COMPOSITION AND POLYMERIZATION PROCESS

专利摘要:
atomizer dried catalyst compositions and polymerization processes that employ them. atomizer dried catalyst compositions comprising a transition metal complex and polymerization processes which employ them are described in this case. one embodiment provides a spray dried catalyst composition comprising a transition metal catalyst component represented by the following formula: and the polymerization process that employs it.
公开号:BR112013029135B1
申请号:R112013029135-4
申请日:2012-03-28
公开日:2020-12-15
发明作者:Wesley R. Mariott；Phuong A. Cao；Daniel P. Zilker；John H. Oskam；Cliff R. Mure
申请人:Univation Technologies, Llc；
IPC主号:

专利说明:

FIELD OF THE INVENTION
[001] Atomizer dried catalyst compositions comprising a transition metal complex and polymerization processes employing them are described in this case. BACKGROUND
[002] Progress in polymerization and catalysts has produced new polymers that have improved physical and mechanical properties useful in a wide variety of products and applications. With the development of new catalysts, the choice of polymerization, such as in solution, in suspension, in high pressure or in the gas phase, to produce a particular polymer has been greatly expanded. Advances in polymerization technology have also provided more efficient, highly productive and economically improved processes.
[003] Metallocene catalysts have been widely used to produce polyolefins such as polyethylene polymers. They provided effective processes and a variety of new and improved polymers. In addition, catalyst compositions have also been used which comprise more than one catalyst or a catalyst component, in effect, which provides more than one active site to polymerize monomers during the polymerization process. Two or more catalyst components have been used, for example, to produce multimodal polymers. However, there is an ongoing focus in the industry for the development of new and improved catalyst compositions. Some kept their focus on designing catalyst compositions to produce new polymers, others on improved operability and still others on improving catalyst productivity.
[004] Polymers produced with a multimodal molecular weight distribution offer unparalleled properties for the product. Multimodal products can be produced by several methods, such as mixing different polymers that produce multimodal polymers under a series of reaction conditions and reacting different catalysts under a single reactor condition. One process that has been proven to be commercially viable is the production of multimodal catalyst systems in which a catalyst system comprises more than one catalyst or catalyst component, thereby, in effect, providing more than one active site for polymerizing monomers during the polymerization process. When fed into a reaction system, each catalyst component concurrently produces a polymer component with distinct product properties. The overall result is a polymer composition with distinct advantages of the product.
[005] Some different processes and techniques have been developed to obtain multimodal catalyst systems and polymers with these multimodal catalyst systems. For example, bimodal catalyst compositions have been used that comprise a combination of a Group 15 containing metal compound (a bisamide compound) and a metallocene compound. One of the advantages of these multimodal catalyst systems is in the division of the molecular weight (proportion of high to low molecular weight polymer produced). The productivity of a catalyst, that is, the amount of polymer produced per gram of the catalyst, as well as the customization of the division of the molecular weight of the polymer produced with these multimodal catalysts can be an important reason for concern for polyolefin producers. Thus, there is an ongoing need for new and improved catalyst and catalyst compositions. SUMMARY
[006] In this case, atomizer dried catalyst compositions are described which comprise a transition metal catalyst component represented by the following formula:
where: M is Fe [II], Fe [III], Co [I], Co [II], Co [III], Mn [I], Mn [II], Mn [III], Mn [IV], Ru [II], Ru [III] or Ru [IV]; X represents an atom or group covalently or ionically bonded to the metal M; T is the oxidation state of the metal; b is the valence of the atom or group X and R1 to R7 are each independently selected from the group consisting of hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, substituted heterohydrocarbyl, aryl, hydrocarbyl substituted aryl, heterohydrocarbyl substituted aryl, benzyl, benzyl substituted with hydrocarbyl, benzyl substituted with heterohydrocarbyl and SiR'3 where each R 'is independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, substituted heterohydrocarbyl and when any two or more of R1 to R7 are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, substituted heterohydrocarbyl, aryl, aryl substituted with hydrocarbyl, aryl substituted with heterohydrocarbyl, benzyl, benzyl substituted with hydrocarbyl or benzyl substituted with heterohydrocarbyl two or more may be linked to form one or more cyclic substituents. BRIEF DESCRIPTION OF THE DRAWINGS
[007] These drawings illustrate certain aspects of the present invention and did not need to be used to limit or define the invention.
[008] FIGS. 1-5 are graphical representations showing gel permeation chromatography coatings for various polyethylene resins produced by atomizer dried catalyst compositions. DETAILED DESCRIPTION
[009] Before the present compounds, components, compositions and / or processes are disclosed and described, it must be understood that unless otherwise indicated this invention is not limited to compounds, components, compositions, reagents, conditions of the reaction, ligands, specific or similar metallocene structures, as they may vary, unless otherwise specified. It also needs to be understood that the terminology used in this case is intended to describe particular modalities only and is not intended to be limiting.
[0010] Atomizer dried catalyst compositions comprising a complex transition metal catalyst component are described in this case. Atomizer dry mixed catalyst compositions are also provided that comprise a complex transition metal catalyst component and a non-metallocene catalyst component, such as a group 15 catalyst component. Atomizer dry mixed catalyst compositions are also provided. complex transition metal catalyst component, a non-metallocene catalyst component and a metallocene catalyst component. Also described herein are polymerization processes that employ atomizer-dried catalyst compositions, processes for obtaining atomizer-dried catalyst compositions and polymer products produced by polymerization processes.
[0011] It has been discovered that the productivity of a complex transition metal catalyst can be improved by spray drying. In addition, it has also been discovered that the productivity of a spray dried mixed catalyst composition comprising a non-metallocene catalyst component and / or a metallocene catalyst component can also be improved by combining with a complex transition metal catalyst. This is significant by the fact that a more economical catalyst system can be provided when it allows the preparation of a polymer at lower temperatures in the reactor and with greater catalyst productivity using the modalities of the catalyst compositions described here. Even further, it has been found that the molecular weight distribution of a multimodal polymer product produced using the atomizer dry mixed catalyst compositions described herein can be limited and the proportion of the melt flow has decreased by incorporating a complex catalyst of transition metal to atomizer dried catalyst composition. In addition, it has also been discovered that multimodal polymer products with lower global molecular weight and therefore higher flow rates can be produced by incorporating a complex transition metal catalyst into the atomizer dry mixed catalyst composition. In addition, the incorporation of complex transition metal catalyst into the atomizer dry mixed catalyst composition comprising a non-metallocene catalyst component and / or a metallocene catalyst component can provide the ability to manipulate the molecular weight and fluidity index of the resulting polymer as well as molecular weight distribution and flow rate ratio while retaining the overall properties of the polymer product.
[0012] In the description below and in the appended claims, the forms in the singular “one,” “one” and “o, a” include references in the plural unless otherwise specified. Thus, for example, the reference to "an exit group" as in a group "replaced with an exit group" includes more than one exit group, such that the group can be replaced with two or more of such groups . Similarly, reference to "a halogen atom" as in a "substituted with a halogen atom" group includes more than one halogen atom, such that the group can be replaced with two or more halogen atoms, the reference to " a substituent ”includes one or more substituents, reference to“ a ligand ”includes one or more ligands and the like.
[0013] As used in this case, all references to the Periodic Table of the Elements and groups thereof are to the NEW NOTATION published in HAWLEY'S CONDENSED CHEMICAL DICTIONARY, Thirteenth Edition, John Wiley & Sons, Inc., (1997) (reproduced here with the permission of IUPAC), unless reference is made to the previous form of IUPAC annotated with Roman numerals (which also appear in the same) or unless otherwise noted.
[0014] The term "catalyst," as used in this case, is used interchangeably with the term "catalyst component" and includes any compound or component or combination of compounds and components, which is capable of increasing the speed of a chemical reaction, such as such as polymerization or oligomerization of one or more olefins.
[0015] The term "catalyst composition" as used in this case, can include any number of catalysts in any combination as described herein, as well as any activator and support in any combination described herein.
[0016] The term "multimodal polymer," as used in this case, means a polymer comprising at least a "bimodal molecular weight distribution," the term of which is understood to have the broadest definition that persons skilled in the art have given to that term as reflected in print publications and granted patents. Thus, a multimodal polymer can have at least two peaks in molecular weight. For example, a single composition that includes polyolefins with at least two identifiable molecular weight distributions is considered to be a "multimodal" polymer, as that term is used in this case. In some modalities, without having different molecular weights, the polymer components can have different levels of comonomer distributions. Complex transition metal catalyst components
[0017] The catalyst compositions described herein may comprise a complex transition metal catalyst component. For example, spray dried catalyst compositions comprising a complex transition metal catalyst component can be used. The modalities of the complex transition metal catalyst components that can be used include a transition metal complex that has a ligand structure that supports bis (imino) pyridyl. An example of a suitable transition metal complex can be represented by the following formula (I):
where: M is Fe [II], Fe [III], Co [I], Co [II], Co [III], Mn [I], Mn [II], Mn [III], Mn [IV], Ru [II], Ru [III] or Ru [IV]; X represents an atom or group covalently or ionically bonded to the metal M; T is the oxidation state of the metal; b is the valence of the atom or group X and R1 to R7 are each independently selected from the group consisting of hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, substituted heterohydrocarbyl, aryl, hydrocarbyl substituted aryl, heterohydrocarbyl substituted aryl, benzyl, benzyl substituted with hydrocarbyl, benzyl substituted with heterohydrocarbyl and SiR'3 where each R 'is independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, substituted heterohydrocarbyl and when any two or more of R1 to R7 are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, substituted heterohydrocarbyl, aryl, aryl substituted with hydrocarbyl, aryl substituted with heterohydrocarbyl, benzyl, benzyl substituted with hydrocarbyl or benzyl substituted with heterohydrocarbyl two or more may be linked to form one or more cyclic substituents.
[0018] In some modalities, M in the formula (I) above is Fe [II], Fe [III], Ru [II], Mn [II], Co [II], Ru [III] or Ru [IV].
[0019] In some modalities of the Formula (I) transition metal complex, R5 can be represented by formula (II) and R7 can be represented by formula (III):
where: R8 to R17 are independently selected from the group consisting of hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl and substituted heterohydrocarbyl, when any two or more of R1 to R4, R6 and R8 to R17 are hydrocarbyl, substituted hydrocarbyl or heterohydrocarbyl substituted, two or more may be linked to form one or more cyclic substituents.
[0020] The Formula (II) and (III) ring systems can each be independently hydrocarbyl-substituted aryl groups, for example, 2, 6-hydrocarbilphenyl, 2, 4, 6-hydrocarbilphenyl or fused ring polyaromatics, for example example, 1-naphthyl, 2-naphthyl, 1-phenanthrenyl and 8-quinolinyl.
[0021] In some embodiments, at least one of R8, R10, R12, R13, R15 or R17 is hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl.For example, at least one of R8, R10 or R12 and at least one of R13, R15 or R17 is hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl.In another example, R8, R10, R12, R13, R15 or R17 are all independently selected from the group consisting of hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl. In yet another example, R8, R10, R12, R13, R15 or R17 are all independently selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, n -pentyl, neopentyl, n-hexyl, 4-methylpentyl, n-octyl, phenyl and benzyl.
[0022] R1 to R4, R6 and R8 to R17 can each be independently selected from the group consisting of hydrogen and C1 to C8 hydrocarbyl, for example, methyl, ethyl, n-propyl, n-butyl, t-butyl, n -hexyl, n-octyl, phenyl and benzyl.For example, R10 and R15 can each be independently selected from the group consisting of hydrogen, C1 to C8 hydrocarbyl (eg, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert.-butyl, n-pentyl, neopentyl, n-hexyl, 4-methylpentyl, n-octyl, phenyl), benzyl, fluorine, chlorine, bromine and iodine.
[0023] In some modalities, R5 is represented by the formula (II); R7 is 1238911141617 represented by formula (III); R, R, R, R, R, R, R, R and R are each hydrogen; R4, R6, R12 and R13 are each represented by methyl and R10 and R15 are each represented by fluorine.
[0024] In some modalities, R5 is represented by the formula (II); R7 is 12391011141516 represented by formula (III); R, R, R, R, R, R, R, R and R are each hydrogen and R4, R6, R8, R12, R13 and R17 are each represented by methyl.
[0025] In some modalities, R5 is represented by the formula (II); R7 is represented by the formula (III); R1, R2, R3, R9, R11, R14 and R16 are each hydrogen and R4 R6 R8 R10 R12 R13 R15 and R17 are each represented by methyl.
[0026] In some modalities, R5 is a group that has the formula — NR18R19, R7 is a group that has the formula — NR20R21, where R18 to R21 are independently selected from the group consisting of hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl , heterohydrocarbyl and substituted heterohydrocarbyl; when any two or more of R1 to R4, R6 and R18 to R21 are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, two or more may be linked to form one or more cyclic substituents.
[0027] Each of the nitrogen atoms is coordinated by a "dative" bond, that is, a bond formed by the donation of a pair of solitary electrons from the nitrogen atom. The remaining bonds in each of these atoms are covalent bonds formed by sharing electrons between the atoms and the organic ligand as presented in the formula defined by the metal complex illustrated above.
[0028] The non-metallocene catalyst components can be used in the catalyst compositions described herein. For example, spray dried mixed catalyst compositions which comprise a complex transition metal catalyst component and a non-metallocene catalyst component can be used.
[0029] The non-metallocene catalyst component can be a Group 15 containing catalyst. As used in this case, the term "Group 15 containing catalyst" includes metal complexes from Group 3 to Group 12, where the metal is 2 to 4 coordinate group and coordination group or groups include at least two atoms from Group 15 and up to four atoms from Group 15. For example, the catalyst containing Group 15 can be a complex of a Group 4 metal and one to four ligands , such that the Group 4 metal is at least 2 coordinated and the coordination group or groups include at least two nitrogens. Examples of suitable Group 15 containing catalyst are described in WO 99/01460; EP 0893454A1 and Pats. No. 5,318,935; 5,889,128; 6,333,389B2; 6,271,325B1 and 7,718,566.
[0030] In some embodiments, the Group 15 containing catalyst may include Group 4 imino-phenol complexes, Group 4 bis (amide) complexes and Group pyridyl-amide complexes that are active with respect to the olefin polymerization to any extent .
[0031] The catalyst containing Group 15 can be described by the following formula (IV): αaβbYgMXn (IV)
[0032] Each X of Formula (IV) can be independently selected from the group consisting of halogen ions, hydrides, C1 to C12 alkyls, C2 to C12 alkenyls, C6 to C12 aryls, C7 to C20 alkylaryls, C1 to C12 alkoxys, C6 to C16 aryloxy, C7 to C18 alkylaryloxis, C1 to C12 halogenated alkyls, C2 to C12 halogenated alkenyls, C6 to C12 halogenated aryls, C7 to C20 halogenated alkylyls, C1 to C12 halogenated alkoxys, C6 to C16 halogenated aryloxy, C7 to C7 to C18 halogenated, C1 to C12 hydrocarbons containing heteroatom and substituted derivatives thereof. Each X can also be selected from the group consisting of alkoxides, phenoxides, carboxylates, sulfonates, triflates, sulfides substituted with halogen and derivatives thereof. Examples of suitable carboxylates include, but are not limited to, trifluoroacetate and pentafluorobenzoate. Examples of suitable sulfonates, but not limited to, trifluoromethanesulfonate ("triflate") and benzene sulfonate. In some embodiments, each X can also be selected from fluorinated alkyl amides, fluorinated alkenyl amides, fluorinated alkylaryl amides, fluorinated alkoxy amides, fluorinated aryloxy amides, fluorinated alkylaryloxys, fluorinated amides and derivatives thereof. In some embodiments, at least one X is a halogenated aryloxy group or a derivative thereof. For example, at least one X may be a pentafluorophenoxy group.
[0033] M of Formula (IV) can be selected from atoms from Group 3 to Group 12 or can be selected from atoms from Group 3 to Group 10 or can be selected from atoms from Group 3 to Group 6 or can be selected from Ni, Cr, Ti, Zr and Hf or can be selected from Zr and Hf.
[0034] Each β and Y of Formula (IV) can be R groups that comprise at least one atom from Group 14 to Group 16 and β (when present) and Y are the groups linked to M through between 2 and 6 atoms of Group 14 to Group 16, at least two atoms being atoms containing Group 15. More particularly, β and y are groups that can be selected from Group 14 and Group 15 containing: alkyls, aryls, alkylaryls and heterocyclic hydrocarbons and chemically bonded combinations thereof or can be selected from Group 14 and Group 15 containing: C1 to C10 alkyl, C6 to C12 aryl, C6 to C18 alkylaryl and C4 to C12 heterocyclic hydrocarbons and chemically bonded combinations thereof or can be selected from C1 to C10 alkylamines, C1 to C10 alkoxys, C6 to C20 alkylaryl amines, C6 to C18 alkylaryloxys and C4 to C12 nitrogen-containing heterocyclic hydrocarbons and C4 to C12 nitrogen-substituted heterocyclic hydrocarbons containing nitrogen and chemically bonded thereto they can be selected from anilinyl, pyridyl, quinolyl, pyrrolyl, pyrimidyl, purinyl, imidazyl, indolyl, C1 to C6 substituted alkyl groups selected from anilinyl, pyridyl, quinolyl, pyrrolyl, pyrimidyl, purinyl, imidazyl, indolyl; substituted C1 to C6 alkylamine groups selected from anilinyls, pyridyls, quinolyls, pyrrolyls, pyrimidyls, purinyls, imidazyls, indolyls, substituted amine anilinyls, pyridyls, quinolyls, pyrrolyls, pyrimidyls, purinyls, imidazyls and indolyls; substituted hydroxy groups selected from anilinyls, pyridyls, quinolyls, pyrrolyls, pyrimidyls, purinyls, imidazyls and indolyls; substituted methyl phenylamines and combinations thereof chemically bonded.
