Catalyst composition, method of preparation and use in polymerization processes

Abstract

Polymerization catalyst compositions and methods for their preparation are provided. The compositions comprise a fatty amine and are advantageously used in olefin polymerization processes. The catalyst compositions comprise at least one supported polymerization catalyst, wherein the catalyst composition is modified with at least one fatty amine, wherein the fatty amine is substantially free of particulate inorganic materials.

Description

[0001] This application is a divisional application of the invention application filed on February 5, 2015, with Chinese application number 201580026437.5 and entitled "Catalyst Composition, Preparation Method and Use in Polymerization Process".

[0002] Cross-reference to related applications

[0003] This application is an international application claiming the benefit and priority of U.S. Patent Application No. 61 / 985,143, filed April 28, 2014, and U.S. Patent Application No. 61 / 974,032, filed April 2, 2014, the disclosure of which is incorporated herein by reference in its entirety. Technical Field

[0004] This invention relates to catalyst compositions, methods for preparing said catalyst compositions, and their use in polymerizing olefins. Specifically, this invention relates to a method for preparing catalyst compositions for metallocene catalyst systems and / or conventional transition metal catalyst systems, as well as aliphatic amine additives. Background Technology

[0005] A major focus in the polyolefin industry in recent years has been the development of novel catalysts that provide new and improved products. In this regard, metallocene catalysts, for example, are now widely used in the production of polyolefin polymers, such as polyethylene. While the use of metallocene catalysts in olefin polymerization offers many advantages, significant challenges remain. For instance, metallocene catalysts, especially supported metallocene catalysts, are more prone to reactor fouling, which can lead to reactor interruptions and premature shutdowns, particularly in particle-forming processes such as gas-phase and slurry-phase processes. Adding other agents to the polymerization process, such as antifouling agents, antistatic agents, or continuous additives / auxiliaries or continuous compositions, has been used to address these fouling problems.

[0006] To address reactor fouling issues caused by highly active metallocene catalysts, additives containing aliphatic amines have been added to polymerization processes, either independently or as part of supported catalyst compositions. However, aliphatic amines invariably contain particulate inorganic materials.

[0007] U.S. Patent Application Publication No. US20010020072 discloses the use of a specific ethoxylated stearamide, AS-990, as an antistatic agent in olefin polymerization. AS-990 contains ethoxylated stearamide and particulate silica. The particulate silica is present in an amount of approximately 10% by weight, based on the weight of the ethoxylated stearamide and silica. The addition of silica improves the processing quality of the ethoxylated stearamide, which is a waxy solid at ambient temperature.

[0008] However, the preparation of such aliphatic amine / silica compositions is time-consuming and often exhibits incompatible properties. Mixing solid or waxy components can lead to the formation of agglomerates, which may make it difficult to dry the material to the low moisture content desired for olefin polymerization.

[0009] Therefore, despite the existence of various polymerization catalysts, challenges remain. Thus, there is a need for catalyst compositions suitable for olefin polymerization that are easy to prepare and process and can also be operated continuously in the polymerization process, offering enhanced reactor operability. Summary of the Invention

[0010] In a first aspect, a catalyst composition is provided comprising at least one supported polymerization catalyst, wherein the supported polymerization catalyst is modified with at least one aliphatic amine, and wherein the aliphatic amine is substantially free of particulate inorganic material. When used in this context, the term "substantially free of" means that the aliphatic amine contains less than 2% by weight, or less than 1% by weight, or less than 0.5% by weight, or 0% by weight of particulate inorganic material.

[0011] Aliphatic amines may be substantially free of particulate inorganic oxides. For example, aliphatic amines may be substantially free of particulate silica or particulate alumina, that is, containing less than 2% by weight, or less than 1% by weight, or less than 0.5% by weight, or 0% by weight of particulate inorganic material or particulate silica or particulate alumina.

[0012] At least one fatty amine can be represented by the following formula:

[0013] (R1) x N(R2OH) y

[0014] in

[0015] R1 is a hydrocarbon group having 8 to 40 carbon atoms;

[0016] R2 is a divalent hydrocarbon group having 1 to 8 carbon atoms;

[0017] as well as

[0018] The value of x is 1 or 2 and x + y = 3.

[0019] R1 can be a hydrocarbon group having 14 to 26 carbon atoms. R2 can be methylene, ethylene, n-propylene, n-butylene, or isopropylene.

[0020] Fatty amines can be ethoxylated stearamides.

[0021] The aliphatic amine may be present in about 0.05 to about 20% by weight, or about 0.1 to about 10% by weight, or about 0.1 to about 5% by weight, or about 0.2 to about 2% by weight, based on the total weight of the catalyst composition.

[0022] The catalyst composition may be in the form of a substantially dry powder or a slurry suitable for use with a liquid medium. The liquid medium may be an aliphatic or aromatic hydrocarbon or a mixture thereof. The liquid medium may also be a mineral oil.

[0023] Supported polymerization catalysts may comprise a support, an activator, and one or more catalyst compounds containing titanium, zirconium, or hafnium atoms. The catalyst compound may comprise:

[0024] (pentamethylcyclopentadienyl)(propylcyclopentadienyl)MX2

[0025] (tetramethylcyclopentadienyl)(propylcyclopentadienyl)MX2

[0026] (tetramethylcyclopentadienyl)(butylcyclopentadienyl)MX2

[0027] Me2Si(indene)2MX2,

[0028] Me2Si(tetrahydroindenyl)2MX2,

[0029] (n-propylcyclopentadienyl)2MX2

[0030] (n-Butylcyclopentadienyl)2MX2

[0031] (1-Methyl, 3-Butylcyclopentadienyl)2MX2,

[0032] HN(CH2CH2N(2,4,6-Me3phenyl))2MX2,

[0033] HN(CH2CH2N(2,3,4,5,6-Me5phenyl))2MX2,

[0034] (propylcyclopentadienyl)(tetramethylcyclopentadienyl)MX2

[0035] (Butylcyclopentadienyl)2MX2

[0036] (propylcyclopentadienyl)2MX2, and mixtures thereof,

[0037] Where M is Zr or Hf, and X is selected from F, Cl, Br, I, Me, benzyl, CH2SiMe3, and C1 to C5 alkyl or alkenyl groups.

