _N ZnR ¹ Et (CH2) 6 3-20 Me (CH2) 6 5-10 Et (CH2) 10 120-150 Pr (CH2) 5 12-25 Et O [SiMe2 (CH2) 212 20-40 R ¹ [Mg-R ² -] _N MgR ¹ Et (CH2) 8 20-30 Me (CH2) 4 75-95 Et (CH2) 10 4-6 R ¹ [BR ¹ -R ² -] nBR ¹ 2 Et (CH2) 7 6-20 Et (CH2) 8 50-80 Me (CH2) 10 45-80 R ¹ [AlR ¹ -R ² -] NAlR ¹ 2 Et (CH2) 7 10-30 Me (CH2) 8 5-8 Et (CH2) 10 40-60 Pr O [SiMe2 (CH2) 312 6-12 Me (CH2) 5 15-40 R ¹ [GaR ¹ -R ² -] _N GaR ¹ 2 Et (CH2) 6 20-40 Et (CH2) 9 10-12 Et (CH2) 10 55-85
Example 4
M _w and Polydispersity Index Predicted for Polymers Obtained Using Linear Double Head Chain Transfer Agents of Various Lengths [0211] A series of calculations were performed in order to estimate the molecular weight (Mw) and the polydispersity index (PDI = M _w / M _n ) of ethylene-propylene block copolymers prepared using double-headed zinc chain transfer agents of varying lengths. These calculations are the
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111/119 result of a statistical analysis of the copolymer, based on the assumption that the eligible valences of each group grow a more likely kinetic chain, when double-headed chain transfer agents having the following formula were prepared:
R ¹ - [Zn-R ² -] _N Zn-R ¹ where
R ¹ in each occurrence is a monovalent hydrocarbyl portion;
R ² in each occurrence is a hydrocarbadiil having from 2 to 20
atoms of carbon, including; and Nor each occurrence is an integer from 2 to 50, including. [0212] Therefore, examples of agents transfer in jail encompassed for this disclosure include those with
N> 1. The following structure illustrates the difference between a double-headed (D) CSA site that constitutes each zinc alkanodiyl bond and a single-headed (M) CSA site that constitutes each zinc alkyl bond. With reference to this structure as a guide, when N> 1, the ratio of multiple-headed sites to single-headed sites, abbreviated to Q, will constitute the ratio of double-headed CSA sites (D) to single-headed CSA sites (M), for linear double-headed zinc chain transfer agents, since all multiple-headed sites are double-headed. In this case, the value of Q is equal to N, and also equal to the number of zinc atoms in the CSA minus 1. Table 5 below illustrates this concept for some double-headed chain transfer agents of the formula R ¹ - [ Zn-R ² -] _N Zn-R ¹ .
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Table 5. Characteristics of Zinc Linear Double Head Chain Transfer Agents
N Zinc Atoms D Sites M Sites Q = D / M 1 2 2 2 1 2 3 4 2 2 3 4 6 2 3 4 5 8 2 4 5 6 10 2 5 6 7 12 2 6 7 8 14 2 7 8 9 16 2 8
[0213] THE as the heads CSA molecule doubles and the value in N increase the reason in CSA sites from heads doubles (D) for sites from CSA in single head (M) also increases, and the properties gives composition of polymer
result can be changed, table 6. For example, the polydispersity of the resulting ethylene copolymers prepared using increasingly long double-headed CSAs is shown to increase as Q increases, table 6. The first row of table 6 provides calculations for the CSAs of double heads having the formula R ¹ -Zn-R ¹ -Zn-R ¹ -R ² -ZnR ¹ , where N and Q are 1 in the formula R ¹ - [Zn-R ² ] _N -Zn-R ₁ . Therefore, as the Q value increases, the overall molecular weight increases while the polydispersity decreases and approaches the values for the double-headed CSA, calculated as having a PDI of 1.5.