[0035] Each α of Formula (IV) can be a bonding group (or “bridging”) that, when present, forms a chemical bond with each of β or two Y, thereby forming a ligand “YαY "The." or "Yαβ" linked to M; α can also comprise an atom from Group 14 to Group 16 which can be linked to M via the atom from Group 14 to Group 16 and more particularly, α can be a divalent bridge-forming group selected from alkyl, aryl, alkenyl, heterocyclic arylene , alkylarylenes, alkylenes containing heteroatom, alkenylenes containing heteroatom and heterocyclic hydrocarbonylenes or α can be selected from the group consisting of C1 to C10 alkenes, C2 to C10 alkenyls, C6 to C12 arylenes, C1 to C10 divalent ethers, C6 to C12 arylenes containing O - or N-, C2 to C10 alkyleneamines, C6 to C12 aryleneamines and substituted derivatives thereof.
[0036] In formula (IV), a is an integer from 0 to 2, b is an integer from 0 to 2 and g is an integer from 1 to 2. In some embodiments, a can be 0 or 1 or a can be 1. In some modalities, a is 1, b is 0 and g is 2. In formula (IV), n is an integer from 0 to 4. In some modalities, n can be an integer from 1 to 3 or n can be an integer from 2 to 3.
[0037] The spray dried mixed catalyst composition may have a molar ratio of the non-metallocene catalyst component to the transition metal catalyst composition complex from approximately 10: 1 to approximately 1: 1, or from approximately 5: 1 up to approximately 1: 1 or from approximately 3: 1 to approximately 1: 1.
[0038] As used in this case, the term "combinations thereof chemically linked" means that adjacent groups, (groups β and Y) can form a chemical bond between them. For example, groups β and Y may be chemically linked through of one or more α groups among themselves.
[0039] As used in this case, the terms "alkyleneamines" and "aryleneamines" describe alkylamines and arylamines (respectively) which are deficient by two hydrogens, thereby forming chemical bonds with two adjacent y groups or with adjacent β and y groups. Thus, an example of an alkyleneamine is —CH2CH2N (CH3) CH2CH2— and an example of a heterocyclic hydrocarbilene or arylene amine is —C5H3N— (divalent pyridine). An "alkylene-arylamine" is a group such as, for example, —CH2CH2 (C5H3N) CH2CH2—. Metallocene Component Catalysts
[0040] Catalysts Metallocene components can be used in the catalyst compositions described herein. For example, spray dried mixed catalyst compositions comprising a complex transition metal catalyst component and a metallocene catalyst component can be used.
[0041] The metallocene catalyst component may include metallocene catalysts typically called "half sandwich," (i.e., at least one ligand) or "complete sandwich," (i.e., at least two ligands) compounds that have one or more Cp ligands (cyclopentadienyl and isolobal ligands to cyclopentadienyl) attached to at least one metal atom from Group 3 to Group 12 and one or more leaving group (s) attached to at least one metal atom. Hereinafter, these compounds will be termed "metallocene (s)" or "metallocene catalyst component (s)."
[0042] Metallocene Component Catalysts can include compounds represented by the formula (V): CpACpBMXn (V)
[0043] The metal atom "M" of the metallocene catalyst component, as described in the specification and in the claims, can be selected from the group consisting of atoms from Groups 3 to 12 atoms and atoms from the Group of lanthanides or can be selected in the group consisting of the atoms of Groups 4, 5 and 6 it can either be a Ti, Zr or Hf atom or it can be a Zr atom.
[0044] The groups attached to the metal atom "M" are such that the compounds described below in the formulas and structures are neutral, unless otherwise indicated. The Cp ligand (s) form at least one chemical bond with the metal atom M to form the metallocene. Cp ligands are distinct from the output groups attached to the catalyst as they are not highly susceptible to substitution / abstraction reactions. In some embodiments, M is as described above; each X is chemically linked to M; each Cp group is chemically linked to M and n is 0 or an integer from 1 to 4 or n is 1 or 2.
[0045] The ligands represented by CpA and CpB in formula (V) can be the same or different cyclopentadienyl ligands or isolobal to cyclopentadienyl ligands, one or both may contain heteroatoms and one or both may be replaced by one or more R groups. For example, CpA and CpB can be independently selected from the group consisting of cyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl and unsubstituted derivatives of each.
[0046] Regardless, each CpA and CpB of Formula (V) can be unsubstituted or substituted with any or combination of R substituent groups. Non-limiting examples of R substituent groups as used in formula (V) include hydrogen, hydrocarbyl radicals, lower hydrocarbyls, substituted hydrocarbyls, heterohydrocarbyls, alkyls, lower alkyls, substituted alkyls, heteroalkyls, alkenyls, lower alkenyls, substituted alkenyls, heteroalkenyls, alkynyls, lower alkynyls, heteroalkynyls, alkoxys, lower alkoxyls, alkyls lower, arylthios, thioxies, aryls, substituted aryls, heteroaryls, aralkyls, aralkylenes, alcaryls, alcarylenes, halides, haloalkyls, haloalkenyls, haloalkylyls, heteroalkyls, heterocycles, heteroaryl, groups containing heteroatines, silylines, amines, phosphines, , cycloalkyls, acyls, ringlets, alkylthio ions, dialkylamines, alkylamides, alkoxycarbonyls, aryloxycarbonyls, carbamoyl, alkyl- and dialkyl-carbamoyl, acyloxis, acylaminos, aroylaminos and combinations thereof.
[0047] Non-limiting examples of more particular alkyl substituents R associated with formula (V) include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl, phenyl, methylphenyl and tert-butylphenyl groups and the like, including all its isomers, for example, tertiary butyl, isopropyl and the like. Other possible radicals include substituted alkyls and aryls such as, for example, fluoromethyl, fluroethyl, difluroethyl, iodopropyl, fluoroethyl, bromohexyl, chlorobenzyl and substituted hydrocarbyl organometalloid radicals that include trimethylsilyl, trimethylgermyl, methyldylethyl and the like and trifluoroethyl radicals that include trifluoroethylsides which include hydrocarbonate. silyl, methylbis (difluoromethyl) silyl, bromomethyldimethylgermyl and the like and disubstituted boron radicals including dimethylboro, for example, and disubstituted radicals of Group 15 including dimethylamine, dimethylphosphine, diphenylamine, methylphenylphosphine, radicals 16 and even ethyl sulfide. Other R substituents include olefins such as but not limited to olefinically unsaturated substituents including vinyl-terminated ligands, for example, 3-butenyl, 2-propenyl, 5-hexenyl and the like. In some embodiments, at least two R Groups, for example two adjacent R Groups, are associated to form a ring structure that has 3 to 30 atoms selected from the group consisting of carbon, nitrogen, oxygen, phosphorus, silicon, germanium, aluminum, boron and combinations thereof. In addition, a substituent R group such as 1-butanyl can form a binding association to the M element.
[0048] Each X in the formula (V) is independently selected from the group consisting of: any leaving group; for example, halogen ions, hydrides, hydrocarbyls, lower hydrocarbyls, substituted hydrocarbyls, heterohydrocarbyls, alkyls, lower alkyls, substituted alkyls, heteroalkyls, alkenyls, lower alkenyls, substituted alkenyls, heteroalkenyls, alkynyls, lower alkyls, substituted alkynyls, alkaline , lower alkoxides, aryloxides, hydroxyls, alkylthio, lower alkylthio, arylthio, thioxis, aryl, substituted aryl, heteroaryl, aralkyl, aralkylenes, alcaryl, alkaryl, halide, haloalkyl, heteroalkyl, heteroalkyl, heteroalkyl, heteroalkyl, heteroalkyl, heteroalkyl silyls, boryls, phosphines, phosphines, amines, amines, cycloalkyls, acyls, aryls, alkylthiols, dialkylamines, alkylamides, alkoxycarbonyls, aryloxycarbonyls, carbomoyls, alkyl- and dialkyl-carbamoyl, acyloxy, acylaminoes, arylaminos and combinations thereof. In some embodiments, X is C1 to C12 alkyl, C2 to C12 alkenyl, C6 to C12 aryl, C7 to C20 alkylaryl, C1 to C12 alkoxy, C6 to C16 aryloxy, C7 to C18 alkylaryloxy, C1 to C12 fluoroalkyl, C6 to C12 fluoroaryl , or C1 to C12 hydrocarbons containing heteroatom and substituted derivatives thereof. In some embodiments, X may be hydride, halogen ions, C1 to C6 alkyl, C2 to C6 alkenyl, C7 to C18 alkylaryl, C1 to C6 alkoxy, C6 to C14 aryloxy, C7 to C16 alkylaryloxis, C1 to C6 alkylcarboxylates, C1 to C6 fluorinated alkylcarboxylates, C6 to C12 arylcarboxylates, C7 to C18 alkylarylcarboxylates, C1 to C6 fluoroalkyls, C2 to C6 fluoroalkenyls or C7 to C18 fluoroalkylyls. In some embodiments, X can be selected from hydride, chloride, fluoride, methyl, phenyl, phenoxy, benzoxy, tosyl, fluoromethyls and fluorophenyls or can be selected from C1 to C12 alkyls, C2 to C12 alkenyls, C6 to C12 aryls, C7 to C20 alkylaryls, C1 to C12 substituted alkyls, C6 to C12 substituted aryls, C7 to C20 substituted alkyls and C1 to C12 alkyls containing heteroatom, C1 to C12 aryls containing heteroatom and C1 to C12 alkylaryls containing heteroatom or can be selected from chloride, fluoride, C1 to C6 alkyls, C2 to C6 alkenyls, C7 to C18 alkylaryls, C1 to C6 halogenated alkyls, C2 to C6 halogenated alkenyls and C7 to C18 halogenated alkyls or can be selected from fluoride, methyl, ethyl, propyl, phenyl, methylphenyl, dimethylphenyl , trimethylphenyl, fluoromethyls (mono-, di- and trifluoromethyls) and fluorophenyls (mono-, di-, tri-, tetra- and pentafluorophenyls). In some embodiments, at least one X is a halogenated aryloxy group or a derivative thereof. For example, at least one X may be a pentafluorophenoxy group.
[0049] The metallocene catalyst component can include those metallocenes of Formula (V) in which CpA and CpB bridge at least through a bridge-forming group, (A), such that the structure is represented by the formula (VI ): CpA (A) CpBMXn (VI)
[0050] These bridged compounds represented by the formula (VI) are known as "bridged metallocenes." CpA, CpB, M, X and n are as defined above for formula (V) and where each Cp ligand is chemically linked to M and (A) is chemically linked to each Cp. Non-limiting examples of the bridging group (A) include divalent alkyls, lower divalent alkyls, substituted divalent alkyls, divalent heteroalkyls, divalent alkenyls, substituted divalent alkenyls, divalent heteroalkenyls, divalent alkynyls, divalent lower alkynyls , divalent heteroalquinyls, divalent alkoxys, lower divalent alkoxys, divalent aryloxies, divalent alkylthioles, lower divalent arylthioles, divalent arylthioles, divalent aryls, divalent heteroaryls, divalent aralkyls, divalent, alkalylalalkyls divalents, divalent haloalkynyls, divalent heteroalkyls, divalent heterocycles, divalent heteroaryls, divalent groups containing heteroatom, divalent hydrocarbons, lower divalent hydrocarbons, substituted divalent hydrocarbons, divalent heterohydrocarbyls, divalent silyls, divalent boryls, divalent phosphines, divalent phosphines, divalent amines, divalent amines, divalent ethers and divalent ethers. Additional non-limiting examples of bridge-forming group A include divalent hydrocarbon groups containing at least one atom from Group 13 to 16, such as, but not limited to, at least one of a carbon, oxygen, nitrogen, silicon atom, aluminum, boron, germanium and tin and combinations thereof; wherein the heteroatom can also be a C1 to C12 alkyl or substituted aryl to satisfy the neutral valence. The bridge-forming group (A) can also contain substituent groups R as defined above for formula (V) including halogen and iron radicals. More particularly, non-limiting examples of the bridge-forming group (A) are represented by C1 to C6 alkylenes, Ci to C6 substituted alkylenes, oxygen, sulfur, R'2C =, R'2Si =, —Si (R ') 2Si ( R'2) -, R'2Ge = R'P = (where "=" represents two chemical bonds), where R 'is independently selected from the group consisting of hydride, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, substituted halocarbyl organometaloid, disubstituted boron, disubstituted Group 15 atoms, substituted Group 16 atoms and halogen radical and where two or more R 'can be associated to form a ring or ring system. In some embodiments, the bridge-shaped metallocene catalyst component of Formula (VI) has two or more bridge-forming groups (A).
[0051] Other non-limiting examples of bridge-forming group (A) include methylene, ethylene, ethylidene, propylidene, isopropylidene, diphenylmethylene, 1, 2-dimethylethylene, 1, 2-diphenylethylene, 1, 1, 2, 2-tetramethylethylene, dimethylsilyl, diethylsilyl, methyl-ethylsilyl, trifluoromethyl-butylsilyl, bis (trifluoromethyl) silyl, di (n-butyl) silyl, di (n-propyl) silyl, di (i-propyl) silyl, di (n-hexyl) silyl, dicyclohexylsilyl, diphenylsilyl, cyclohexylphenylsilyl, t-butylcyclohexylsilyl, di (t-butylphenyl) silyl, di (p-tolyl) silyl and the corresponding groups in which the Si atom is replaced by a Ge or C atom; dimethylsilyl, diethylsilyl, dimethylgermyl and diethylgermyl.
[0052] In another embodiment, the bridge-forming group (A) can also be cyclic, comprising, for example, 4 to 10, 5 to 7 members in the ring in a more particular modality. The members in the ring can be selected from the elements mentioned above, from one or more of B, C, Si, Ge, N and O in a particular modality. Non-limiting examples of ring structures that may be present as or part of the bridge-forming group are cyclobutylidene, cyclopentylidene, cyclohexylidene, cycloheptylidene, cyclooctylidene and the corresponding rings in which one or two carbon atoms are replaced by at least one of Si, Ge, N and O, in particular, Si and Ge. The bonding arrangement between the ring and the Cp groups can be cis-, trans- or a combination.
[0053] The cyclic bridging group (A) can be saturated or unsaturated and / or contain one or more substituents and / or be fused to one or more other ring structures. If present, one or more substituents can be a hydrocarbyl (for example, alkyl such as methyl) or halogen (for example, F, Cl). One or more Cp groups whose previous cyclic bridge-forming groups can optionally be fused can be saturated or unsaturated and are selected from the group consisting of those having 4 to 10, more particularly 5, 6 or 7 ring elements (selected from the group consisting of C, N, O and S in a particular embodiment), such as, for example, cyclopentyl, cyclohexyl and phenyl. Furthermore, these ring structures may themselves be fused together, as, for example, in the case of a naphthyl group. In addition, these ring structures (optionally fused) may contain one or more substituents. Non-limiting examples illustrating these substituents are hydrocarbyl groups (particularly alkyl) and halogen atoms.
[0054] The CpA and CpB ligands of Formula (V) and (VI) may be different from each other in some modalities and may be the same in other modalities.
[0055] Metallocene Component Catalysts may include mono-ligand metallocene compounds (e.g., cyclopentadienyl mono-component catalysts) as described in WO 93/08221.
[0056] The metallocene catalyst component can be a "half sandwich" metallocene without bridge represented by the formula (VII): CpAMQqXn (VII)
[0057] In formula VII, CpA is defined as for the Cp groups in formula (V) and is a ligand that is linked to M; each Q is independently linked to M; Q is also linked to CpA in one embodiment; X is a leaving group as described above in formula (V); n is in the range from 0 to 3 and is 1 or 2 in one mode; q is in the range from 0 to 3 and is 1 or 2 in one mode. In one embodiment, CpA is selected from the group consisting of cyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, substituted versions of them and combinations thereof.
[0058] In formula (VII), Q can be selected from the group consisting of ROO-, RO-, R (O) -, -NR-, -CR2-, -S-, -NR2, -CR3, -SR , -SiR3, -PR2, -H and substituted and unsubstituted aryl groups, where R is selected from the group consisting of hydrocarbyls, lower hydrocarbyls, substituted hydrocarbyls, heterohydrocarbyls, alkyls, lower alkyls, substituted alkyls, heteroalkyls, alkenyls, alkenyls lower, substituted alkenyls, heteroalkenyls, alkynyls, lower alkynyls, substituted alkynyls, heteroalkynyls, alkoxys, lower alkoxis, aryloxis, hydroxyls, alkylthio, lower alkylthio, arylthio, thioxis, aryl, substituted aryls, heteroaryl, aralkyls, aralkyls, aralkyls, aralkyls halides, haloalkyls, haloalkenyls, haloalkynyls, heteroalkyls, heterocycles, heteroaryl, groups containing heteroatom, silyl, boryls, phosphines, phosphines, amines, amines, cycloalkyls, acyls, aryls, alkylthioles, dialkylamines, alkyl uylamides, alkoxycarbonyls, aryloxycarbonyls, carbomoyls, alkyl- and dialkyl-carbamoyl, acyloxis, acylaminos, aroylaminos and combinations thereof. In some embodiments, R can be selected from C1 to C6 alkyls, C6 to C12 aryls, C1 to C6 alkylamines, C6 to C12 alkylarylamines, C1 to C6 alkoxys, C6 to C12 aryloxy and the like. Non-limiting examples of Q include C1 to groups C12 carbamates, C1 to C12 carboxylates (e.g., pivalate), C2 to C20 allyls and C2 to C20 heteroalyl.
[0059] Otherwise described, the "half sandwich" metallocenes above can be described as in formula (VIII), as described, for example, in US 6,069,213: CpAM (Q2GZ) XnouT (CpAM (Q2GZ) Xn) m (VIII)
[0060] In formula (VIII), M, CpA, X and n are as defined above and Q2GZ forms a podentated ligand unit (for example, pivalate), in which at least one of the Q groups forms a bond with M and is defined such that each Q is independently selected from the group consisting of -O-, -NR-, -CR2— and -S-; G is carbon or silicon and Z is selected from the group consisting of R, -OR, -NR2, -CR3, -SR, -SiR3, -PR2 and hydride, provided that when Q is -NR-, then Z is selected in group consisting of -OR, -NR2, -SR, -SiR3, -PR2 and provided that the neutral valence for Q is satisfied by Z and each R is independently selected from the group consisting of substituted hydrocarbons, lower hydrocarbons, hydrocarbyl , heterohydrocarbyls, alkyls, lower alkyls, substituted alkyls, heteroalkyls, alkenyls, lower alkenyls, substituted alkenyls, heteroalkenyls, alkynyls, lower alkynyls, substituted alkynyls, heteroalquinyls, alkoxys, lower alkoxys, aryloxis, hydroxyls, alkylthyls, lower alkyls , aryls, substituted aryls, heteroaryls, aralkyls, aralkylenes, alcaryls, alkarylenes, halides, haloalkyls, haloalkenyls, haloalquinyls, heteroalkyls, heterocycles, heteroaryls, groups containing heteroatom, silyls, boryls, phosphines, phosphines, amines, amines, cycloalkyls, acyls, aryls, alkylthiols, dialkylamines, alkylamides, alkoxycarbonyls, aryloxycarbonyls, carbomoyls, alkyl- and dialkyl-carbamoyl, acyloxy, acylaminoes, arylaminos and combinations thereof. In another embodiment, R is selected from the group consisting of groups containing C1 to C10 heteroatom, C1 to C10 alkyls, C6 to C12 aryls, C6 to C12 alkylaryls, C1 to C10 alkoxys and C6 to C12 aryloxis. n is 1 or 2.
[0061] In formula (VIII), m is an integer from 1 to 7; m is an integer from 2 to 6 in a more particular mode and T is a bridge-forming group selected from the group consisting of C1 to C10 alkylenes, C6 to C12 arylenes and groups containing C1 to C10 heteroatom and groups C6 to C12 heterocyclics; where each T group forms a bridge adjacent to “CpAM (Q2GZ) Xn” groups and is chemically linked to the Cps group and
[0062] The metallocene catalyst component can be described more particularly in structures (IXa-i), (IXa-ii), (IXb), (IXc), (IXd), (IXe) and (IXf):