[0038] Supported polymerization catalysts may comprise two or more catalyst compounds containing titanium, zirconium, or hafnium atoms. The two or more catalyst compounds may comprise one or more metallocene compounds and one or more compounds containing Group 15 metals. The metallocene compounds may include:

[0039] (pentamethylcyclopentadienyl)(propylcyclopentadienyl)MX2

[0040] (tetramethylcyclopentadienyl)(propylcyclopentadienyl)MX2

[0041] (tetramethylcyclopentadienyl)(butylcyclopentadienyl)MX2

[0042] Me2Si(indene)2MX2,

[0043] Me2Si(tetrahydroindenyl)2MX2,

[0044] (n-propylcyclopentadienyl)2MX2

[0045] (n-Butylcyclopentadienyl)2MX2

[0046] (1-Methyl, 3-Butylcyclopentadienyl)2MX2,

[0047] (propylcyclopentadienyl)(tetramethylcyclopentadienyl)MX2

[0048] (Butylcyclopentadienyl)2MX2

[0049] (propylcyclopentadienyl)2MX2, and mixtures thereof,

[0050] Where M is Zr or Hf, and X is selected from F, Cl, Br, I, Me, benzyl, CH2SiMe3, and C1 to C5 alkyl or alkenyl groups; and compounds containing Group 15 metals may include:

[0051] HN(CH2CH2N(2,4,6-Me3phenyl))2MX2 or

[0052] HN(CH2CH2N(2,3,4,5,6-Me5phenyl))2MX2,

[0053] Where M is Zr or Hf, and X is selected from F, Cl, Br, I, Me, benzyl, CH2SiMe3, and C1 to C5 alkyl or alkenyl groups.

[0054] The fatty amines used in this paper have advantages over those amines utilized in prior art. For example, the time-consuming process of treating fatty amines with silica can be eliminated. The fatty amines can optionally be dried under vacuum, and further optionally by means of nitrogen purging and / or spraying, minimizing agglomerate formation. The fatty amines can be dried to low moisture content in a relatively short time, exhibiting excellent batch-to-batch consistency.

[0055] The catalyst compositions disclosed herein may possess advantageous properties. Supported catalysts treated with aliphatic amines as disclosed herein unexpectedly provide catalyst compositions that exhibit good catalytic activity and / or process continuity in continuous olefin polymerization processes.

[0056] This article also discloses a method for manufacturing a catalyst composition and a polymerization process using the catalyst composition.

[0057] Therefore, this article also provides a method for manufacturing a catalyst composition, the method comprising the steps of contacting at least one supported catalyst with at least one aliphatic amine, as described above, wherein the aliphatic amine is substantially free of particulate inorganic material.

[0058] The method can be carried out in the presence of one or more liquid mediators. The liquid mediator can be an aliphatic or aromatic hydrocarbon. Preferably, the liquid mediator is an aromatic hydrocarbon.

[0059] The method may include the following steps:

[0060] As disclosed herein, at least one supported catalyst is contacted with at least one aliphatic amine in at least one liquid medium to form a slurry of the catalyst composition in the liquid medium.

[0061] The method may also include the following steps:

[0062] a) Combining at least one supported catalyst with a liquid medium to form a slurry; and

[0063] b) Add at least one fatty amine to the slurry to form a slurry of the catalyst composition in the liquid medium.

[0064] The method may also include the following steps:

[0065] a) Combining at least one fatty amine with a liquid mediator; and

[0066] b) Combining at least one supported catalyst with the mixture formed in a) to form a slurry of the catalyst composition in the liquid medium.

[0067] The method may further include the step of drying the slurry formed in the method disclosed herein to provide substantially dry and / or free-flowing powder.

[0068] In any of the methods disclosed herein, the aliphatic amine is soluble in a liquid medium. The liquid medium may be an aromatic solvent, such as toluene.

[0069] Aliphatic amines can be pre-dried at temperatures above ambient, optionally by means of a vacuum, and further optionally by means of nitrogen purging and / or spraying.

[0070] This article also discloses a process for polymerizing olefins, the process comprising:

[0071] In polymerization conditions, olefins are contacted in a reactor with one or more catalyst compositions as disclosed above to produce olefin polymers or copolymers.

[0072] This application involves the following technical content:

[0073] 1. A catalyst composition comprising at least one supported polymerization catalyst, wherein the catalyst composition is modified with at least one aliphatic amine, wherein the aliphatic amine is substantially free of particulate inorganic material.

[0074] 2. The catalyst composition according to claim 1, wherein the aliphatic amine contains less than 1% by weight of particulate inorganic material.

[0075] 3. The catalyst composition according to claim 1 or 2, wherein the aliphatic amine contains less than 0.5% by weight of particulate inorganic material.

[0076] 4. The catalyst composition according to any one of claims 1 to 3, wherein the particulate inorganic material comprises particulate silica.

[0077] 5. The catalyst composition according to any one of claims 1 to 4, wherein the at least one aliphatic amine is represented by the following formula:

[0078] (R1) x N(R2OH) y

[0079] in

[0080] R1 is a hydrocarbon group having 8 to 40 carbon atoms;

[0081] R2 is a hydrocarbon group having 1 to 8 carbon atoms;

[0082] as well as

[0083] The value of x is 1 or 2 and x + y = 3.

[0084] 6. The catalyst composition according to any one of claims 1 to 5, wherein R1 is a hydrocarbon group having 14 to 26 carbon atoms, and R2 is methyl, ethyl, n-propyl, n-butyl, or isopropyl.

[0085] 7. The catalyst composition according to any one of items 1 to 6, wherein the fatty amine is ethoxylated stearamide.

[0086] 8. The catalyst composition according to any one of claims 1 to 7, wherein the fatty amine is present in an amount of about 0.1% to about 20% by weight of the catalyst composition.

[0087] 9. The catalyst composition according to any one of claims 1 to 8, wherein the supported polymerization catalyst comprises a support, an activator, and one or more catalyst compounds comprising titanium, zirconium, or hafnium atoms.

[0088] 10. The catalyst composition according to any one of claims 1 to 9, wherein the supported polymerization catalyst comprises a catalyst compound selected from:

[0089] (pentamethylcyclopentadienyl)(propylcyclopentadienyl)MX2

[0090] (tetramethylcyclopentadienyl)(propylcyclopentadienyl)MX2

[0091] (tetramethylcyclopentadienyl)(butylcyclopentadienyl)MX2

[0092] Me2Si(indene)2MX2,

[0093] Me2Si(tetrahydroindenyl)2MX2,

[0094] (n-propylcyclopentadienyl)2MX2

[0095] (n-Butylcyclopentadienyl)2MX2

[0096] (1-Methyl, 3-Butylcyclopentadienyl)2MX2,

[0097] HN(CH2CH2N(2,4,6-Me3phenyl))2MX2,

[0098] HN(CH2CH2N(2,3,4,5,6-Me5phenyl))2MX2,

[0099] (propylcyclopentadienyl)(tetramethylcyclopentadienyl)MX2

[0100] (Butylcyclopentadienyl)2MX2

[0101] (propylcyclopentadienyl)2MX2, and combinations thereof,

[0102] Where M is Zr or Hf, and X is selected from the group consisting of: F, Cl, Br, I, Me, benzyl, CH2SiMe3, and C1 to C5 alkyl or alkenyl groups.