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Table 6. M _w Global and Polydispersity Predicted for CSAs of
Double Linear Heads against Q. ^A
N &Q Global Single Head Double Heads Mw PDI F (mass) Mw PDI F (mass) Mw PDI 1 1.250 M 1,875 0.500 M 2 0.500 1.5 M 1.5 2 1.333 M 1,778 0.332 M 2 0.667 1.5 M 1.5 3 1.375 M 1,719 0. 250 M 2 0. 750 1.5 M 1.5 4 1,400 M 1,680 0.200 M 2 0.800 1.5 M 1.5 5 1.417 M 1.653 0. 167 M 2 0.833 1.5 M 1.5 6 1. 429 M 1,633 0. 143 M 2 0.857 1.5 M 1.5 7 1.438 M 1,617 0.125 M 2 0.875 1.5 M 1.5 8 1.444 M 1.605 0.11 M 2 0.889 1.5 M 1.5 9 1.450 M 1.595 0.100 M 2 0.900 1.5 M 1.5 10 1,455 M 1,587 0.01 M 2 0.917 1.5 M 1.5 11 1.458 M 1.580 0.083 M 2 0.923 1.5 M 1.5 12 1. 462 M 1.574 0.07 M 2 0.923 1.5 M 1.5 13 1. 464 M 1.599 0.071 M 2 0.929 1.5 M 1.5 14 1. 467 M 1. 564 0.067 M 2 0.933 1.5 M 1.5 15 1. 469 M 1. 561 0.063 M 2 0.938 1.5 M 1.5 16 1,471 M 1.557 0.059 M 2 0.941 1.5 M 1.5 17 1,472 M 1.554 0.056 M 2 0.944 1.5 M 1.5 18 1,474 M 1.551 0.053 M 2 0.947 1.5 M 1.5 19 1.475 M 1. 549 0.050 M 2 0.950 1.5 M 1.5
Mw is the molecular weight of the weight average kinetic chain.
Example 5
Preparation and Use of Chain Transfer Agents
Double Headed Aluminum of the form Al [(CH ₂ ) _m ] ₃ Al [0214] A sample of 5,000 g of triisobutyl aluminum (23.55 mmoles) and 5.046 g (36.50 mmoles) of 1,9-decadiene were combined in about 30 ml of mesitylene (p.ebul. 164-165 ° C). This mixture was heated to reflux (164-165 ° C) for about 4 hours in a 4-ounce vessel connected to the reflux tube, in a glove box. After the reflux temperature of the solvent, the isobutylene by-product was expected to have been extracted from the solution. After this time, heating was stopped, the mixture was allowed to cool to room temperature, and was kept at this temperature.
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114/119 temperature for about 2.5 days. The product was a gel. The product description in the diagram below is representative of the empirical formula of the CSA product, which is polymeric. Therefore, by describing these chain-transfer agents using general formulas such as Al [(CH ₂ ) _m ] ₃ Al and illustrating their structures as shown in the diagram below, it is intended to reflect a medium stoichiometry and an empirical formula that is intended to include all species in which (CH2) m plots of a single metal bond to more than one additional metal.
Layout 4
Example 6
Preparation and Use of Cyclic Double Head Magnesium Chain Transfer Agents of the Mg [(CH ₂ ) _m ] ₂ Mg form [0215] Cyclic Magnesium Chain Transfer Agents of the Mg [(CH ₂ ) _m ] ₂ Mg form , containing only R ² groups and not R ¹ groups, can be prepared in a manner analogous to the preparation of the corresponding aluminum reagents as illustrated by the synthesis of Al [(CH2) 10] 3Al in scheme 4. Synthesis and examples of zinc compounds similar are found in J. Organometallic Chem., 1982, 224, 217, which is incorporated herein in its entirety by reference, and magnesium compounds may also be prepared
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115/119 similar. Chain transfer agents of the formula Mg [(CH ₂ ) _m ] ₂ Mg that can be used in the described catalytic processes include those compounds having n = 6, 7, 8, and the like.