[0063] In structures (IXa-i) to (IXf), M can be selected from the group consisting of atoms from Group 3 to Group 12 or can be selected from Group 3 to Group 10 or can be selected from atoms in Group 3 to Group 6 can either be selected from the group consisting of atoms from Group 4 or can be selected from Zr or Hf or can be Zr.
[0064] In structures (IXa-i) to (IXf), Q can be selected from the group consisting of hydrocarbyls, lower hydrocarbyls, substituted hydrocarbyls, heterohydrocarbyls, alkyls, lower alkyls, substituted alkyls, heteroalkyls, alkenyls, lower alkenyls substituted, heteroalkenyls, alkynyls, lower alkynyls, substituted alkynyls, alkoxys, lower alkoxis, aryloxis, hydroxyls, alkylthio, lower alkylthio, arylthio, thioxis, aryl, substituted aryl, heteroaryl, aralkyl, aralkyl, halo, alkyl , haloalkenyls, haloalkynyls, heteroalkyls, heterocycles, heteroaryls, groups containing heteroatom, silyls, boryls, phosphines, phosphines, amines, amines, cycloalkyls, acyls, aryls, alkylthiols, dialkylamines, alkylamides, alkoxycarbonyls, aryloxycarbonyls, aryloxycarbonyls, aryloxycarbonyls, aryloxycarbonyls; carbamoyl, acyloxy, acylamino, arylamino, alkylene, aryl, aryl lenos, alkoxides, aryloxys, amines, arylamines (e.g., pyridyl) alkylamines, phosphines, alkylphosphines, substituted alkyls, substituted aryls, substituted alkoxides, substituted aryloxys, substituted amines, substituted alkylamines, substituted phosphines, substituted alkylsulfates, heterosulfates, carbamates, carbamates (non-limiting examples of suitable carbamates and carboxylates include trimethylacetate, trimethylacetate, methylacetate, p-toluate, benzoate, diethylcarbamate and dimethylcarbamate), fluorinated alkyls, fluorinated aryls and fluorinated alkylcarboxylates; wherein the saturated groups that define Q may comprise from 1 to 20 carbon atoms and where the aromatic groups may comprise from 5 to 20 carbon atoms.
[0065] In structures (IXa-ii) to (IXf), each R * can be independently selected from the group consisting of divalent alkyls, lower divalent alkyls, substituted divalent alkyls, divalent heteroalkyls, divalent alkenyls, lower divalent alkenyls, divalent alkenyls substituted, divalent heteroalkenyls, divalent alkynyls, lower divalent alkynyls, substituted divalent alkynyls, divalent alkoxys, lower divalent alkoxys, divalent aryloxies, divalent alkylthyls, lower divalent alkyls, divalent aryls, divalent aryls divalent aralkyls, divalent aralkylenes, divalent alkylenes, divalent alkylenes, divalent haloalkyls, divalent haloalkenyls, divalent haloalkynyls, divalent heteroalkyls, divalent heterocycles, divalent heteroaryls, divalent groups containing heteroatomes, hydrocarbons divalent, lower divalent hydrocarbyl, substituted divalent hydrocarbyl, divalent heterohydrocarbyl, divalent silyl, divalent boryls, divalent phosphines, divalent phosphines, divalent amines, divalent amines, divalent ethers, divalent thioethers. In some embodiments, each R * can be independently selected from divalent hydrocarbyls and hydrocarbyls containing heteroatom, or can be selected from alkyls, substituted alkylenes and hydrocarbyls containing heteroatom, or can be selected from C1 to C12 alkylenes, C1 to C12 substituted alkylenes and C1 to C12 hydrocarbilenes containing heteroatom or can be selected from C1 to C4 alkylenes. In some modalities (IXb) to (IXf), both groups R * are the same.
[0066] In structures (IXa-i) to (IXf), A is as described above for (A) in structure (VI). In some embodiments, A can be selected from a chemical bond, -O-, -S-, -SO2-, -NR-, = SiR2, = GeR2, = SnR2, -R2SÍSÍR2-, RP =, C to C12 alkylene, C1 to C12 substituted alkylenes, C4 to C12 divalent cyclic hydrocarbons and substituted and unsubstituted aryl groups or can be selected from C5 to C8 cyclic hydrocarbons, -CH2CH2-, = CR2 and = SiR2.
[0067] In structures (IXa-i) to (IXf), each R can be independently selected from alkyls, cycloalkyls, aryls, alkoxies, fluoroalkyls and hydrocarbons containing heteroatom or can be selected from C1 to C6 alkyls, substituted phenyls, phenyl and C1 to C6 alkoxys or can be selected from methoxy, methyl, phenoxy and phenyl. In some embodiments, A may be absent, in which case each R * is defined as for R1-R13; each X is as described above in (I); n is an integer from 0 to 4 and 1 to 3 in another modality and 1 or 2 in yet another modality and R1 to R13 are independently selected from hydrogen radicals, hydrocarbons, lower hydrocarbyls, substituted hydrocarbyls, heterohydrocarbyls, alkyls, lower alkyls , substituted alkyls, heteroalkyls, alkenyls, lower alkenyls, substituted alkenyls, heteroalkenyls, alkynyls, lower alkynyls, substituted alkynyls, heteroalkynyls, alkoxys, lower alkoxys, aryloxis, hydroxyls, alkylthyls, lower alkylthyls, aryls, hypoxyls, aryls, aryls, aryls, aryls , aralkyls, aralkylenes, alcaryls, alkarylenes, halides, haloalkyls, haloalkenyls, haloalkynyls, heteroalkyls, heterocycles, heteroaryls, groups containing heteroatom, silyl, boryls, phosphines, phosphines, amino, amines, cycloalkyls, alkylamines, acylamyls, alkylamines, acylamines, alkylamines , alkoxycarbonyls, aryloxycarbonyls, carbomoyls, alkyl- and dialkyl carbamoyl, acyloxis, acylaminos and aroylaminos. R1 to R13 can also be selected independently from C1 to C12 alkyls, C2 to C12 alkenyls, C6 to C12 aryls, C7 to C20 alkylaryls, C1 to C12 alkoxides, C1 to C12 fluoroalkyls, C6 to C12 fluoroaryl and C1 to C12 hydrocarbons containing heteroatom and substituted derivatives thereof; or can be selected from hydrogen radical, fluorine radical, chlorine radical, bromine radical, C1 to C6 alkyls, C2 to C6 alkenyls, C7 to C18 alkylaryls, C1 to C6 fluoroalkyls, C2 to C6 fluoroalkenyls or C7 to C18 fluoroalkylyls; or it can be selected from hydrogen radical, fluorine radical, chlorine radical, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, hexyl, phenyl, groups 2, 6-di-methylphenyl and 4-butylphenyl tertiary; wherein the adjacent R groups can form a ring, saturated, partially saturated or completely saturated.
[0068] The structure of the metallocene catalyst component represented by (IXa) can take many forms as described in US 5,026,798, US 5,703,187 and US 5,747,406, including a dimer or oligomeric structure, as described, for example, in US 5,026,798 and US 6,069,213.
[0069] In a particular modality of the metallocene represented in (Vd), R1 and R2 form a 6-element conjugated carbon ring system that may or may not be substituted.
[0070] It is considered that the metallocene catalyst components described above include their structural or optical or enanciomeric isomers (racemic mixture) and can be a pure enanciomer in one modality.
[0071] As used in this case, a simple, asymmetrically substituted, metallocene catalyst component that has a racemic and / or meso isomer itself does not constitute at least two different bridged Component Metallocene Catalysts.
[0072] The "metallocene catalyst compound", also called in this case the "metallocene catalyst component" can comprise any combination of any "modality" described herein.
[0073] The metallocene compounds and catalysts are known in the art and any one or more can be used in this case. Suitable metallocenes include, but are not limited to, all metallocenes described in the U.S. Patents cited above, as well as those described and cited in Pats. No. 7,779,876, 7,169,864, 7,157,531, 7,129,302, 6,995,109, 6,958,306, 6,884748, 6,689,847, Pat. U.S. Pub. No. 2007/0055028 and Published PC. Pat. Applications No. WO 97/22635, WO 00/699/22, WO 01/30860, WO 01/30861, WO 02/46246, WO 02/50088, WO 04/026921 and WO 06/019494. Additional catalysts suitable for use in this case include those described in Pats. No. 6,309,997, 6,265,338, U.S. Pat. U.S. Pub. 2006/019925 and the following articles: Chem Rev 2000, 100, 1253, Resconi; Chem Rev 2003, 103, 283; Chem Eur. J. 2006, 12, 7546 Mitsui; J Mol Catal A 2004, 213, 141; Macromol Chem Phys, 2005, 206, 1847 and J Am Chem Soc 2001, 123, 6847. Activators
[0074] The catalyst compositions can also comprise an activator. As used in this case, the term "activator" refers to any compound or component or combination of compounds and components, capable of improving the ability of a catalyst to oligomerize or polymerize unsaturated monomers, such as olefins. It needed to be understood that the catalyst compositions can be activated for oligomerization and / or polymerization catalysis in any manner sufficient to allow coordination or cationic oligomerization and or polymerization.
[0075] In general, the catalyst modalities can contain a formal anionic ligand, such as hydride or hydrocarbyl, with an adjacent coordination site accessible to an unsaturated monomer. The coordination of an unsaturated monomer to the adjacent coordination site allows for a migratory introduction reaction to form an alkyl metal. The repetition of this process causes the growth of the chain associated with oligomerization and / or polymerization. An activator in this way can be any compound or component or combination of compounds and components, which facilitates the formation of a transition metal compound that contains an adjacent coordinated olefin and hydride or hydrocarbyl.
[0076] When the transition metal compound contains, for example, at least one hydride or hydrocarbyl ligand, activation can be achieved by removing formal anionic or neutron ligand (s), of higher binding affinity than than the unsaturated monomer. This removal process, also called abstraction, can have a kinetic speed that is either first order or not first order in relation to the activator. Activators that remove anionic ligands are called ionization activators. Alternatively, activators that remove Neutral ligands are called non-ionization activators. Examples of activators can include strong Lewis acids that can play the role of an ionization activator or a non-ionization activator.
[0077] When the transition metal compound does not contain, for example, at least one hydride or hydrocarbyl ligands, then the activation can be a one-step process or a multi-step process. A step in this process may include coordinating a hydride or hydrocarbyl group with the metal compound. A separate activation step may include the removal of anionic or neutral ligands with higher binding affinity than the unsaturated monomer. These activation steps can occur, for example, in the presence of an olefin and occur either in series or in parallel. More than one sequence of activation steps is possible to achieve activation. The activator can also act as a coordinate for the hydride or hydrocarbyl group to the transition metal compound. When the transition metal compound does not contain at least one hydride or hydrocarbyl ligand, but does not contain at least one functional group ligand, activation can be carried out by replacing the functional group with a substituted hydride, hydrocarbyl or hydrocarbyl group. This substitution can be carried out with appropriate hydride or alkyl reagents from the group of 1, 2, 12, 13 elements as are known in the art to achieve activation, it may also be necessary to remove anionic or neutral ligands with higher binding affinity than unsaturated monomer.
[0078] In some embodiments, the activator can also act to coordinate a hydride or hydrocarbyl group to the transition metal compound. If the transition metal compound does not contain anionic ligands, then a hydride, a hydrocarbyl or a substituted hydrocarbyl can be coordinated to a metal using electrophilic proton or alkyl transfer reagents represented by H + (LB) nA-, (R) + (LB) nA-. R can be a hydrocarbyl or a substituted hydrocarbyl; LB is a Lewis base and where n = 0, 1 or 2. Non-limiting examples of Lewis bases are diethyl ether, dimethyl ether, ethanol, methanol, water, acetonitrile, N, N-dimethylaniline. A- is an anion, in one embodiment, a substituted hydrocarbon, a functional group or a non-coordinating anion. Non-limiting examples of A- may include halides, carboxylates, phosphates, sulfates, sulfonates, borates, aluminates, alkoxides, thioalkoxides, substituted anionic hydrocarbons, anionic metal complexes and the like.
Additional examples of suitable activators include those described in WO 98/07515, such as tris fluoroaluminate (2, 2 ', 2 "- nonafluorobiphenyl). Combinations of activators are also considered, for example, alumoxanes and ionization activators in combination as described in the following references, EP-B1 0 573 120, WO 94/07928, WO 95/14044 and U.S. Pat. We. 5,153,157 and 5,453,410, WO 98/09996 describes the activation of metallocene catalyst compounds with perchlorates, periodates and iodates including their hydrates. WO 98/30602 and WO 98/30603 describe the use of lithium (2,2'-bisphenylditrimethylsilicate) .4THF as an activator for a metallocene catalyst compound. WO 99/18135 describes the use of organo-boron-aluminum activators. EP-B1-0 781 299 describes the use of a silyl salt in combination with a compatible non-coordinating anion. WO 2007/024773 suggests the use of support-activators that can comprise a chemically treated solid oxide, clay mineral, silicate mineral or any combination thereof. In addition, activation processes such as the use of radiation (see, for example, EP-B1-0 615 981), electrochemical oxidation and the like are also considered as activation processes for the purposes of making the catalyst compound metallocene or precursor a metallocene cation capable of polymerizing olefins. Other activators or processes for the activation of a metallocene catalyst compound are described, for example, in Pats. U.S. Nos. 5,849,852, 5,859,653 and 5,869,723 and in PCT WO 98/32775.
[0080] The alumoxane activators can be used as an activator in the catalyst composition of the invention. Alumoxanes are generally oligomeric compounds that contain --Al (R) - O-- subunits, where R is an alkyl group. Examples of alumoxanes include methylalumoxane (MAO), modified methylalumoxane (MMAO), ethylalumoxane and isobutylalumoxane. Alkylalumoxanes and modified alkylalumoxanes are suitable as activating catalysts, particularly when the abstractable ligand is a halide. Mixtures of different alumoxanes and modified alumoxanes can also be used. Alumoxanes are also described, for example, in U.S. Pat. No. 4,665,208, 4,952,540, 5,041,584, 5,091,352, 5,206,199, 5,204,419, 4,874,734, 4,924,018, 4,908,463, 4,968,827, 5,329,032, 5,248,801, 5,235. 081, 5,157,137, 5,103,031 and EP 0 561 476 A1, EP 0 279 586 B1, EP 0 516 476 A, EP 0 594 218 A1 and WO 94/10180,
[0081] When the activator is an alumoxane (modified or unmodified), some modalities select the maximum amount of activator to a 5000-fold molar excess of Al / M in relation to the precursor catalyst (per metal catalytic site). The minimum molar ratio of activator to catalyst-precursor is 1: 1, for example.
[0082] Alumoxanes can be produced by hydrolysis of the respective trialkylaluminum compound. For example, MMAO can be produced by hydrolysis of trimethylaluminum and a higher trialkylaluminium such as triisobutylalumin. MMAO’s are generally more soluble in aliphatic solvents and more stable during storage. There are a variety of processes for preparing alumoxane and modified alumoxanes, the non-limiting examples of which are described, for example, in Pats. U.S. Nos. 4,665,208,4,952,540,5,091,352,5,206,199.5,204,419,4,874,734,4,924,018, 4,908,463.4,968,827.5,308,815.5,329,032,5,248,801,5,235. 081,5,157,137, 5,103,031.5,391,793,5,391,529,5,693,838,5,731,253,5,731,451,5,744,656, 5,847,177,5,854,166,5,856,256 and 5,939,346 and European publications EP-A-0 561 476, EP-B1-0 279 586, EP-A-0 594-218 and EP-B1-0 586 665, WO 94/10180 and WO 99/15534. A visually transparent methylalumoxane may be used. A cloudy or gelled alumoxane can be filtered to produce a clear solution or the clear alumoxane can be decanted from the cloudy solution. Another alumoxane is a modified methyl alumoxane (MMAO) of the cocatalyst type 3A (commercially available from Akzo Chemicals, Inc. under the trade name Modified methylalumoxane type 3A, described in U.S. Pat. No. 5,041,584).
[0083] An ionization or stoichiometric activator, neutral or ionic, such as tri (n-butyl) ammonium tetrakis (pentafluorophenyl) boron, a metalloid precursor trisperfluorophenyl boron or a metalloid precursor trisperfluorophile boron, heteroborane anions (heteroborane polyethers) see, for example, WO 98/43983), boric acid (see, for example, US Pat. No. 5,942,459) or a combination thereof. Also within the scope of this description is the use of neutral or ionic activators alone or in combination with alumoxane or modified alumoxane activators.
[0084] Examples of neutral stoichiometric activators may include tri-substituted boron, tellurium, aluminum, gallium and indium or mixtures thereof. The three substituent groups can each be independently selected from the group of alkyls, alkenyls, halogen, substituted alkyls, aryls, aryl halides , alkoxy and halides. In modalities, the three substituent groups can be independently selected from the group of halogen, mono- or multicyclic (including halosubstituted) aryl, alkyl and alkenyl compounds and mixtures thereof; in a class of modalities are alkenyl groups that have 1 to 20 carbon atoms, alkyl groups that have 1 to 20 carbon atoms, alkoxy groups that have 1 to 20 carbon atoms and aryl groups that have 3 to 20 carbon atoms (including substituted arils). Alternatively, the three groups are alkyls that have 1 to 4 carbon, phenyl, naphthyl groups or mixtures thereof. In other modalities, the three groups are halogenated aryl groups, in a fluorinated modality. In other illustrative modalities, the neutral stoichiometric activator is trisperfluorophenyl boron or trisperfluoronaphyl boron.