[0103] 11. The catalyst composition according to any one of claims 1 to 10, wherein the supported catalyst comprises two or more catalyst compounds, the catalyst compounds comprising one or more metallocene compounds and one or more compounds containing a Group 15 metal,

[0104] The one or more metallocene compounds mentioned above are selected from:

[0105] (pentamethylcyclopentadienyl)(propylcyclopentadienyl)MX2

[0106] (tetramethylcyclopentadienyl)(propylcyclopentadienyl)MX2

[0107] (tetramethylcyclopentadienyl)(butylcyclopentadienyl)MX2

[0108] Me2Si(indene)2MX2,

[0109] Me2Si(tetrahydroindenyl)2MX2,

[0110] (n-propylcyclopentadienyl)2MX2

[0111] (n-Butylcyclopentadienyl)2MX2

[0112] (1-Methyl, 3-Butylcyclopentadienyl)2MX2,

[0113] (propylcyclopentadienyl)(tetramethylcyclopentadienyl)MX2

[0114] (Butylcyclopentadienyl)2MX2 and

[0115] (propylcyclopentadienyl)2MX2,

[0116] And the one or more compounds containing Group 15 metals are selected from:

[0117] HN(CH2CH2N(2,4,6-Me3phenyl))2MX2 and

[0118] HN(CH2CH2N(2,3,4,5,6-Me5phenyl))2MX2,

[0119] Where M is Zr or Hf, and X is selected from the group consisting of: F, Cl, Br, I, Me, benzyl, CH2SiMe3, and C1 to C5 alkyl or alkenyl groups.

[0120] 12. The catalyst composition according to any one of claims 1 to 11, comprising at least one other continuous additive.

[0121] 13. The catalyst composition according to claim 12, wherein the other continuous additive comprises at least one metal carboxylate.

[0122] 14. A method for manufacturing a catalyst composition, the method comprising the step of contacting at least one supported catalyst with at least one aliphatic amine, wherein the aliphatic amine is substantially free of particulate inorganic material.

[0123] 15. The method according to item 14, the method comprising the following steps:

[0124] At least one supported catalyst is contacted with at least one fatty amine in at least one liquid medium to form a slurry of the catalyst composition in the liquid medium.

[0125] 16. The method according to item 15, the method comprising the following steps:

[0126] a) Combining at least one supported catalyst with a liquid medium to form a slurry; and

[0127] b) Add at least one fatty amine to the slurry to form a slurry of the catalyst composition in the liquid medium.

[0128] 17. The method according to item 15, the method comprising the following steps:

[0129] a) Combining at least one fatty amine with a liquid mordant; and

[0130] b) Combining at least one supported catalyst with the mixture formed in a) to form a slurry of the catalyst composition in the liquid medium.

[0131] 18. The method according to any one of items 15 to 17, wherein the liquid medium is an aromatic hydrocarbon.

[0132] 19. The method according to any one of claims 15 to 18, wherein the method further comprises the step of drying the slurry to provide a substantially free-flowing powder.

[0133] 20. The method according to any one of items 14 to 19, wherein the at least one fatty amine is represented by the following formula:

[0134] (R1) x N(R2OH) y

[0135] in

[0136] R1 is a hydrocarbon group having 9 to 40 carbon atoms;

[0137] R2 is a hydrocarbon group having 1 to 8 carbon atoms;

[0138] as well as

[0139] The value of x is 1 or 2 and x + y = 3.

[0140] 21. A method for polymerizing olefins, the method comprising:

[0141] Under polymerization conditions, olefins are contacted in a reactor with one or more catalyst compositions according to any one of claims 1 to 13 to produce olefin polymers or copolymers. Detailed Implementation

[0142] Before disclosing and describing the compounds, components, compositions, and / or methods of the present invention, it should be understood that, unless otherwise indicated, the invention is not limited to specific compounds, components, compositions, reactants, reaction conditions, ligands, metallocene structures, etc., and therefore variations are possible unless otherwise stated. It should also be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting.

[0143] It must also be noted that, as used in the specification and appended claims, unless otherwise stated, the singular forms “a,” “an,” and “the” include multiple indicators. Thus, for example, in the section “substituted with a leaving group,” a reference to “leaving group” includes more than one leaving group, such that the portion can be substituted with two or more of the said groups. Similarly, in the section “substituted with a halogen atom,” a reference to “a halogen atom” includes more than one halogen atom, such that the portion can be substituted with two or more halogen atoms; a reference to “a substituent” includes one or more substituents; a reference to “a ligand” includes one or more ligands, etc.

[0144] As used herein, all references to the periodic table and its groups refer to the new notation published in the 13th edition of HAWLEY'S CONDENSED CHEMICAL DICTIONARY, John Wiley & Sons, Inc. (1997) (reproduced with permission from the International Union of Theoretical and Applied Chemistry (IUPAC), unless reference is made to the previous IUPAC notation with Roman numerals (which also appears therein), or unless otherwise indicated.

[0145] This document discloses catalyst compositions for olefin polymerization that are advantageous for preparation and use. The catalyst compositions are characterized by being modified, contacted with, or treated with at least one aliphatic amine, which is substantially free of particulate inorganic material. The catalyst compositions can be operated continuously in polymerization processes, providing enhanced reactor operability. This document also discloses methods for manufacturing the catalyst compositions and polymerization processes utilizing the catalyst compositions for manufacturing olefin polymers.

[0146] catalyst

[0147] Any catalyst or combination of catalysts used for the polymerization of olefins is suitable for the polymerization process of this invention. The following is a discussion of various catalysts for illustrative purposes and not for limitation.

[0148] General definition

[0149] As used herein, a “catalyst composition” includes one or more catalyst components for polymerizing olefins and may also include at least one activator or, alternatively, at least one co-catalyst. The catalyst composition may also include other components, such as a support, and is not limited to catalyst components and / or activators or co-catalysts in individual or combined forms. A catalyst composition may include any suitable number of catalyst components in any combination as described herein, and any activator or co-catalyst in any combination as described herein. The “catalyst composition” may also contain one or more additional components known in the art for reducing or eliminating reactor fouling, such as continuous additives.

[0150] As used herein, a “catalyst compound” may include any compound that, when activated, is capable of catalyzing the polymerization or oligomerization of olefins, wherein the catalyst compound comprises at least one group 3 to group 12 atom and optionally at least one leaving group bonded thereto.