Example 7
Use of Cyclic Double Head Chain Transfer Agents to Prepare Acyclic Double Head Chain Transfer Agents [0216] Schemes 5 and 6 illustrate synthetic methods by which cyclic double head chain transfer agents of the form M ^A [R ² ] 2M ^A could be used to prepare acyclic CSAs of the general formula R ^{* 1 2} [M ^A -R ² -] NM ^A R ¹ . The specific examples are applicable to compounds of the formula M ^A [(CH2) m] 2M ^A where M ^A is Zn or Mg, and are illustrated for zinc. Scheme 5 demonstrates how the rapid balance between the alkyl groups in the zinc system could be used to provide CSAs of N> 1 of the Et [Zn (CH ₂ CH ₂ )] _N ZnEt form from the N compound
Et [Zn (CH2CH2)] ZnEt and the cyclic CSA
Zn [(CH ₂ ) ₄ ] ₂ Zn. In this scheme, to provide R ¹ [M ^A -R ² ] _N M ^A R ¹ , in ₂ all R plots are equal.
similar zinc that could be used to provide
CSAs that
N> 1 from the compound of
EtZn (CH ₂ ) ₈ ZnEt
Cyclic CSA Zn [(CH ₂₎ 4] ₂ Zn, to provide a CSA that contains
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116/119 different R ² plots. In this scheme, a general formula CSA
R ¹ [M ^A -R ^2A -M ^A ] z [M ^to R ^2a -M ^a ] R ^2b -M ^a ] ZR ¹ formed, where R ^2a is (CH ₂ ) ₈ and R ^2b is (CH ₂ ) ₄ . While Z = 1 is illustrated in scheme 6, which corresponds to a CSA of N> 1, it is expected that the addition of an additional cyclic CSA Zn [(CH2) 4] 2Zn will provide CSAs of Z> 1, in this specific example, Formula CSAs
Et [Zn (CH2) 4] Z [Zn (CH2) 8Zn] [CH2) 4Zn] ZZnEt. As provided in Table 1, structures and compositions such as R ¹ [M ^A -R ^2B -] _Z [M ^A R -M] [- R -M] ZR are readily described by the Newkome nomenclature.
Layout 6
Et
Example 8
Preparation and Use of a Multi-Headed Zinc Chain Transfer Agent Precursor, I [Zn (CH ₂ ) ₈ ZnI [0218] With reference to scheme 7, a sample of 1,8diiodooctane (dried over CaH2 and filtered through activated alumina; 10.61 g) was weighed in a 40 ml amber flask containing a PTFE coated stir bar and diluted with THF to a total volume of about 20 ml. Activated Zn dust (obtained as a THF solution, filtered and dried in vacuo, 4.55 g) was added slowly to the stirred solution.
An exotherm was observed by adding zinc to the 1,8-diiodooctane solution. When the reaction mixture cooled to room temperature, the resulting slurry was heated with stirring at 60 ° C for 2.5 days. After this time, the reaction
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117/119 was filtered through Celite and the precipitate was washed with toluene. The filtrate was concentrated in vacuo to give a thick yellow liquid. Analysis of this material by H ¹ NMR spectroscopy (C ₆ D ₆ ) confirmed the formation of the desired product, I [Zn (CH ₂ ) ₈ ZnI, together with approximately 20% IZnCH ₂ (CH ₂ ) ₆ CH ₃ , and THF.
Layout 7
[0219]
The product I [Zn (CH2) 8ZnI of scheme 7 can be used in the same way as EtZn (CH2) 8ZnEt of scheme 6, that is, to vary the value of N and generate new CSAs. If desired, the product I [Zn (CH ₂ ) ₈ ZnI can be used in a metathesis reaction such as alkylation or alkoxylation, to form a number of species of type R ¹ [Zn (CH2) 8] ZnR ¹ , where R ¹ may be hydrocarbyl, hydrocarbyl oxide, hydrocarbilamide, tri (hydrocarbyl) silyl, and the like.
Example 9
Preparation and Usefulness of a Chain Transfer Agent
Dendritic [0220] This constructive example is described with reference to scheme 8. In a glove box purged with nitrogen, diethylborane (1 mmol) is added dropwise to a stirred solution of trialylmethane (10 mmoles) in toluene at -40 ° Ç. This mixture is stirred for 2 hours at room temperature, after which time the solvent and excess trialylmethane are removed in vacuo. Diethylzinc (1.5 mmol) is added slowly to the hydrobored trialylmethane and the mixture
Petition 870190033519, of 4/8/2019, p. 130/135
The resulting 118/119 is stirred at room temperature overnight. The resulting mixture is suspended in toluene (15 ml) and filtered through a syringe frit. The resulting solution is placed under vacuum to remove volatile by-products and solvent.