[0085] The ionic stoichiometric activator compounds may contain an active proton or some other associated cation, with however not coordinated with or only loosely coordinated with the remaining ion of the ionizing compound. Such compounds and the like are described, for example, in European publications EP-A-0 570 982, EP-A-0 520 732, EP-A-0 495 375, EP-B1-0 500 944, EP-A-0 277 003 and EP-A-0 277 004 and in U.S. Pat. Nos. 5,153,157, 5,198,401, 5,066,741, 5,206,197, 5,241,025, 5,384,299 and 5,502,124 and in U.S. Pat. No. 08 / 285,380, filed on August 3, 1994. Supported Catalyst Compositions
[0086] The catalyst compositions can also comprise a support. For example, each component of the catalyst composition can be supported on a support. Atomizer drying can be used to combine the catalyst components with one or more supports. Spray drying of the catalyst composition can result in catalyst compositions that have higher catalyst productivity compared to other techniques for preparing the catalyst.
[0087] As used in this case, the term "supported" refers to one or more compounds that are deposited on, in contact with, vaporized with, adsorbed or absorbed on or on, a support or vehicle. The terms "support" and "vehicle," for the purposes of this specification, are used interchangeably and are any support material, such as a porous support material, including inorganic or organic support materials.
[0088] Non-limiting examples of suitable supports include compounds comprising Group 2, 3, 4, 5, 13 and 14 oxides and chlorides. Suitable supports can include, for example, silica, magnesia, titania, zirconia, montmorillonite, phyllosilicate , alumina, silica-alumina, silica-chromium, silica-titania, magnesium chloride, graphite, magnesia, titania, zirconia, montmorillonite, phyllosilicate and the like. Combinations of supports may also be suitable, including, for example, silica-chrome, silica-alumina, silica-titania and the like. In one embodiment, smoky silica is a suitable support.
[0089] The support can have an average particle size in the range of approximately 0.1 to approximately 50 μm or from approximately 1 to approximately 40 μm or from approximately 5 to approximately 40 μm.
[0090] The support, such as an inorganic oxide, can have a surface area in the range of approximately 10 to approximately 700 m2 / g, a pore volume in the range of approximately 0.1 to approximately 4.0 cm3 / g an average particle size in the range of approximately 1 to approximately 500 μm. In some embodiments, the support may have a surface area in the range of approximately 50 to approximately 500 m2 / g, a pore volume of approximately 0.5 to approximately 3.5 cm3 / g and an average particle size of approximately 10 to approximately 200 μm. In some embodiments, the support may have a surface area in the range of approximately 100 to approximately 400 m2 / g, a pore volume of from approximately 0.8 to approximately 3.0 cm3 / g and an average particle size is from approximately 5 to approximately 100 μm. In some embodiments, the average pore size of the support can be from approximately 1 to approximately 50 μm. In some embodiments, the average pore size of the support can range from approximately 10 to approximately 1000 Á, from approximately 50 to approximately 500 Á, or from approximately 75 to approximately 350 Á.
[0091] The catalyst components can be supported on the same or on separate supports together with an activator or the activator can be used in an unsupported form or can be deposited on a support different from the supported catalyst components or any combination thereof.
[0092] As described earlier, spray drying can be used to combine the catalyst components with one or more supports. Spray drying of a catalyst composition can result in catalyst compositions that have higher catalyst productivity compared to other techniques for preparing the catalyst. Examples of techniques for spray drying a catalyst composition are described, for example, in U.S. Patent Nos. 5,648,310; 5,674,795 and 5,672,669 and EP0668295 B1.
[0093] The catalyst component (s) and / or activators (s) can be combined with a particulate support material and then dried in an atomizer, for example to form a free-flowing powder. For example, the catalyst components and optionally the activator (s) can be placed in solution, allowing them to react, then a filler material such as silica or Cabosil ™ is added and then forcing the solution at high pressure through a nozzle. The solution can be sprayed onto a surface or sprayed so that the droplets dry in the midair space. In some embodiments, the filler material (such as silica) can be dispersed in toluene, then stirred in the activator solution and then stirred in the catalyst components. Typical concentrations of the suspension are around 5-8% by weight, for example. This formulation can stand as a suspension for as long as 30 minutes with light agitation or manual agitation to maintain it as a suspension before spray drying. In some embodiments, the replacement of the dry material can be from approximately 40-50% by weight of activator (for example, alumoxane), around 50-60% by weight of filler material (for example, SiO2) and around 2% by weight of catalyst components.
[0094] In some embodiments, the catalyst components can be added together in the desired proportion in the last step. In some embodiments, more complex procedures are possible, such as adding a first catalyst component to the activator / filler material for a specified period of time, followed by the addition of a second catalyst component, mixed for another specified period of time, then from which the mixture is co-sprayed. For example, an additive, such as 1-hexene (for example, around 10% by volume), may be present in the activator / charge mixture before adding the first catalyst component.
[0095] In some embodiments, a metallocene catalyst component can be combined with a catalyst composition dried in an atomizer and then introduced into a reactor.
[0096] In some embodiments, binders can be added to the mixture. For example, binders can be added as a means to improve particle morphology, that is, to limit the particle size distribution, to decrease particle porosity and to be responsible for a reduced amount of alumoxane, which is acting as the binder. Polymerization processes
[0097] The modalities of the polymerization processes can include the polymerization of olefins in the presence of an atomizer dried catalyst composition comprising a complex transition metal catalyst component. Polymerization can take place in the presence of an atomizer dried catalyst composition comprising a complex non-metallocene transition metal catalyst component, such as a group 15 containing catalyst component or it can occur in the presence of an atomizer dry mixed catalyst composition which comprises a complex transition metal catalyst component, a non-metallocene catalyst component and a metallocene catalyst component.
[0098] Polymerization processes may include solution, gas phase, phase in suspension and a high pressure process or a combination thereof. In illustrative embodiments, a polymerization is provided can include gas phase or suspension phase polymerization of one or more olefins, at least one of which is ethylene or propylene.
[0099] The atomizer dried catalyst compositions described above are suitable for use in any pre-polymerization and / or polymerization process over a wide range of temperatures and pressures. Temperatures, for example, can be in the range of approximately 60 ° C to approximately 280 ° C or from approximately 50 ° C to approximately 200 ° C or from approximately 60 ° C to approximately 120 ° C or from approximately 70 ° C to approximately 100 ° C or from approximately 80 ° C to approximately 95 ° C.
[00100] The polymerization process can be a process of polymerization in solution, at high pressure, in suspension or in gas phase of one or more olefin monomers that have from 2 to 30 carbon atoms, alternatively from 2 to 12 atoms of carbon or alternatively from 2 to 8 carbon atoms. For example, the polymerization can be two or more olefins or comonomers such as ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene or the like.
[00101] Non-limiting examples of other olefins useful in the polymerization process include ethylenically unsaturated monomers, diolefins having 4 to 18 carbon atoms, conjugated or unconjugated dienes, polyenes, vinyl monomers and cyclic olefins. Non-limiting examples of useful monomers include, but are not limited to, norbornene, norbornadiene, isobutylene, isoprene, vinylbenzocyclobutane, styrenes, substituted alkyl styrene, ethylidene norbornene, dicyclopentadiene and cyclopentene.
[00102] The polymerization process can produce an ethylene copolymer, in which ethylene and a comonomer that have at least one alpha-olefin that have from 4 to 15 carbon atoms or from 4 to 12 carbon atoms or from 4 to 8 carbon atoms are polymerized in a gas phase process.
[00103] In some embodiments, ethylene or propylene can be polymerized with at least two different comonomers, optionally one of which can be a diene, to form a terpolymer.
[00104] The polymerization process may include a gas phase polymerization process in which a continuous cycle can be employed, in which part of the reactor system cycle, a recycle gas stream, also known as a recycle stream or fluidization medium is heated in the reactor by the heat of polymerization. This heat can be removed from the recycling composition in another part of the cycle by an external cooling system for the reactor. In general, in a gas fluidized bed process for the production of polymers, a gas stream containing one or more monomers can be continuously recycled through a fluidized bed in the presence of a catalyst under reaction conditions. The gas stream can be removed from the fluidized bed and recycled back to the reactor. Simultaneously, the polymer product can be removed from the reactor and no monomer is added to replace the polymerized monomer. Gas phase polymerization processes are described in more detail, for example, in U.S. Pat. No. 4,543,399, 4,588,790, 5,028,670, 5,317,036, 5,352,749, 5,405,922, 5,436,304, 5,453,471, 5,462,999, 5,616,661 and 5,668,228.
[00105] The reactor pressure in a gas phase process can vary, for example, from approximately atmospheric pressure to approximately 4137 kPa (600 psig), or from approximately 690 kPa (100 psig) to approximately 3448 kPa (500 psig), or from approximately 1379 kPa (200 psig) to approximately 2759 kPa (400 psig), or from approximately 1724 kPa (250 psig) to approximately 2414 kPa (350 psig).
[00106] The reactor temperature in a gas phase process can vary, for example, from approximately 30 ° C to approximately 120 ° C, or from approximately 60 ° C to approximately 115 ° C, or from approximately 70 ° To approximately 110 ° C, or from approximately 70 ° C to approximately 95 ° C.
[00107] Additional examples of gas phase processes that can be used include those described in U.S. Pat. No. 5,627,242, 5,665,818 and 5,677,375 and in European Publications EP-A-0 794 200, EP-A-0 802 202, EP-A20 891 990 and EP-B-634 421.
[00108] The modalities of the polymerization process can include a suspension polymerization process. In the suspension polymerization process, pressures can range from approximately 1 to approximately 50 atmospheres and temperatures can range from approximately 0 ° C to approximately 120 ° C. In a suspension polymerization, a solid, particulate polymer suspension can be formed in a liquid polymerization diluent medium to which ethylene and comonomers and often hydrogen together with the catalyst are added. The suspension that includes diluent can be removed intermittently or continuously from the reactor where the volatile components are separated from the polymer and recycled, optionally after distillation, to the reactor. The liquid diluent used in the polymerization medium can typically be an alkane having 3 to 7 carbon atoms, preferably a branched alkane. The medium used had to be liquid under the conditions of polymerization and relatively inert. When using a propane medium the process needed to be operated, for example, above the critical temperature and pressure of the reaction diluent. In some embodiments, hexane or isobutane is used. Continuity Additives / Static Control Agents
[00109] In the processes described here, it may also be desired to additionally use one or more static control agents or continuity additives to help regulate static levels in the reactor. For the purposes in this case, the terms "static control agents" and "continuity additives" are used interchangeably. As used in this case, a static control agent is a chemical composition that, when introduced into a fluidized bed reactor, can influence or trigger the static charge (negatively, positively or even zero) in the fluidized bed. The specific static control agent used may depend on the nature of the static charge and the choice of static control agent may vary depending on the polymer being produced and the catalyst being used. For example, the use of static control agents is described in European Patent No. 0229368 and in U.S. Patent No. 5,283,278 and in the references cited therein.
[00110] The static control agent used can be selected for its ability to receive the static charge in the fluidized bed without adversely affecting productivity. Suitable static control agents may also include aluminum stearate, aluminum distearate, ethoxylated amines, polyethers, amine-terminated polyethers and antistatic compositions such as those provided by Innospec Inc. under the trade name OCTASTAT. For example, OCTASTAT 2000 is a mixture of a polysulfone copolymer, a polymeric polyamine and oil soluble sulfonic acid.
[00111] Other useful static control agents include those described, for example, in WO 01/44322, listed under the heading Metal Carboxylate Salt. In some embodiments, a metal carboxylate salt can be combined with an amine-containing control agent (for example, a metal carboxylate salt with any family member belonging to KEMAMINA (available from Crompton Corporation) or ATMER (available by ICI Americas Inc.) product family). In addition, the metal carboxylate salt can also be combined with a polyether or with an amine-terminated static polyether control agent. Other useful static control agents are described in US 2008/0045663, for example.
[00112] The static control agent added to the reactor can be a combination of two or more of the static control agents listed above. The static control agent (s) can be added to the reactor in the form of a solution or a suspension and can be added to the reactor as an individual feed stream or can be combined with other feeds prior to addition to the reactor. For example, the static control agent can be combined with the catalyst or with the suspension of the catalyst before feeding the combined catalyst-static control agent mixture to the reactor.
[00113] The static control agent can be added to the reactor in an amount ranging from 0.05 to 200 ppm or from 2 to 100 ppm or from 4 to 50 ppm, based on the weight of all feeds for the reactor, excluding recycling. Polymer Products
[00114] The polymers produced by the polymerization processes described here can be used in a wide variety of products and end-use applications. The polymers produced herein may include, but are not limited to, low density linear polyethylene, low density polyethylene and high density polyethylene.
[00115] Polymers, including polymers based on ethylene and propylene, can have a density, in the range of approximately 0.86 g / cm3 to approximately 0.97 g / cm3 or in the range of approximately 0.88 g / cm3 cm3 to approximately 0.965 g / cm3, or in the range of approximately 0.900 g / cm3 to approximately 0.96 g / cm3.
[00116] Polymers may have a molecular weight distribution, an average molecular weight by weight for average molecular weight in number (Mw / Mn), for example, from approximately 1.5 to approximately 25 or from approximately 2 to approximately 20 or from approximately 2.2 to 15.
[00117] Polymers can have a melt index (MI) or (I2) in the range of from 0.01 dg / min to 1000 dg / min or from approximately 0.01 dg / min to approximately 100 dg / min or from from approximately 0.1 dg / min to approximately 100 dg / min.
[00118] Polymers can have a flow rate ratio (I21 / I2) of from 5 to 300 or from approximately 10 to 250 or from 15 to 200, or from 20 to 180.
[00119] Polymers can be mixed and / or coextruded with any other polymer. Non-limiting examples of other polymers include linear low density polyethylenes produced by conventional and / or single site catalysis, elastomers, plastomers, low pressure high density polyethylene, high density polyethylene, polypropylene and the like.