[0151] As used herein, the term "continuous additive" refers to a component, additive, or auxiliary agent, such as a solid or liquid, suitable for gas-phase or slurry-phase polymerization processes to reduce or eliminate reactor fouling, wherein "fouling" can manifest itself through a variety of phenomena, including flaking of reactor walls, blockage of inlet and outlet pipes, formation of large aggregates, or other forms of reactor disturbance known in the art.

[0152] conventional catalysts

[0153] Conventional catalysts are those well-known in the art, such as traditional Ziegler-Natta catalysts and Phillips-type chromium catalysts. Examples of conventional types of transition metal catalysts are disclosed in U.S. Patents 4,115,639, 4,077,904, 4,482,687, 4,564,605, 4,721,763, 4,879,359, and 4,960,741. Conventional types of transition metal catalyst compounds that can be used in this invention include (but are not limited to) transition metal compounds from Groups III to VIII of the periodic table.

[0154] These conventional types of transition metal catalysts can be represented by the following formula: MR x In the formula, M is a metal from Group IIIB to Group VIII, preferably Group IVB, and more preferably titanium; R is a halogen or alkyl group; and x is the valence state of metal M. Non-limiting examples of R may include alkoxy, phenoxy, bromide, chloride, and fluoride. Conventional transition metal catalysts in which M is titanium may include (but are not limited to) TiCl4, TiBr4, Ti(OC2H5)3Cl, Ti(OC2H5)Cl3, Ti(OC4H9)3Cl, Ti(OC3H7)2Cl2, Ti(OC2H5)2Br2, TiCl3.1 / 3AlCl3, and Ti(OC4H9)2Cl2. 12 H 25 )Cl3.

[0155] Conventional types of transition metal catalyst compounds based on magnesium / titanium electron-donator complexes suitable for the present invention are described, for example, in U.S. Patent Nos. 4,302,565 and 4,302,566. MgTiCl6(ethyl acetate)4 derivatives are one such example. British Patent Application 2,105,355 describes various conventional types of vanadium catalyst compounds. Non-limiting examples of conventional types of vanadium catalyst compounds include vanadium trihalides, vanadium alkoxyhalides, and vanadium alkoxyoxides, such as VOCl3, VOCl2(OBu) (where Bu = butyl), and VO(OC2H5)3; vanadium tetrahalides and vanadium alkoxyhalides, such as VCl4 and VCl3(OBu); vanadium acetylacetonate and vanadium oxyacetylacetonate, such as V(AcAc)3 and VOCl2(AcAc) (where (AcAc) is acetylacetonate). Examples of conventional types of vanadium catalyst compounds are VOCl3, VCl4, and VOCl2-OR (where R is a hydrocarbon group, preferably C1 to C1). 10Aliphatic or aromatic hydrocarbon groups, such as ethyl, phenyl, isopropyl, butyl, propyl, n-butyl, isobutyl, tert-butyl, hexyl, cyclohexyl, naphthyl, etc., as well as vanadium acetylacetonate.

[0156] Chromium catalyst compounds of conventional types suitable for use in this invention (commonly referred to as Phillips-type catalysts) may include CrO3, chromium dicyclopentadiene, silyl chromate, chromyl chloride (CrO2Cl2), chromium 2-ethylhexanoate, chromium acetylacetonate (Cr(AcAc)3), etc. Non-limiting examples are disclosed, for example, in U.S. Patent Nos. 3,242,099 and 3,231,550.

[0157] Other conventional types of transition metal catalyst compounds and catalyst systems applicable to the present invention are disclosed in U.S. Patents 4,124,532, 4,302,565, 4,302,566, and 5,763,723, and in published EP-A2 0 416 815A2 and EP-A1 0 420 436. The conventional types of transition metal catalysts of the present invention may also have the general formula M'1M″X. 2t Y u E, where M' is Mg, Mn, and / or Ca; t is a number from 0.5 to 2; M″ is a transition metal Ti, V, and / or Zr; X is a halogen, preferably Cl, Br, or I; Y can be the same or different and is a halogen or acetylacetonate anion of oxygen alone or in combination, --NR2, --OR, --SR, --COOR, or --OSOOR (where R is a hydrocarbon group, specifically alkyl, aryl, cycloalkyl, or aralkyl); u is a number from 0.5 to 20; E is an electron-donating compound selected from the following compound classes: (a) esters of organic carboxylic acids; (b) alcohols; (c) ethers; (d) amines; (e) esters of carbonic acid; (f) nitriles; (g) phosphoramides; (h) esters containing phosphoric acid and phosphoric acid; and (j) phosphorus oxychloride. Non-limiting examples of complexes conforming to the above formula include: MgTiCl5.2CH3COOC2H5, Mg3Ti2Cl 12 7CH3COOC2H5, MgTiCl5.6C2H5OH, MgTiCl5.10OCH3OH, MgTiCl5 tetrahydrofuran, MgTi2Cl 12 7C6H5CN, MgTi2 Cl 12 6C6H5COOC2H5, MgTiCl62CH3COOC2H5, MgTiCl66C5H5N, MgTiCl5(OCH3)2CH3COOC2H5, MgTiCl5N(C6H5)23CH3COOC2H5, MgTiBr2Cl42(C2H5)O, MnTiCl54C2H5OH, Mg3V2Cl 12.7CH3COOC2H5, MgZrCl64 tetrahydrofuran. Other catalysts may include cationic catalysts such as AlCl3 and other cobalt and iron catalysts well known in the art.

[0158] The conventional types of transition metal catalyst compounds disclosed herein can be activated using one or more of the conventional types of cocatalysts described below.

[0159] Conventional cocatalysts and other components

[0160] Conventional co-catalyst compounds used for the above-mentioned conventional types of transition metal catalyst compounds can be derived from formula M. 3 M 4 v X 2 c R 3 b-c It means that M 3 Metals belonging to Groups IA, IIA, IIB, and IIIA of the periodic table; M 4 For each element, X represents a group IA metal in the periodic table; v is a number from 0 to 1; each X... 2 For any halogen; c is a number from 0 to 3; each R 3 It is a monovalent hydrocarbon group or hydrogen; b is a number from 1 to 4; and bc is at least 1. Other conventional types of organometallic co-catalysts used for the above conventional types of transition metal catalysts have the formula M. 3 R 3 k M 3 Metals belonging to Group IA, Group IIA, Group IIB, or Group IIIA, such as lithium, sodium, beryllium, barium, boron, aluminum, zinc, cadmium, and gallium; k equals 1, 2, or 3, depending on M. 3 The valence of M, in turn, usually depends on M. 3 The specific number of families to which it belongs; and each R 3 It can be any monovalent hydrocarbon group.