The resulting zinc compound is hydroborated with diethylborane at -40 ° C while dissolved in toluene. The volatiles are removed under vacuum. Excess of diethylzinc (about 4 equivalents relative to the zinc compound) is added to the intermediate and the reaction is stirred overnight at room temperature. The resulting mixture is dissolved in toluene, filtered through a syringe frit, and volatile by-products are removed under vacuum. The dendritic zinc chain transfer agent as shown in scheme 8 is provided. Similar reaction schemes using different reagents to provide the desired dendritic chain transfer agent are contemplated.
Petition 870190033519, of 4/8/2019, p. 131/135
119/119 [0221] With reference to scheme 8 and reagents A to G, scheme 9 below illustrates a method by which larger dendritic chain transfer agents could be constructed by altering the reaction sequence of scheme 8. It is not intended that this scheme is limiting, since the use of other reagents such as F can be contemplated to build the size and complexity of the dendrimer of
CSA by a slightly different process.
Layout 9
1 B -C 1) B (-F) Λ --- AND ................................................. .........................> G 2) D 2) D Ç 1) B C 1) B _G - E - G t ' ; 2) D 2) D
Petition 870190033519, of 4/8/2019, p. 132/135

权利要求:
Claims (4)
[1]
1. Chain transfer agent, characterized by the fact that it has the formula:
R ¹ [M ^A -R ² -] _N M ^A R ¹ or a derivative thereof containing Lewis base, or any combination thereof; Where
M ^a is Zn;
R ¹ in each occurrence is independently selected from hydrogen, halide, amide, hydrocarbyl, hydrocarbilamide, dihydrocarbilamide, hydrocarbyl oxide, hydrocarbyl sulfide, dihydrocarbyl phosphide, tri (hydrocarbil) silyl; any hydrocarbyl group being optionally substituted with at least one halide, amide, hydrocarbilamide, dihydrocarbilamide, or hydrocarbyl oxide; and each R ¹ containing carbon having from 1 to 20 carbon atoms, inclusive;
₂
R in each occurrence is independently selected from (CH2) m, O [CH2) nCH2CH2] 2, S [(CH2) nCH2CH2] 2, RAN [(CH2) nCH2CH2] 2, (RB) 2Si [(CH2) nCH2CH2] 2 , (RB) 3SiOSiRB [(CH2) nCH2CH2] 2, or [Si (R ^B ) 2 (CH2) nCH2CH2] 2O;
where n in each occurrence is independently an integer from 1 to 20, inclusive; m is an integer from 2 to 20, inclusive; R ^A is H or a hydrocarbyl having from 1 to 12 carbon atoms, inclusive; and R ^B at each occurrence is a hydrocarbyl having 1 to 12 carbon atoms, inclusive; and
N, on average, in each occurrence is a number from 5 to 150, inclusive.
[2]
2. Process for the polymerization of at least one addition-curable monomer to form a composition of
Petition 870190033519, of 4/8/2019, p. 133/135
2/2 polymer, the process characterized by the fact that it comprises:
- contacting at least one polymerizable monomer by addition with a catalyst composition under polymerization conditions; the catalyst composition comprising the contact product of at least one polymerization catalyst precursor, at least one cocatalyst, and the chain transfer agent, as defined in claim 1.
[3]
3. Multi-block copolymer, characterized by the fact that it is obtained by the process, as defined in claim 2.
[4]
4. Catalyst composition, characterized by the fact that it comprises the contact product of at least one polymerization catalyst precursor, at least one cocatalyst, and the transfer agent, as defined in claim 1.

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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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2019-06-11| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2019-08-20| 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 20/07/2010, OBSERVADAS AS CONDICOES LEGAIS. (CO) 20 (VINTE) ANOS CONTADOS A PARTIR DE 20/07/2010, 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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US22961009P| true| 2009-07-29|2009-07-29|

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US61/229,610|2009-07-29|

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PCT/US2010/042605|WO2011016991A2|2009-07-29|2010-07-20|Dual- or multi-headed chain shuttling agents and their use for the preparation of block copolymers|

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