[00120] The polymers produced by the processes described here and their mixtures are useful in such forming operations as film, tube, sheet and fiber extrusion and co-extrusion as well as insufflation molding, injection molding and rotation molding. Films include blown or molded films formed by coextrusion or lamination useful as shrink film, cling film, stretch film, sealing films, oriented films, snack packaging, heavy duty bags, grocery packaging, grocery packaging, packaging for cooked and frozen food, medicine packaging, industrial coatings, membranes, etc. applications in contact with food and without contact with food. Fibers may include, but are not limited to, molten state spinning, solution spinning and molten state inflated fiber operations for use in the form of fabric or nonwovens and obtaining filters, fabrics not to be limited to, spinning in the molten state, solution spinning and molten state fiber operations for use in the form of fabric or non-woven fabric and for obtaining filters, diaper fabrics, for medical clothing, geotextiles etc. Extruded articles may include medical tubing, wire and cable coatings, geomembranes and tank linings. Molded articles include single and multiple layer constructions in the form of bottles, tanks, large hollow articles, rigid containers for food and toys, etc. Test Processes
[00121] The density values are based on ASTM D1505.
[00122] The fluidity index (MI), I2, is measured according to ASTM-D-1238-E (190 ° C, 2.16 kg in weight).
[00123] The fluidity index (MI5), I5, is measured according to ASTM-D-1238-G (190 ° C, 5 kg in weight).
[00124] The fluidity index (FI), I21, is measured according to ASTM-D-1238-F (190 ° C, 21.6 kg in weight).
[00125] The Flow Rate Ratio (MFR5, I21 / I5) is the ratio of I21 to I5 as determined by ASTM D1238.
[00126] SEC measurements are provided according to the following procedure, which uses Polymer Laboratories instrument; Model: HT-GPC-220, Columns: Shodex, Run Temperature: 140 ° C, Calibration Standard: traceable to NIST, Solvent: 1, 2, 4-Trichlorobenzene. EXAMPLES
[00127] The following examples are presented in order to provide those skilled in the art with a complete description and a description of how to obtain and use the compounds of the invention and it is not intended to limit the scope of what the inventors regard as their invention. All parts, proportions and percentages are by weight unless otherwise indicated. All examples were performed in oxygen and solvent free environments unless otherwise indicated.
[00128] The complex transition metal catalyst component used in the examples below comprised 2,6-diacetylpyridinabis (2,4,6-trimethyl-phenylamine) FeCl2, which was prepared in a manner substantially as described in Small, BL and others , J. Am. Chem. SOC. 1998, 120, 4049 - 1050. The transition metal catalyst complex is presented by these examples as TMC-1 and the structure of TMC-1 is presented below:
EXAMPLE 1
[00129] The following example refers to gas phase ethylene polymerization procedures carried out under laboratory gas phase reactor conditions. The reactor was used to evaluate different support processes for a catalyst composition that comprises a transition metal catalyst component. Table 1 demonstrates the productivity of the catalyst for the catalyst compositions using the different support processes. Support Process A
[00130] In Support Process A, component TMC-1 was supported on silica impregnated with MAO (silica grade Davison 955 calcined at 600 ° C) according to the following procedure: 1.00 g of silica impregnated with MAO and 0.026 g of TMC-1 were combined and suspended in 10 ml of toluene. The suspension was left under stirring for two hours at room temperature (around 25 ° C) before the volatiles were removed from the suspension under vacuum. The supported transition metal catalyst composition was recovered as a light beige free-flowing powder in almost quantitative yield. The recovered supported transition metal catalyst composition is referred to in the examples as TMC-A. Support Process B
[00131] In the Support_B Process, for the spray drying process a supported catalyst composition was used. An example of a typical procedure used is as follows: a suspension was prepared by combining 5.58 kg (12.3 pounds) of a 10 wt% solution of MAO in toluene, 0.76 kg (1.7 pounds) of a smoky silica charge of approximately 8 kg of toluene. The suspension was mixed for one hour at 40 ° C before adding 35.7 g of TMC-1 to the mixture and an additional hour of mixing at 40 ° C. The above suspension was then spray dried using a pilot scale spray dryer. The suspension was spray fed to the dryer at a feed rate of 38.4 kg (85.5 pounds per hour. The atomizer speed was maintained at 90%. The condenser outlet temperature was maintained at approximately 80 ° C. Atomizer-dried particles have an iron charge of 0.0406 mmol / g, an Al charge of 5.99 mmol / g and an Al / M ratio of 148: 1. The atomizer-dried catalyst composition is cited in examples like TMC-B. Polymerization of Ethylene in a Gas Phase Laboratory Reactor
[00132] The supported catalyst compositions described above were used in polymerization reactions conducted in a gas scale reactor on a laboratory scale. The gas-phase reactor used is a 1.65 liter stainless steel autoclave, equipped with a variable speed mechanical stirrer. For maximum mixing, the reactor is normally operated at an angle of 45 degrees with its vertical position during polymerization. In a standard HDPE run, the reactor was first charged with 400 g of NaCl and dried by heating at 95 ° C under a nitrogen stream for one hour. After heating the reactor, the temperature is lowered to around 60 ° C to introduce 5 g of SMAO (methylaluminoxane supported on silica) as an expelling agent with the help of nitrogen pressure. After the addition of SMAO, the reactor was sealed and the components were stirred carefully. The reactor was then charged with the desired amounts of hydrogen and 1-hexene, if any. The reactor is then pressurized with ethylene (1104 kPa - 1587 kPa (160 - 230 psig)). As soon as the system reaches a regular state, the catalyst is charged to the reactor using a stainless steel pump to initiate polymerization. The reactor temperature is then brought up to the specified temperature (100 ° C) and maintained at this temperature throughout the run. Polymerization is typically carried out for 60 minutes and during this time hydrogen, the C6 / C2 ratio and the ethylene pressure are kept constant. At the end of the 60 minute run time period, the reactor is cooled, aerated and opened. The resulting mixture is then washed with water, with methanol and dried. Table 1 provides a brief summary of the process conditions and catalyst productivities for the polymerization reactions with the catalyst compositions in this example. As can be seen in Table 1, the use of process A support provides an activated transition metal catalyst composition complex with only moderate productivities (<2,000 g / g). Surprisingly, the use of process B support (spray drying) provides a complex catalyst component of activated transition metal with more than twice the productivity of support processes A. Table 1
EXAMPLE 2
[00133] Gas phase polymerization procedures were carried out in a pilot-scale fluidized bed reactor to better evaluate the use of atomizer dried catalyst compositions that comprise a complex transition metal catalyst component. Table 2 below demonstrates the productivity of the catalyst for the spray dried catalyst composition which comprises a complex transition metal catalyst component compared to a comparative catalyst composition. Catalyst compositions
[00134] In this example, the atomizer dry TMC-B transition metal complex was compared to a comparative catalyst composition. The comparative catalyst composition (CCC-1) was a bimetallic catalyst consisting of (tetramethylcyclopentadiene) dichloride (N-propylcyclopentadiene) zirconium and bis (2- (pentamethylphenylamido) ethyl) dibenzyl amine zirconium, supported on smoked silica. Processes for preparing CCC-1 are described, for example, in U.S. Patent No. 6,271,325. Polymerization of Ethylene in a Pilot Scale Gas Reactor
[00135] The catalyst compositions in this example were used in polymerization reactions conducted in a gas-phase reactor on a pilot scale of a fluidized bed of 0.35 meter internal diameter and 2.3 meters of bed height. Each run was operated using the same continuous fluidized gas phase reactor. The fluidized bed consists of polymer granules. The gas streams supplying ethylene and hydrogen together with the liquid comonomer were mixed in a “T” mixing arrangement and introduced below the reactor bed to the recycling gas line. 1-hexene was used as the comonomer. The individual flows of ethylene, hydrogen and comonomer were controlled to maintain fixed targets of the composition. The ethylene concentration was controlled to maintain a constant partial pressure of ethylene. Hydrogen was controlled to maintain a constant molar ratio of hydrogen to ethylene. The concentration of all gases was measured by an in-line gas chromatograph to ensure a relatively constant composition in the recycle gas stream.
[00136] The catalyst compositions (TMC-B and CCC-1) were injected directly into the reactor as a suspension in purified mineral oil and the feed rate of the catalyst in the suspension was adjusted to maintain a constant rate of polymer production. For CCC-1, a pre-catalyst compound (tetramethylcyclopentadiene) (N-propylcyclopentadiene) zirconium dimethyl was added to the catalyst feed stream prior to its injection into the reactor to adjust the product's targeted properties. A continuity additive (a mixture of aluminum distearate and an ethoxylated amine type compound) was injected directly into the fluidized bed regardless of the catalyst composition that uses purified nitrogen as a vehicle. The continuity additive feed rate was adjusted to keep the proportion of continuity additive constant.
[00137] The bed for the reaction of growing polymer particles was maintained in a fluidized state by the continuous flow of the replacement feed and the recycle gas through the reaction zone. A surface gas velocity of 0.54 - 0.63 meters / second (1.8 - 2.1 feet / second) was used to achieve this. The reactor was operated at a total pressure of approximately 2414 kPa (350 psig) to keep the reactor temperature constant, the temperature of the recycle gas was continuously adjusted up or down to accommodate any variations in the heat generation speed due to polymerization.
[00138] The fluidized bed was kept at a constant height by removing part of the bed at a rate equal to the rate of formation of the particulate product. The product was removed semi-continuously by means of a series of valves in a fixed volume chamber, which was simultaneously aerated back to the reactor. This allows for a highly effective removal of the product, while recycling a large part of the unreacted gases back to the reactor. This product was purged to remove entrapped hydrocarbons and treated with a small amount of humidified nitrogen vapor to deactivate any trace amounts of residual catalyst.
[00139] Table 2 provides a brief summary of the process conditions, resin properties and catalyst productivities for the polymerization reactions. Table 2
1Parts per million based on production rate
[00140] As illustrated by Table 2, slightly higher productivity of the catalyst was observed for TMC-B compared to CCC-1 at the reactor temperature of 105 ° C. Surprisingly, lowering the reactor temperature to 95 ° C provided an increase of approximately 65% in productivity (12,243 g / g v. 7,724 g / g for ex. 2a and 8,896 g / g for ex. 2b) for TMC -B. Even so, as shown by FIG. 1, TMC-B provided a polyethylene resin with substantially a higher global molecular weight and a broader molecular weight distribution at the lower reactor temperature.
[00141] Additionally, FIGS. 2 and 3 demonstrate that the GPC coatings of the resins produced in this example at the reactor temperatures of 105 ° C and 95 ° C, respectively. At 105 ° C, the molecular weight distribution of the polymer made with TMC-B overlapped mainly with the low and medium molecular weight regimes of the polymer made with CCC-1 (example 2a), while at 95 ° C the amplitude The molecular weight distribution of the TMC-B polymer covers most of the bimodal molecular weight distribution of comparative example 2c. EXAMPLE 3
[00142] Additional gas phase polymerization procedures were carried out in a pilot scale gas phase fluidized bed reactor to better evaluate the use of mixed atomizer dry catalyst compositions that comprise a complex transition metal catalyst component. Table 4 below demonstrates the catalyst productivity for spray dried mixed catalyst compositions comprising a transition metal complex. Catalyst Preparation
[00143] The TMC-B transition metal complex as well as two mixed catalyst compositions comprising the TMC-1 transition metal complex were spray dried as described above in Example 1 using Support Process B. For the compositions of mixed catalysts (“M-1” and “M-2”), TMC-1 and bis (2- (pentamethylphenyl starch) ethyl) zirconium dibenzyl amine (“Comp. A”) both a suspension in MAO toluene and smoky silica charge. The suspension was allowed to mix for one hour at 40 ° C before being spray dried. As noted below in Table 3, two mixed catalyst compositions were prepared which comprise the TMC-1 transition metal complex and Comp. A with different levels of charge of the catalyst components. Table 3
1 Determined by ICP-OES Polymerization of Ethylene in a Pilot Scale Gas Reactor
[00144] The catalyst compositions in this example were used in polymerization reactions conducted in a continuous fluid bed reactor in a gas phase on a pilot scale. The reactor was operated as described above in Example 2 with a (tetramethylcyclopentadiene) compound (N-propylcyclopentadiene) zirconium dimethyl was added to the catalyst feed stream prior to its injection into the reactor in the case of polymerization reactions with the mixed compositions of catalysts (M-1 and M-2) to adjust the product's target properties. Table 4 provides a brief summary of the process conditions, the properties of the resin and the productivities of the catalyst for the polymerization reactions. Table 4
1 Parts per million based on production rate.
[00145] As illustrated by Table 4, M-2 exhibits better catalyst productivity compared to M-1 at both reactor temperatures examined (105 ° C and 95 ° C). In addition, compared to comparative examples 2a and 2c (Table 2), the atomizer-dried M-2 has substantially higher catalyst productivity (example 3d, Table 4). Surprisingly, it was also observed that, at similar values of I21 of the resin, the catalyst compositions of this example reached a higher value of I5 and thus a lower proportion of I21 / I5 when compared to examples 2a and 2c with the catalyst CCC- 1. FIGS. 4 and 5 show the GPC coating of the resin produced by atomizer dry mixed catalyst compositions of this example and the CCC-1 catalyst at the reactor temperatures of 105 ° C and 95 ° C, respectively. The molecular weight distribution of the resin produced in this example showed a reduction in Mw as well as an overall reduction in molecular weight distribution (Mw / Mn) when compared to examples 2a and 2c. It was also observed that the molecular weight distribution of the resin produced using M-1 and M-2 is slightly limited with the increase of TMC-1 content at both reactor temperatures. Interestingly, when compared to the CCC-1 catalyst (examples 2a and 2c), the spray-dried mixed catalyst compositions present “supply” of the valley in the multimodal molecular weight distribution at both reactor temperatures of 105 ° C and 95 ° C . Additionally, a slightly less pronounced valley of multimodal molecular weight distribution was observed for the resin produced using M-1 compared to that produced by M-2.
[00146] Although the invention has been described in relation to some modalities and some examples, those skilled in the art, who have the privilege of this description, will consider that other modalities can be planned that do not fall outside the scope and spirit of the invention as described here. Although individual modalities are discussed, the invention encompasses all combinations of all these modalities.
[00147] Although the compositions, processes and processes are described herein in terms of "comprises," "contains," "has," or "includes" various components or steps, compositions and processes can also "consist essentially in ”or“ consist of ”various components and steps. The expressions, unless otherwise specified, “consists essentially of” and “that consists essentially of” do not exclude the presence of other steps, elements or materials, whether or not specifically mentioned in this specification, provided that such steps, elements or materials, do not affect the basic and new features of the invention, additionally, they do not exclude impurities and variances normally associated with the elements and materials used.
[00148] For the sake of brevity, only certain ranges are explicitly described in this case. However, it is in the range from any lower limit to be combined with any upper limit to quote a range not explicitly quoted, just as it is in the range from any lower limit to be combined with any other lower limit to quote a range not explicitly quoted , likewise, it is in the range of since any upper limit can be combined with any other upper limit to quote a range not explicitly mentioned.
[00149] All documents cited herein are fully incorporated as a reference for all jurisdictions in which such incorporation is permitted and to the extent that such description is consistent with the specification of the present invention.