[0161] Examples of conventional organometallic cocatalyst compounds of Group IA, IIA, and IIIA that can be used with the conventional types of catalyst compounds described above include (but are not limited to) methyllithium, butyllithium, dihexylmercuric, butylmagnesium, diethylcadmium, benzyl potassium, diethylzinc, tri-n-butylaluminum, diisobutylethylboron, diethylcadmium, di-n-butylzinc, and tri-n-pentylboron, and more specifically, alkylaluminum, such as trihexylaluminum, triethylaluminum, trimethylaluminum, and triisobutylaluminum. Other conventional types of cocatalyst compounds may include monoorganohalides and hydrides of Group IIA metals and mono- or diorganohalides and hydrides of Group IHA metals. Non-limiting examples of such conventional type of cocatalyst compounds may include diisobutylaluminum bromide, isobutylboron dichloride, methylmagnesium chloride, ethylberyllium chloride, ethylcalcium bromide, diisobutylaluminum hydride, methylcadmium hydride, diethylboron hydride, hexylberyllium hydride, dipropylboron hydride, octylmagnesium hydride, butylzinc hydride, dichloroboron hydride, dibromoaluminum hydride, and cadmium bromine hydride. Conventional type organometallic cocatalyst compounds are known to those skilled in the art, and a more complete discussion of these compounds can be found in U.S. Patent Nos. 3,221,002 and 5,093,415.

[0162] Metallocene catalysts

[0163] Metallocene catalysts may include "half-sandwich" compounds (i.e., at least one ligand) and "full-sandwich" compounds (i.e., at least two ligands), said compounds having one or more Cp ligands (cyclopentadienyl and isovalent ligands of cyclopentadienyl) bonded to at least one group 3 to group 12 metal atom and one or more leaving groups bonded to at least one metal atom. Hereinafter, these compounds will be referred to as "metallocene" or "metallocene catalyst components".

[0164] One or more metallocene catalyst components can be represented by formula (I):

[0165] Cp A Cp B MX n (I)

[0166] As described throughout the specification and claims, the metal atom "M" of the metallocene catalyst compound may be selected from the group consisting of Group 3 to Group 12 atoms and lanthanide atoms; the group consisting of Group 4, Group 5, and Group 6 atoms; Ti, Zr, Hf atoms, or Zr. The group bonding the metal atom "M" is such that, unless otherwise indicated, the compound described below in the formulas and structures is a neutral group. The Cp ligand forms at least one chemical bond with the metal atom M to form the "metallocene catalyst compound". The Cp ligand differs from the leaving group bonded to the catalyst compound in that it is not highly sensitive to substitution / extraction reactions.

[0167] M is as described above; each X is chemically bonded to M; each Cp group is chemically bonded to M; and n is an integer from 0 or 1 to 4, or 1 or 2.

[0168] From Cp in equation (I) A and Cp B The ligands represented can be the same or different cyclopentadienyl ligands or ligands isovalent with cyclopentadienyl, and either or both may contain heteroatoms and either or both may be substituted by a group R. A and Cp B It can be independently selected from the group consisting of: cyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, and substituted derivatives of each group.

[0169] Independently, each Cp of equation (I) A and Cp B It may be unsubstituted or substituted with any one or combination of substituents R. Non-limiting examples of substituents R used in structure (I) include hydroxyl, hydrocarbon, lower hydrocarbon, substituted hydrocarbon, heteroalkyl, alkyl, lower alkyl, substituted alkyl, heteroalkyl, alkenyl, lower alkenyl, substituted alkenyl, heteroalkenyl, alkynyl, lower alkenyl, substituted alkenyl, heteroalkynyl, alkoxy, lower alkoxy, aryloxy, hydroxyl, alkylthio, lower alkylthio, arylthio, thiooxy, aryl, substituted aryl, heteroaryl, etc. Alkyl, arylene alkyl, alkylene aryl, halides, haloalkyl, haloenyl, haloynyl, heteroalkyl, heterocyclic, heteroaryl, heteroatom-containing groups, silyl, boronyl, phosphinyl, phosphine, amino, amine, cycloalkyl, acyl, aromatic acyl, alkylthiol, dialkylamine, alkylamide, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, alkyl-carbamoyl and dialkyl-carbamoyl, acyloxy, acylamino, aromatic acylamino and combinations thereof.

[0170] More specific, non-limiting examples of alkyl substituents R associated with formula (i) include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl, phenyl, methylphenyl and tert-butylphenyl, etc., including all their isomers such as tert-butyl, isopropyl and so on. Other possible groups include substituted alkyl and aryl groups, such as fluoromethyl, fluoroethyl, difluoroethyl, iodopropyl, bromohexyl, chlorobenzyl, and alkyl-substituted organometallic groups, including trimethylsilyl, trimethylgermanyl, methyldiethylsilyl, etc.; and halocarbon-substituted organometallic groups, including tri(trifluoromethyl)silyl, methylbis(difluoromethyl)silyl, bromomethyldimethylgermanyl, etc.; and disubstituted boron groups, including, for example, dimethylboron; and disubstituted Group 15 groups, including dimethylamine, dimethylphosphine, diphenylamine, methylphenylphosphine; and Group 16 groups, including methoxy, ethoxy, propoxy, phenoxy, dimethyl sulfide, and diethyl sulfide. Other substituents R include alkenes, such as (but not limited to) alkenyl unsaturated substituents, including vinyl-terminated ligands, such as 3-butenyl, 2-propenyl, 5-hexenyl, etc. Two adjacent R groups, if present, can connect to form a ring structure having 3 to 30 atoms, the atoms being selected from the group consisting of carbon, nitrogen, oxygen, phosphorus, silicon, germanium, aluminum, boron, and combinations thereof. Furthermore, substituent R groups, such as 1-butyl, can form bonds with element M.

[0171] Each X in formula (I) may be independently selected from the group consisting of: any leaving group, such as halide ions, hydrides, hydrocarbon groups, lower hydrocarbon groups, substituted hydrocarbon groups, heteroalkyl groups, alkyl groups, lower alkyl groups, substituted alkyl groups, heteroalkyl groups, alkenyl groups, lower alkenyl groups, substituted alkenyl groups, heteroalkenyl groups, alkynyl groups, lower alkynyl groups, aryloxy groups, hydroxyl groups, alkylthio groups, lower alkylthio groups, arylthio groups, thiooxy groups, aryl groups, substituted aryl groups. alkyl, heteroaryl, aralkyl, arylene, alkylaryl, alkylenearyl, halide, haloalkyl, haloenyl, haloynyl, heteroalkyl, heterocyclic, heteroaryl, groups containing heteroatoms, silyl, boronyl, phosphinyl, phosphine, amino, amine, cycloalkyl, acyl, aromatic acyl, alkylthiol, dialkylamine, alkylamide, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, alkyl-carbamoyl and dialkyl-carbamoyl, acyloxy, acylamino, aromatic acylamino and combinations thereof. X may also be C1 to C1. 12 Alkyl, C2 to C 12 alkenyl, C6 to C 12 Aryl, C7 to C 20 Alkyl aryl, C1 to C 12 Alkyl groups, C6 to C 16 aryloxy group, C7 to C 18 Alkyl aryloxy, C1 to C 12Fluoroalkyl, C6 to C 12 Fluoroaryl and C1 to C 12 Hydrocarbons containing heteroatoms, and their substituted derivatives. X may also be selected from hydrides, halide ions, C1 to C6 alkyl groups, C2 to C6 alkenyl groups, C7 to C6 hydrocarbon groups, and C6 alkyl groups. 18 alkylaryl, C1 to C6 alkoxy, C6 to C 14 aryloxy group, C7 to C 16 Alkyl aryloxy, C1 to C6 alkyl carboxylic esters, C1 to C6 fluorinated alkyl carboxylic esters, C6 to C 12 Aryl carboxylic esters, C7 to C 18 Alkyl aryl carboxylic esters, C1 to C6 fluoroalkyl, C2 to C6 fluoroolefin, and C7 to C6 fluoroalkyl. 18 Fluoroalkylaryl. X may also be selected from hydrides, chlorides, fluorides, methyl, phenyl, phenoxy, benzoyloxy, toluenesulfonyl, fluoromethyl, and fluorophenyl. X may be selected from C1 to C2. 12 Alkyl, C2 to C 12 alkenyl, C6 to C 12 Aryl, C7 to C 20 Alkyl aryl, substituted C1 to C 12 Alkyl groups, substituted C6 to C6 12 Aryl, substituted C7 to C 20 Alkyl aryl and C1 to C 12 Alkyl groups containing heteroatoms, C1 to C 12 Aryl groups containing heteroatoms and C1 to C 12 Alkyl aryl groups containing heteroatoms; chlorides, fluorides, C1 to C6 alkyl groups, C2 to C6 alkenyl groups, C7 to C6 alkenyl groups. 18 Alkyl aryl, halogenated C1 to C6 alkyl, halogenated C2 to C6 alkenyl, and halogenated C7 to C 18 Alkyl aryl. X may be selected from fluoride, methyl, ethyl, propyl, phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, fluoromethyl (monofluoromethyl, difluoromethyl and trifluoromethyl) and fluorophenyl (monofluorophenyl, difluorophenyl, trifluorophenyl, tetrafluorophenyl and pentafluorophenyl).

[0172] Metallocene catalyst compounds and / or components may include those of formula (I), wherein Cp A and Cp B Bridged to each other by at least one bridging base (A), such that the structure is represented by equation (II):

[0173] Cp A (A)Cp B MX n (II)

[0174] These bridging compounds, represented by formula (II), are called "bridged metallocenes".A Cp B M, X, and n are as defined above with respect to formula (I); and each Cp ligand is chemically bonded to M, and (A) is chemically bonded to each Cp. Non-limiting examples of the bridging group (A) include divalent alkyl, divalent lower alkyl, divalent substituted alkyl, divalent heteroalkyl, divalent alkenyl, divalent lower alkenyl, divalent substituted alkenyl, divalent heteroalkenyl, divalent alkynyl, divalent lower alkynyl, divalent substituted alkynyl, divalent heteroalynyl, divalent alkoxy, divalent lower alkoxy, divalent aryloxy, divalent alkylthio, divalent lower alkylthio, divalent arylthio, divalent aryl, divalent substituted... Aryl, divalent heteroaryl, divalent arylalkyl, divalent arylenealkyl, divalent alkylaryl, divalent arylenealkyl, divalent haloalkyl, divalent haloalkenyl, divalent haloynyl, divalent heteroalkyl, divalent heterocyclic, divalent heteroaryl, divalent heteroatom-containing group, divalent hydrocarbon group, divalent lower hydrocarbon group, divalent substituted hydrocarbon group, divalent heterohydrocarbon group, divalent silyl, divalent boronyl, divalent phosphinyl, divalent phosphine, divalent amino, divalent amine, divalent ether, divalent sulfide. Additional non-limiting examples of bridging group A include divalent hydrocarbon groups containing at least one atom from Group 13 to Group 16 (e.g., but not limited to, at least one of carbon, oxygen, nitrogen, silicon, aluminum, boron, germanium, and tin atoms and combinations thereof); wherein the heteroatom may also be a substituted C1 to C2 group satisfying a neutral valence. 12 Alkyl or aryl. The bridging group (A) may also contain substituents R, including halogen groups and iron, as defined above with respect to formula (I). More specific, non-limiting examples of bridging groups (A) are represented by C1 to C6 alkylene groups, substituted C1 to C6 alkylene groups, oxygen, sulfur, R'2C═, R'2Si═, ─Si(R')2Si(R'2)─, R'2Ge═, R'P═ (where “═” indicates two chemical bonds), wherein R' is independently selected from the group consisting of: hydrides, hydrocarbon groups, substituted hydrocarbon groups, halocarbon groups, substituted halocarbon groups, hydrocarbon-substituted organometallic compounds, halocarbon-substituted organometallic compounds, disubstituted boron, disubstituted Group 15 atoms, substituted Group 16 atoms, and halogen groups; and wherein two or more R' may be linked to form a ring or ring system. The bridged metallocene catalyst component of formula (II) may have two or more bridging groups (A).

[0175] Other non-limiting examples of bridging group (A) include methylene, ethylene / ethylidene, propylene, isopropylidene, diphenylmethylene, 1,2-dimethylethylene, 1,2-diphenylethylene, 1,1,2,2-tetramethylethylene, dimethylsilyl, diethylsilyl, methyl-ethylsilyl, trifluoromethylbutylsilyl, bis(trifluoromethyl)silyl, di(n-butyl)silyl, di(n-propyl)silyl, di(isopropyl)silyl, di(n-hexyl)silyl, dicyclohexylsilyl, diphenylsilyl, cyclohexylphenylsilyl, tert-butylcyclohexylsilyl, di(tert-butylphenyl)silyl, di(p-tolyl)silyl and the corresponding portion wherein the Si atom is replaced by a Ge or C atom, dimethylsilyl, diethylsilyl, dimethylgermanyl and diethylgermanyl.

[0176] The bridging group (A) may also be cyclic, containing, for example, 4 to 10 or 5 to 7 ring members. The ring members may be selected from the elements mentioned above, or from one or more of B, C, Si, Ge, N, and O. Non-limiting examples of ring structures that may exist as a bridging portion or part of a bridging portion are cyclobutylene, cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene, and the corresponding ring in which one or two carbon atoms are substituted with at least one of Si, Ge, N, and O (specifically, Si and Ge). The bond arrangement between the ring and the Cp group may be cis, trans, or a combination thereof.