权利要求:
Claims (14)
[0001]
1. Composition, characterized by the fact that it comprises: - an atomizer-dried catalyst composition comprising a transition metal catalyst component represented by the following formula:
[0002]
2. Composition according to claim 1, characterized by the fact that: R5 of the transition metal catalyst component is represented by the following formula:
[0003]
3. Composition according to claim 2, characterized by the fact that R1 to R4, R6 and R8 to R17 are each independently selected from the group consisting of hydrogen, halogen C1 to C8 hydrocarbyl.
[0004]
4. Composition according to claim 2, characterized by the fact that R10 and R15 are each independently selected from the group consisting of hydrogen, C1 to C8 hydrocarbyl, benzyl, fluorine, chlorine, bromine and iodine.
[0005]
5. Composition according to claim 2, characterized by the fact that R1, R2, R3, R9, R11, R14 and R16 are each hydrogen; and R4, R6, R8, R10, R12, R13, R15 and R17 are each represented by methyl.
[0006]
6. Composition according to claim 1, characterized in that the spray dried catalyst composition also comprises a non-metallocene catalyst component, wherein the non-metallocene catalyst component is a catalyst containing Group 15.
[0007]
7. Composition according to claim 6, characterized by the fact that the non-metallocene catalyst component is represented by the following formula: αaβbYgMXn where: M is a metal atom; X is independently selected from the group consisting of halogen ions, hydrides, C1 to C12 alkyls, C2 to C12 alkenyls, C6 to C12 aryls, C7 to C20 alkylaryls, C1 to C12 alkoxys, C6 to C16 aryloxis, C7 to C18 alkylaryloxis, halogenated C1 to C12 halogenated alkyls, C2 to C12 halogenated alkenyls, C6 to C12 halogenated aryls, C7 to C20 halogenated aryls, C1 to C12 halogenated alkoxys, C6 to C16 halogenated aryloxies, C7 to C18 halogenated alkoxyls, C1 to C12 hydrocarbons and halogenated hydrocarbons substituted derivatives thereof; β and Y are groups that each comprise at least one atom from Group 14 to one atom from Group 16; α is a bond group that forms a chemical bond to each of β and Y; and a, b, g and n are each integers from 1 to 4.
[0008]
Composition according to either of Claims 6 and 7, characterized in that the molar ratio of the non-metallocene component to the transition metal catalyst component is in the range of 1: 1 to 5: 1.
[0009]
Composition according to any one of claims 1 to 8, characterized in that the spray dried catalyst composition also comprises a metallocene catalyst component.
[0010]
10. Composition according to claim 9, characterized by the fact that the metallocene catalyst componenter is represented by the following formula: CpACpBMXn where: M is a metal atom; CpA and CpB are each individually substituted or unsubstituted cyclopentadienyl ligands; X is a leaving group; and N is zero or an integer from 1 to 4.
[0011]
Composition according to claim 1, characterized in that the atomizer dry catalyst composition also comprises a support and an activator.
[0012]
12. Polymerization process, characterized by the fact that it comprises combining an olefin with the composition defined in claim 1.
[0013]
13. Polymerization process according to claim 12, characterized in that the olefin comprises a C4 to C15 alpha olefin.
[0014]
14. Polymerization process according to either of claims 12 or 13, characterized in that the polymerization process takes place in a gas-phase reactor.