[0177] The cyclic bridging group (A) can be saturated or unsaturated and / or carry one or more substituents and / or fused with one or more other ring structures. If present, the one or more substituents can be selected from the group consisting of hydrocarbon groups (e.g., alkyl, such as methyl) and halogens (e.g., F, Cl). The one or more Cp groups optionally fused with the above-described cyclic bridging portion can be saturated or unsaturated and are selected from those groups having 4 to 10, more precisely 5, 6, or 7 ring members (selected from the group consisting of C, N, O, and S), such as the group consisting of cyclopentyl, cyclohexyl, and phenyl. Furthermore, these ring structures can be self-fused, for example, in the case of naphthyl. Additionally, these (optionally fused) ring structures can carry one or more substituents. Illustrative, non-limiting examples of these substituents are hydrocarbon groups (especially alkyl) and halogen atoms.

[0178] Ligands Cp of formulas (I) and (II) A and Cp B They can be different from each other or the same as each other.

[0179] Metallocene catalyst components may include monoligand metallocene compounds (e.g., monocyclopentadienyl catalyst components) as described, for example, in WO 93 / 08221, which is incorporated herein by reference.

[0180] At least one metallocene catalyst component may be an unbridged “semi-sandwich” metallocene represented by formula (IV).

[0181] Cp A MQ q X n (IV)

[0182] Where Cp A As defined in (I) regarding the Cp group and as a ligand bonded to M; each Q is independently bonded to M; Q is also bonded to Cp. A X is a leaving base as described in (I); n is in the range of 0 to 3, or 1 or 2; q is in the range of 0 to 3, or 1 or 2. A The following groups can be freely selected: cyclopentadienyl, indenyl, tetrahydroindenyl, fumonyl, their substituted forms, and combinations thereof.

[0183] In equation (IV), Q is selected from the following group: ROO - RO-, R(O)-, -NR-, -CR2-, -S-, -NR2, -CR3, -SR, -SiR3, -PR2, -H, and substituted and unsubstituted aryl groups, wherein R is selected from the group consisting of: alkyl, lower alkyl, substituted alkyl, heteroalkyl, alkyl, lower alkyl, substituted alkyl, heteroalkyl, alkenyl, lower alkenyl, substituted alkenyl, heteroalkenyl, alkynyl, lower alkenyl, substituted alkenyl, heteroalkenyl, alkoxy, lower alkoxy, aryloxy, hydroxy, alkylthio, lower alkyl alkylthio, arylthio, thiooxy, aryl, substituted aryl, heteroaryl, aralkyl, arylene, alkylaryl, alkylene, halide, haloalkyl, haloenyl, haloynyl, heteroalkyl, heterocyclic, heteroaryl, heteroatom-containing group, silyl, boronyl, phosphinyl, phosphine, amino, amine, cycloalkyl, acyl, aromatic acyl, alkylthiol, dialkylamine, alkylamide, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, alkyl-carbamoyl and dialkyl-carbamoyl, acyloxy, acylamino, aromatic acylamino and combinations thereof. R can be selected from C1 to C6 alkyl, C6 to C 12 Aryl, C1 to C6 alkylamine, C6 to C 12 Alkyl arylamines, C1 to C6 alkoxy groups and C6 to C 12 Aryloxy groups. Non-limiting examples of Q include C1 to C2. 12 Carbamates, C1 to C 12 Carboxylic acid esters (e.g., pivalate), C2 to C 20Allyl and C2 to C 20 Heteroallyl moiety.

[0184] Alternatively, the above-mentioned "semi-sandwich" metallocene can be described as in formula (II), for example, as described in US 6,069,213:

[0185] Cp A M(Q2GZ)X n or T(Cp) A M(Q2GZ)X n ) m (V)

[0186] Where M and Cp A X and n are as defined above;

[0187] Q2GZ forms a polydentate ligand unit (e.g., a pivalate ester), wherein 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 hydrides, provided that when Q is -NR-, Z is selected from the group consisting of -OR, -NR2, -SR, -SiR3, and -PR2; and is constrained by satisfying the neutral valence of Q through Z; and wherein each R is independently selected from the group consisting of: alkyl, lower alkyl, substituted alkyl, heteroalkyl, alkyl, lower alkyl, ... Substituted alkyl, heteroalkyl, alkenyl, lower alkenyl, substituted alkenyl, heteroalkenyl, alkynyl, lower alkynyl, substituted alkynyl, heteroalkynyl, alkoxy, lower alkoxy, aryloxy, hydroxyl, alkylthio, lower alkylthio, arylthio, thiooxy, aryl, substituted aryl, heteroaryl, aralkyl, arylene alkyl, alkylaryl, arylene aryl, halides, haloalkyl, haloalkenyl, haloalkynyl, heteroalkyl, heterocyclic, heteroaryl, groups containing heteroatoms, silyl, boronyl, phosphinyl, phosphine, amino, amine, cycloalkyl, acyl, aromatic acyl, alkylthiol, dialkylamine, alkylamide, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, alkyl-carbamoyl and dialkyl-carbamoyl, acyloxy, acylamino, aromatic acylamino and combinations thereof. R may be selected from the group consisting of: C1 to C1. 10 Groups containing heteroatoms, C1 to C 10 Alkyl, C6 to C 12 Aryl, C6 to C 12 Alkyl aryl, C1 to C 10 Alkyl groups and C6 to C 12 aryloxy;

[0188] n can be 1 or 2;

[0189] T is a selection from C1 to C2. 10 Alkylene, C6 to C 12 Aromatic and C1 to C 10 Groups containing heteroatoms and C6 to C6 12 A bridging group consisting of heterocyclic groups; wherein each T group bridges adjacent "Cp" groups. A M(Q2GZ)X n "group, and chemically bonded to Cp A Group;

[0190] m can be an integer from 1 to 7; or m can be an integer from 2 to 6.