类似技术:

---

公开号 | 公开日 | 专利标题

---

BR112013029135B1|2020-12-15|COMPOSITION AND POLYMERIZATION PROCESS

---

ES2858098T3|2021-09-29|Production of catalyst compositions

---

BRPI0820630B1|2021-07-20|POLYMERIZATION CATALYST SYSTEM AND METHOD FOR OLEFIN POLYMERIZATION

---

RU2479593C2|2013-04-20|Method of controlling bimodal catalyst activity during polymerisation

---

ES2798272T3|2020-12-10|Methods of preparing a catalytic system

---

ES2873521T3|2021-11-03|Multiple catalyst system comprising metallocenes and nitrogen-based tridentate ligand complexes for olefin polymerization

---

KR20110082539A|2011-07-19|Catalyst compositions and methods of making and using the same

---

JP5941476B2|2016-06-29|Process for the polymerization of olefins using extracted metal carboxylate salts

---

BR112014010906B1|2020-12-01|method for producing a polyolefin

---

ES2852023T3|2021-09-10|Spray Dried Catalyst Compositions, Methods for Their Preparation and Use in Olefin Polymerization Processes

---

ES2752705T3|2020-04-06|Continuity compositions and olefin polymerization method using them

---

ES2723878T3|2019-09-03|Methods for preparing catalytic systems with increased productivity

---

BR112015023596B1|2021-01-05|process to produce a multimodal polyolefin

---

BR112013012545B1|2020-04-14|catalyst composition, production process of a catalyst composition and polymerization process

---

BR112015018250B1|2021-02-23|process to produce a catalyst composition and polymerization process

---

ES2718760T3|2019-07-04|Synthesis method of zirconium and hafnium monocyclopentadienyl complexes

---

CN106459248B|2020-03-03|Catalyst composition, preparation method and use in polymerization process

---

EP3708596A1|2020-09-16|Novel metallocene catalyst compound for production of polyolefin resin or method of preparing same

---

BR112019022049A2|2020-05-12|A HAFNIUM COMPLEX; A SUPPORTED HASSLE COMPLEX; METHODS FOR FORMING A POLYMER USING SUCH COMPLEXES

---

BR112017022154B1|2021-12-07|METHOD FOR SYNTHESIS OF A CATALYST COMPOUND, METHOD FOR FORMING A POLYETHYLENE COPOLYMER AND METHOD FOR SYNTHESIS OF A MONOCYCLOPENTADIENYL COMPOUND

---

BR112016022935B1|2021-12-07|CATALYST COMPOSITION, METHODS OF PREPARATION AND USE IN A POLYMERIZATION PROCESS

---

BR112017019133B1|2021-11-23|METHOD FOR PRODUCING A SUPPORTED CATALYST COMPOSITION FOR OLEFIN POLYMERIZATION

---

RU2588129C2|2016-06-27|Catalyst composition with improved looseness characteristics, and methods for production and use thereof

---

JP2015526583A|2015-09-10|Polymerization process using reactor components suspended in a hydrocarbon gel

同族专利:

---

公开号 | 公开日

---

US9637567B2|2017-05-02|

---

RU2598023C2|2016-09-20|

---

CN103534279A|2014-01-22|

---

EP2707398A1|2014-03-19|

---

US20150133615A1|2015-05-14|

---

WO2012158260A1|2012-11-22|

---

RU2013155222A|2015-06-20|

---

BR112013029135A2|2017-02-07|

---

EP2707398B1|2017-08-09|

---

ES2641112T3|2017-11-07|

---

CN103534279B|2016-08-17|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

US4543399A|1982-03-24|1985-09-24|Union Carbide Corporation|Fluidized bed reaction systems|

---

US4588790A|1982-03-24|1986-05-13|Union Carbide Corporation|Method for fluidized bed polymerization|

---

US4665208A|1985-07-11|1987-05-12|Exxon Chemical Patents Inc.|Process for the preparation of alumoxanes|

---

DE3600610A1|1986-01-11|1987-07-16|Basf Ag|USE OF ANTISTATICS TO PREVENT COATING IN THE PRODUCTION OF ETHYLENE POLYMERISATS IN GAS PHASE REACTORS|

---

EP0287666B1|1986-09-24|1993-05-26|Mitsui Petrochemical Industries, Ltd.|Process for polymerizing olefins|

---

JPH0780933B2|1986-11-20|1995-08-30|三井石油化学工業株式会社|Olefin Polymerization Method|

---

IL85097A|1987-01-30|1992-02-16|Exxon Chemical Patents Inc|Catalysts based on derivatives of a bisgroup ivb metal compound,their preparation and their use in polymerization processes|

---

US5241025A|1987-01-30|1993-08-31|Exxon Chemical Patents Inc.|Catalyst system of enhanced productivity|

---

US5384299A|1987-01-30|1995-01-24|Exxon Chemical Patents Inc.|Ionic metallocene catalyst compositions|

---

US5198401A|1987-01-30|1993-03-30|Exxon Chemical Patents Inc.|Ionic metallocene catalyst compositions|

---

US5153157A|1987-01-30|1992-10-06|Exxon Chemical Patents Inc.|Catalyst system of enhanced productivity|

---

PL276385A1|1987-01-30|1989-07-24|Exxon Chemical Patents Inc|Method for polymerization of olefines,diolefins and acetylene unsaturated compounds|

---

JPH0742301B2|1987-02-14|1995-05-10|三井石油化学工業株式会社|Particulate aluminoxane, its manufacturing method and its use|

---

JP2538588B2|1987-04-03|1996-09-25|三井石油化学工業株式会社|Method for producing solid catalyst for olefin polymerization|

---

US5206199A|1987-04-20|1993-04-27|Mitsui Petrochemical Industries, Ltd.|Catalyst for polymerizing an olefin and process for polymerizing an olefin|

---

FR2634212B1|1988-07-15|1991-04-19|Bp Chimie Sa|APPARATUS AND METHOD FOR POLYMERIZATION OF GASEOUS OLEFINS IN A FLUIDIZED BED REACTOR|

---

US5091352A|1988-09-14|1992-02-25|Mitsui Petrochemical Industries, Ltd.|Olefin polymerization catalyst component, olefin polymerization catalyst and process for the polymerization of olefins|

---

US5041584A|1988-12-02|1991-08-20|Texas Alkyls, Inc.|Modified methylaluminoxane|

---

US4908463A|1988-12-05|1990-03-13|Ethyl Corporation|Aluminoxane process|

---

US5103031A|1989-02-21|1992-04-07|Ethyl Corporation|Falling film aluminoxane process|

---

US4968827A|1989-06-06|1990-11-06|Ethyl Corporation|Alkylaluminoxane process|

---

US4924018A|1989-06-26|1990-05-08|Ethyl Corporation|Alkylaluminoxane process|

---

NZ235032A|1989-08-31|1993-04-28|Dow Chemical Co|Constrained geometry complexes of titanium, zirconium or hafnium comprising a substituted cyclopentadiene ligand; use as olefin polymerisation catalyst component|

---

US5026798A|1989-09-13|1991-06-25|Exxon Chemical Patents Inc.|Process for producing crystalline poly-α-olefins with a monocyclopentadienyl transition metal catalyst system|

---

US6265338B1|1989-09-13|2001-07-24|Exxon Chemical Patents, Inc.|Monocyclopentadienyl titanium metal compounds for ethylene-α-olefin copolymer production catalysts|

---

US5066741A|1990-03-22|1991-11-19|The Dow Chemical Company|Process for preparation of syndiotactic vinyl aromatic polymers|

---

FR2660926B1|1990-04-11|1992-07-31|Bp Chemicals Snc|ALPHA-OLEFIN PREPOLYMER CONTAINING A TRANSITIONAL METAL AND PROCESS FOR THE POLYMERIZATION OF ALPHA-OLEFIN IN THE GAS PHASE USING THE PREPOLYMER.|

---

JP3115595B2|1990-07-24|2000-12-11|三井化学株式会社|Polymerization catalyst for α-olefin and method for producing poly-α-olefin using the same|

---

EP0569388B1|1990-12-27|1996-03-13|Exxon Chemical Patents Inc.|An amido transition metal compound and a catalyst system for the production of isotactic polypropylene|

---

US5189192A|1991-01-16|1993-02-23|The Dow Chemical Company|Process for preparing addition polymerization catalysts via metal center oxidation|

---

US5206197A|1991-03-04|1993-04-27|The Dow Chemical Company|Catalyst composition for preparation of syndiotactic vinyl aromatic polymers|

---

US5341124A|1991-05-29|1994-08-23|Se-Kure Controls, Inc.|Mountable product sensor and display stand|

---

US5721185A|1991-06-24|1998-02-24|The Dow Chemical Company|Homogeneous olefin polymerization catalyst by abstraction with lewis acids|

---

US5308815A|1991-07-26|1994-05-03|Ethyl Corporation|Heterogeneous methylaluminoxane catalyst system|

---

US5157137A|1991-07-26|1992-10-20|Ethyl Corporation|Method of making gel free alkylaluminoxane solutions|

---

US5278272A|1991-10-15|1994-01-11|The Dow Chemical Company|Elastic substantialy linear olefin polymers|

---

KR100262023B1|1992-01-06|2000-07-15|그레이스 스티븐 에스.|Improved catalyst composition|

---

US5329032A|1992-03-18|1994-07-12|Akzo Chemicals Inc.|Polymethylaluminoxane of enhanced solution stability|

---

US5235081A|1992-03-18|1993-08-10|Ethyl Corporation|Method of removing gel forming materials from methylaluminoxanes|

---

US5436304A|1992-03-19|1995-07-25|Exxon Chemical Patents Inc.|Process for polymerizing monomers in fluidized beds|

---

US5352749A|1992-03-19|1994-10-04|Exxon Chemical Patents, Inc.|Process for polymerizing monomers in fluidized beds|

---

US5462999A|1993-04-26|1995-10-31|Exxon Chemical Patents Inc.|Process for polymerizing monomers in fluidized beds|

---

US5434115A|1992-05-22|1995-07-18|Tosoh Corporation|Process for producing olefin polymer|

---

BE1005957A5|1992-06-05|1994-04-05|Solvay|Preparation method of catalyst system, process polymerization of olefins and polymer at least one olefine.|

---

ES2137266T3|1992-07-01|1999-12-16|Exxon Chemical Patents Inc|OLEPHINE POLYMERIZATION CATALYSTS BASED ON TRANSITIONAL METALS.|

---

US5248801A|1992-08-27|1993-09-28|Ethyl Corporation|Preparation of methylaluminoxanes|

---

DE69312306T2|1992-10-02|1997-11-13|Dow Chemical Co|APPLICATION OF HOMOGENIC COMPLEX CATALYST FOR OLEFIN POLYMERIZATION|

---

US5317036A|1992-10-16|1994-05-31|Union Carbide Chemicals & Plastics Technology Corporation|Gas phase polymerization reactions utilizing soluble unsupported catalysts|

---

US5391793A|1992-11-02|1995-02-21|Akzo Nobel N.V.|Aryloxyaluminoxanes|

---

US5939346A|1992-11-02|1999-08-17|Akzo Nobel N.V.|Catalyst system comprising an aryloxyaluminoxane containing an electron withdrawing group|

---

US5391529A|1993-02-01|1995-02-21|Albemarle Corporation|Siloxy-aluminoxane compositions, and catalysts which include such compositions with a metallocene|

---

TW298593B|1993-02-12|1997-02-21|Hoechst Ag|

---

RU2120947C1|1993-04-26|1998-10-27|Эксон Кемикэл Пейтентс Инк.|Method of gas-phase polymerization in fluidized layer|

---

BE1007148A3|1993-05-17|1995-04-11|Solvay|Support for catalyst, method for producing gel precursor media for catalyst, method for preparing a catalyst support, catalyst for olefin polymerization and method for olefin polymerization using the catalyst .|

---

ZA943399B|1993-05-20|1995-11-17|Bp Chem Int Ltd|Polymerisation process|

---

CA2127822A1|1993-07-13|1995-01-14|Yoshinori Morita|Process for gas phase polymerization of olefin|

---

JPH09505340A|1993-11-19|1997-05-27|エクソン・ケミカル・パテンツ・インク|Polymerization catalyst system, production method and use thereof|

---

JPH07144455A|1993-11-25|1995-06-06|Canon Inc|Ink jet recording apparatus|

---

US5648310A|1993-12-23|1997-07-15|Union Carbide Chemicals & Plastics Technology Corporation|Spray dried, filled metallocene catalyst composition for use in polyolefin manufacture|

---

US5672669A|1993-12-23|1997-09-30|Union Carbide Chemicals & Plastics Technology Corporation|Spray dried, filled metallocene catalyst composition for use in polyolefin manufacture|

---

EP0668295B1|1994-02-17|1998-06-03|Union Carbide Chemicals & Plastics Technology Corporation|Spray dried, filled metallocene catalyst composition for use in polyolefin manufacture|

---

US5453471B1|1994-08-02|1999-02-09|Carbide Chemicals & Plastics T|Gas phase polymerization process|

---

US5625087A|1994-09-12|1997-04-29|The Dow Chemical Company|Silylium cationic polymerization activators for metallocene complexes|

---

DE69600892T2|1995-02-21|1999-04-01|Mitsubishi Chem Corp|Catalysts for olefin polymerization and process for producing olefin polymers obtained therewith|

---

US5616661A|1995-03-31|1997-04-01|Union Carbide Chemicals & Plastics Technology Corporation|Process for controlling particle growth during production of sticky polymers|

---

DE69617371T2|1995-06-08|2002-08-08|Showa Denko Kk|Ionic compounds and catalyst for olefin polymerization using the compounds|

---

US5677375A|1995-07-21|1997-10-14|Union Carbide Chemicals & Plastics Technology Corporation|Process for producing an in situ polyethylene blend|

---

US5731253A|1995-07-27|1998-03-24|Albemarle Corporation|Hydrocarbylsilloxy - aluminoxane compositions|

---

US5693838A|1995-11-13|1997-12-02|Albemarle Corporation|Aluminoxane process and product|

---

WO1997022639A1|1995-12-19|1997-06-26|Exxon Chemical Patents Inc.|High temperature solution polymerization process|

---

US5856256A|1996-02-20|1999-01-05|Northwestern University|Organo-Lewis acid as cocatalyst for cationic homogeneous Ziegler-Natta olefin polymerizations|

---

US5665818A|1996-03-05|1997-09-09|Union Carbide Chemicals & Plastics Technology Corporation|High activity staged reactor process|

---

US5627242A|1996-03-28|1997-05-06|Union Carbide Chemicals & Plastics Technology Corporation|Process for controlling gas phase fluidized bed polymerization reactor|

---

US5731451A|1996-07-12|1998-03-24|Akzo Nobel Nv|Modified polyalkylauminoxane composition formed using reagent containing aluminum trialkyl siloxide|

---

US5854166A|1996-08-19|1998-12-29|Northwestern University|Synthesis and use of fluoro-aluminate anion|

---

EP0927201B1|1996-09-06|2004-04-14|Hyundai Petrochemical Co., Ltd.|Catalyst system for polymerization of olefins and process for the preparation of olefin polymers using the catalyst system|

---

US5847177A|1996-10-10|1998-12-08|Albemarle Corporation|Production of hydrocarbon-soluble hydrocarbylaluminoxanes|

---

US5744656A|1996-10-25|1998-04-28|Boulder Scientific Company|Conversion of hexafluorobenzene to bromopentafluorobenzene|

---

US6620895B1|1999-03-22|2003-09-16|E. I. Du Pont De Nemours And Company|Processing polyethylenes|

---

US6432862B1|1996-12-17|2002-08-13|E. I. Du Pont De Nemours And Company|Cobalt catalysts for the polymerization of olefins|

---

IL129929D0|1996-12-17|2000-02-29|Du Pont|Polymerization of ethylene with specific iron or cobalt complexes novel pyridinebis and novel complexes of pyridinebis with iron and cobalt|

---

US6423848B2|1996-12-17|2002-07-23|E. I. Du Pont De Nemours And Company|Tridentate ligand|

---

US6214761B1|1996-12-17|2001-04-10|E. I. Du Pont De Nemours And Company|Iron catalyst for the polymerization of olefins|

---

US5747406A|1997-01-10|1998-05-05|Union Carbide Chemicals & Plastics Technology Corporation|Catalyst composition for the production of olefin polymers|

---

ES2226005T3|1997-01-14|2005-03-16|Sabic Polypropylenes B.V.|A PROCEDURE FOR POLYMERIZING OLEFINS.|

---

NL1004992C2|1997-01-14|1998-07-15|Dsm Nv|Use of compounds containing Si, Ge, Sn or Pb as a cocatalyst in the polymerization of olefins.|

---

FI970349A|1997-01-28|1998-07-29|Borealis As|New activator systems for metallocene compounds|

---

EP0893454A4|1997-02-07|2001-01-24|Mitsui Chemicals Inc|Olefin polymerization catalyst and process for the production of olefin polymers|

---

EP0975641A4|1997-04-03|2003-03-12|Univ Colorado State Res Found|Polyhalogenated monoheteroborane anion compositions|

---

US5889128A|1997-04-11|1999-03-30|Massachusetts Institute Of Technology|Living olefin polymerization processes|

---

TW420693B|1997-04-25|2001-02-01|Mitsui Chemicals Inc|Olefin polymerization catalysts, transition metal compounds, and <alpha>-olefin/conjugated diene copolymers|

---

US6103657A|1997-07-02|2000-08-15|Union Carbide Chemicals & Plastics Technology Corporation|Catalyst for the production of olefin polymers|

---

PL348825A1|1998-12-18|2002-06-17|Univation Technologies|Olefin polymerization catalyst system, polymerization process and polymer therefrom|

---

US6239235B1|1997-07-15|2001-05-29|Phillips Petroleum Company|High solids slurry polymerization|

---

ID24448A|1997-09-05|2000-07-20|Bp Chemical Ltd|POLYMERIZATION CATALYSTS|

---

ID24920A|1997-09-19|2000-08-31|Teh Dow Chemical Company|ACTIVATED MATERIALS MODIFIED ALUMOXIC CATALYST|

---

DE19744102A1|1997-10-06|1999-04-15|Targor Gmbh|Metallocene catalyst system useful in polyolefin production|

---

US6069213A|1997-12-16|2000-05-30|Union Carbide Chemicals & Plastics Technology Corporation|Mixed catalyst system|

---

US6232259B1|1998-03-31|2001-05-15|E. I. Du Pont De Nemours And Company|Preparation of transition metal imine complexes|

---

JP2002517526A|1998-05-29|2002-06-18|イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー|Olefin copolymerization|

---

US6252022B1|1998-05-29|2001-06-26|E. I. Du Pont De Nemours And Company|Molecular weight control in olefin polymerization|

---

GB9819847D0|1998-09-12|1998-11-04|Bp Chem Int Ltd|Novel compounds|

---

JP4467189B2|1998-10-26|2010-05-26|イネオスユーロープリミテッド|Polymerization catalyst|

---

US6333389B2|1998-12-18|2001-12-25|Univation Technologies, Llc|Olefin polymerization catalysts, their production and use|

---

JP2004506745A|1999-02-22|2004-03-04|イーストマン　ケミカル　カンパニー|Catalyst containing N-pyrrolyl-substituted nitrogen donor|

---

US7056996B2|2000-02-18|2006-06-06|E. I. Du Pont De Nemours And Company|Productivity catalysts and microstructure control|

---

US6458979B1|1999-04-29|2002-10-01|E. I. Du Pont De Nemours And Company|Polymerization of ethylene|

---

US6365690B1|1999-05-06|2002-04-02|E. I. Du Pont De Nemours And Company|Polymerization of ethylene|

---

US6271325B1|1999-05-17|2001-08-07|Univation Technologies, Llc|Method of polymerization|

---

US6281303B1|1999-07-27|2001-08-28|Eastman Chemical Company|Olefin oligomerization and polymerization catalysts|

---

US6441117B1|1999-09-01|2002-08-27|E. I. Du Pont De Nemours And Company|High density polyethylene packaging|

---

AT257491T|1999-09-29|2004-01-15|Du Pont|PRODUCTION OF CURABLE POLYMERS|

---

BR0015235A|1999-10-22|2002-12-31|Univation Tech Llc|Catalyst compositions, polymerization methods, and polymers thereof|

---

DE60021405T2|1999-10-22|2006-05-18|Univation Technologies, LLC, Houston|Catalyst systems and their use in a polymerisation process|

---

US6274684B1|1999-10-22|2001-08-14|Univation Technologies, Llc|Catalyst composition, method of polymerization, and polymer therefrom|

---

US6699955B1|1999-11-19|2004-03-02|E. I. Du Pont De Nemours And Company|Copolymerization of ethylene and dienes|

---

US6482903B1|1999-12-15|2002-11-19|Univation Technologies, Llc|Method for preparing a supported catalyst system and its use in a polymerization process|

---

US6281306B1|1999-12-16|2001-08-28|Univation Technologies, Llc|Method of polymerization|

---

US6531424B2|1999-12-17|2003-03-11|E. I. Du Pont De Nemours And Company|Polymerization of olefins|

---

US6586541B2|2000-02-02|2003-07-01|E. I. Du Pont De Nemours And Company|Process for production of polyolefins|

---

US6521724B2|2000-03-10|2003-02-18|E. I. Du Pont De Nemours And Company|Polymerization process|

---

US6964937B2|2000-11-30|2005-11-15|Univation Technologies, Llc|Bimetallic catalyst for producing polyethylene resins with bimodal molecular weight distribution, its preparation and use|

---

US20020137861A1|2000-12-04|2002-09-26|Woo Min Song|Polymerization process|

---

WO2002046246A2|2000-12-04|2002-06-13|Univaton Technologies, Llc|Polimerization process|

---

US6605675B2|2000-12-04|2003-08-12|Univation Technologies, Llc|Polymerization process|

---

US6518444B1|2000-12-18|2003-02-11|Univation Technologies, Llc|Preparation of polymerization catalysts|

---

US6900153B2|2001-03-28|2005-05-31|E.I. Du Pont De Nemours And Company|Supported olefin polymerization catalysts|

---

US6936675B2|2001-07-19|2005-08-30|Univation Technologies, Llc|High tear films from hafnocene catalyzed polyethylenes|

---

CA2466612A1|2001-11-30|2003-06-12|Exxonmobil Chemical Patents Inc.|Bimetallic catalysts with higher activity|

---

US7148175B2|2002-01-09|2006-12-12|E. I. Du Pont De Nemours And Company|Catalyst for olefin polymerization|

---

RU2002116724A|2002-06-21|2004-01-20|Институт катализа им. Г.К. Борескова СО РАН|Supported Ziegler-type catalyst for ethylene polymerization and polymerization method|

---

US6982237B2|2002-07-15|2006-01-03|Univation Technologies, Llc|Spray-dried polymerization catalyst and polymerization processes employing same|

---

US6884748B2|2002-09-04|2005-04-26|Univation Technologies, Llc|Process for producing fluorinated catalysts|

---

AU2003270780A1|2002-09-20|2004-04-08|Exxonmobil Chemical Patents Inc.|Polymer production at supercritical conditions|

---

NZ539796A|2002-11-21|2006-11-30|Kowa Co|Peritoneal dialysis method comprising adenosine triphosphate|

---

US6958306B2|2003-08-28|2005-10-25|Univation Technologies, Llc|Activated catalyst systems from substituted dialuminoxane complexes|

---

US7022787B2|2003-09-25|2006-04-04|E. I. Du Pont De Nemours And Company|Olefin polymerization catalyst|

---

US7741417B2|2004-01-07|2010-06-22|Exxonmobil Chemical Patents Inc.|Preparation of polymerization catalyst activators utilizing indole-modified silica supports|

---

RU2248374C1|2004-01-29|2005-03-20|Институт Катализа Им. Г.К. Борескова Сибирского Отделения Российской Академии Наук|Method for scouring of blast furnace, two-component immobilized catalyst for ethylene polymerization, method for production the same , and method for production of polyethylene using this catalyst|

---

US6967184B2|2004-02-17|2005-11-22|Univation Technologies, Llc|Fluoroalcohol leaving group for non-metallocene olefin polymerization catalysts|

---

US20050182210A1|2004-02-17|2005-08-18|Natarajan Muruganandam|De-foaming spray dried catalyst slurries|

---

US7157531B2|2004-06-21|2007-01-02|Univation Technologies, Llc|Methods for producing polymers with control over composition distribution|

---

US7741420B2|2004-07-14|2010-06-22|Exxonmobil Chemical Patents Inc.|Polymer production at supercritical conditions|

---

US7169864B2|2004-12-01|2007-01-30|Novolen Technology Holdings, C.V.|Metallocene catalysts, their synthesis and their use for the polymerization of olefins|

---

US7312283B2|2005-08-22|2007-12-25|Chevron Phillips Chemical Company Lp|Polymerization catalysts and process for producing bimodal polymers in a single reactor|

---

KR101408618B1|2006-06-27|2014-06-17|유니베이션 테크놀로지즈, 엘엘씨|Improved polymerization processes using metallocene catalysts, their polymer products and end uses|

---

CN102712715B|2010-01-21|2014-10-29|巴塞尔聚烯烃股份有限公司|Process for the preparation of ethylene copolymer compositions in the presence of an oligomerization catalyst|WO2016145179A1|2015-03-10|2016-09-15|Univation Technologies, Llc|Spray dried catalyst compositions, methods for preparation and use in olefin polymerization processes|

---

WO2016172099A1|2015-04-20|2016-10-27|Exxonmobil Chemical Patents Inc.|Polyethylene composition|

---

US10533063B2|2015-04-20|2020-01-14|Exxonmobil Chemical Patents Inc.|Supported catalyst systems and processes for use thereof|

---

WO2017039994A1|2015-08-31|2017-03-09|Exxonmobil Chemical Patents Inc.|Aluminum alkyls with pendant olefins on clays|

---

CN107922527A|2015-08-31|2018-04-17|埃克森美孚化学专利公司|The aluminium alkyl with pendency alkene for polyene hydrocarbon reaction|

---

US10626200B2|2017-02-28|2020-04-21|Exxonmobil Chemical Patents Inc.|Branched EPDM polymers produced via use of vinyl transfer agents and processes for production thereof|

---

US10618988B2|2015-08-31|2020-04-14|Exxonmobil Chemical Patents Inc.|Branched propylene polymers produced via use of vinyl transfer agents and processes for production thereof|

---

US9982067B2|2015-09-24|2018-05-29|Exxonmobil Chemical Patents Inc.|Polymerization process using pyridyldiamido compounds supported on organoaluminum treated layered silicate supports|

---

US10000593B2|2015-10-02|2018-06-19|Exxonmobil Chemical Patents Inc.|Supported Salan catalysts|

---

US9982076B2|2015-10-02|2018-05-29|Exxonmobil Chemical Patents Inc.|Supported bis phenolate transition metals complexes, production and use thereof|

---

US9994657B2|2015-10-02|2018-06-12|Exxonmobil Chemical Patents Inc.|Polymerization process using bis phenolate compounds supported on organoaluminum treated layered silicate supports|

---

US9975973B2|2015-10-02|2018-05-22|Exxonmobil Chemical Patents Inc.|Asymmetric fluorenyl-substituted salan catalysts|

---

US10414887B2|2015-10-02|2019-09-17|Exxonmobil Chemical Patents Inc.|Supported catalyst systems and methods of using same|

---

US9994658B2|2015-10-02|2018-06-12|Exxonmobil Chemical Patents Inc.|Polymerization process using bis phenolate compounds supported on organoaluminum treated layered silicate supports|

---

US10562987B2|2016-06-30|2020-02-18|Exxonmobil Chemical Patents Inc.|Polymers produced via use of quinolinyldiamido transition metal complexes and vinyl transfer agents|

---

EP3538570A1|2016-11-08|2019-09-18|Univation Technologies, LLC|Polyethylene composition|

---

EP3559058A1|2016-12-22|2019-10-30|ExxonMobil Chemical Patents Inc.|Spray-dried olefin polymerization catalyst compositions and polymerization processes for using the same|

---

WO2018151903A1|2017-02-20|2018-08-23|Exxonmobil Chemical Patents Inc.|Supported catalyst systems and processes for use thereof|

---

US10723819B2|2017-02-20|2020-07-28|Exxonmobil Chemical Patents, Inc.|Supported catalyst systems and processes for use thereof|

---

US10676551B2|2017-03-01|2020-06-09|Exxonmobil Chemical Patents Inc.|Branched ethylene copolymers produced via use of vinyl transfer agents and processes for production thereof|

---

CN111108130A|2017-08-04|2020-05-05|埃克森美孚化学专利公司|Has the advantages ofcontaining-CH2-SiMe3Hybrid catalysts of partially unbridged hafnocenes|

---

US10844150B2|2017-08-04|2020-11-24|Exxonmobil Chemical Patents Inc.|Mixed catalysts with 2,6-bispyridyl iron complexes and bridged hafnocenes|

---

WO2019070329A1|2017-10-06|2019-04-11|Exxonmobil Chemical Patents Inc.|Polyethylene extrudates and methods of making the same|

---

US10703838B2|2017-10-31|2020-07-07|Exxonmobil Chemical Patents Inc.|Mixed catalyst systems with four metallocenes on a single support|

---

US10926250B2|2017-12-01|2021-02-23|Exxonmobil Chemical Patents Inc.|Catalyst systems and polymerization processes for using the same|

---

EP3717522A1|2017-12-01|2020-10-07|ExxonMobil Chemical Patents Inc.|Catalyst systems and polymerization processes for using the same|

---

US10865258B2|2018-01-31|2020-12-15|Exxonmobil Chemical Patents Inc.|Mixed catalyst systems containing bridged metallocenes with a pendant group 13 element, processes for making a polymer product using same, and products made from same|

---

US10851187B2|2018-01-31|2020-12-01|Exxonmobil Chemical Patents Inc.|Bridged metallocene catalysts with a pendant group 13 element, catalyst systems containing same, processes for making a polymer product using same, and products made from same|

---

WO2021202486A1|2020-04-01|2021-10-07|Dow Global Technologies Llc|Bimodal linear low density polyethylene copolymer|

法律状态:
2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|

---

2020-04-14| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|

---

2020-09-08| B09A| Decision: intention to grant|

---

2020-12-15| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 28/03/2012, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

---

申请号 | 申请日 | 专利标题

---

US201161485724P| true| 2011-05-13|2011-05-13|

---

US61/485,724|2011-05-13|

---

PCT/US2012/030805|WO2012158260A1|2011-05-13|2012-03-28|Spray-dried catalyst compositions and polymerization processes employing the same|

---