[0191] The metallocene catalyst components can be more precisely described in structures (VIa), (VIb), (VIc), (VId), (VIe), and (VIf):

[0192]

[0193]

[0194] In structures (VIa) to (VIf), M is selected from groups consisting of atoms from Groups 3 to 12, groups consisting of atoms from Groups 3 to 10, groups consisting of atoms from Groups 3 to 6, groups consisting of atoms from Group 4, and groups consisting of Zr and Hf or Zr; Q in (VIa) to (VIf) is selected from the following groups: hydrocarbon group, lower hydrocarbon group, substituted hydrocarbon group, heterohydrocarbon group, alkyl group, lower alkyl group, substituted alkyl group, heteroalkyl group, alkenyl group, lower alkenyl group, substituted alkenyl group, heteroalkenyl group, alkynyl group, lower alkenyl group, substituted alkenyl group, heteroalkenyl group, alkoxy group, lower alkoxy group, aryloxy group, hydroxyl group, alkylthio group, lower alkylthio group aryl, arylthio, thiooxy, aryl, substituted aryl, heteroaryl, aralkyl, arylene, alkylaryl, alkylene, halide, haloalkyl, haloenyl, haloynyl, heteroalkyl, heterocyclic, heteroaryl, heteroatom-containing group, silyl, boronyl, phosphinyl, phosphine, amino, amine, cycloalkyl, acyl, arylyl, alkylthiol, dialkylamine, alkylamide, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, alkyl-carbamoyl and dialkyl-carbamoyl, acyloxy, acylamino, arylylamino, alkylene, aryl, arylene, alkoxy, aryloxy, amine, arylamine (e.g., pyridyl), alkylamine, phosphine, alkylphosphine, substituted alkyl, substituted aryl, substituted alkoxy, substituted... The group may contain substituted aryloxy groups, substituted amines, substituted alkylamines, substituted phosphines, substituted alkylphosphines, carbamates, heteroallyl groups, carboxylic esters (non-limiting examples suitable for carbamates and carboxylic esters include trimethyl acetate, trimethyl acetate, methyl acetate, p-methylbenzoate, benzoate, diethylcarbamate, and dimethylcarbamate), fluorinated alkyl groups, fluorinated aryl groups, and fluorinated alkyl carboxylic esters; wherein the saturated group defined as Q may contain 1 to 20 carbon atoms; and wherein the aromatic group may contain 5 to 20 carbon atoms; wherein R* may be selected from divalent alkyl groups, divalent lower alkyl groups, substituted divalent alkyl groups, divalent heteroalkyl groups, divalent alkenyl groups, divalent lower alkenyl groups, and substituted divalent alkenyl groups. Divalent heteroalkenyl, divalent alkynyl, divalent lower alkynyl, substituted divalent alkynyl, divalent heteroalkenyl, divalent alkoxy, divalent lower alkoxy, divalent aryloxy, divalent alkylthio, divalent lower alkylthio, divalent arylthio, divalent aryl, substituted divalent aryl, divalent heteroaryl, divalent aralkylene, divalent alkylene aryl, divalent alkylene aryl, divalent haloalkyl, divalent haloalkenyl, divalent haloalkynyl, divalent heteroalkyl, divalent heterocyclic, divalent heteroaryl, divalent heteroatom-containing group, divalent hydrocarbon, divalent lower hydrocarbon, substituted divalent hydrocarbon, divalent heterohydrocarbon, divalent silyl, divalent boronyl, divalent phosphinyl, divalent phosphine, divalent amino, divalent amine, divalent ether, divalent thioether. Additionally, R* can be from the group consisting of divalent alkylene groups and heteroatom-containing alkylene groups, specifically from the group consisting of alkylene groups, substituted alkylene groups, and heteroatom-containing alkylene groups, and from C1 to C2.12 Alkylene, C1 to C 12 Substituted alkylene groups and C1 to C 12 Groups consisting of heteroatoms or groups selected from C1 to C4 alkylene groups. The R* group may be the same in the structure (VIf).

[0195] As described above in (A) of structure (II), and more precisely, free chemical bonds are selected: -O-, -S-, -SO2-, -NR-, ═SiR2, ═GeR2, ═SnR2, ─R2SiSiR2─, RP═, C1 to C 12 Alkylene, substituted C1 to C 12 Alkylene, divalent C4 to C 12 The group consisting of cyclic hydrocarbons and substituted and unsubstituted aryl groups; or the group consisting of C5 to C8 cyclic hydrocarbons, -CH2CH2-, ═CR2, and ═SiR2; wherein R is selected from the group consisting of alkyl, cycloalkyl, aryl, alkoxy, fluoroalkyl, and heteroatom-containing hydrocarbons; R is selected from the group consisting of C1 to C6 alkyl, substituted phenyl, phenyl, and C1 to C6 alkoxy; or R is selected from the group consisting of methoxy, methyl, phenoxy, and phenyl; or A may be absent, in which case each R* is as per R 1 To R 13 Defined; each X as described in (I); n is an integer from 0 to 4, or from 1 to 3, or 1 or 2; and R 1 To R 13 Independently selected from the group consisting of: hydroxyl, hydrocarbon, lower hydrocarbon, substituted hydrocarbon, heteroalkyl, alkyl, lower alkyl, substituted alkyl, heteroalkyl, alkenyl, lower alkenyl, substituted alkenyl, heteroalkenyl, alkynyl, lower alkenyl, substituted alkenyl, heteroalkynyl, alkoxy, lower alkoxy, aryloxy, hydroxyl, alkylthio, lower alkylthio, arylthio, thiooxy, aryl, substituted aryl, heteroaryl, aralkyl, arylene alkyl, alkylaryl, alkylaryl, halide, haloalkyl, haloalkenyl, heteroalkyl, heterocyclic, heteroaryl, heteroatom-containing group, silyl, boronyl, phosphinyl, phosphine, amino, amine, cycloalkyl, acyl, arylyl acyl, alkyl thiol, dialkylamine, alkylamide, alkoxy carbonyl, aryloxy carbonyl, carbamoyl, alkyl-carbamoyl and dialkyl-carbamoyl, acyloxy, acylamino, arylamino. To R 13 It can also be independently selected from C1 to C. 12 Alkyl, C2 to C 12 alkenyl, C6 to C 12 Aryl, C7 to C 20 Alkyl aryl, C1 to C 12 Alkoxy, C1 to C 12 Fluoroalkyl, C6 to C12 Fluoroaryl and C1 to C 12 Hydrocarbons containing heteroatoms and their substituted derivatives; selected from the group consisting of: hydroxyl, fluorine, chloro, bromine, C1 to C6 alkyl, C2 to C6 alkenyl, C7 to C6 alkyl, C8 to C9 alkyl, C9 ... 18 Alkyl aryl, C1 to C6 fluoroalkyl, C2 to C6 fluoroolefin, C7 to C 18 Fluoroalkylaryl; or hydrogen, fluorine, chloro, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, hexyl, phenyl, 2,6-dimethylphenyl and 4-tert-butylphenyl; wherein adjacent R groups may form a saturated, partially saturated or fully saturated ring.

[0196] The structure of the metallocene catalyst component represented by (VIa) can take many forms, as disclosed in, for example, US 5,026,798, US 5,703,187 and US 5,747,406, including dimer or oligomeric structures, as disclosed in, for example, US 5,026,798 and US 6,069,213.

[0197] For metallocenes represented in (VId), R1 and R2 form a substituted or non-substituted conjugated 6-membered carbon ring system.

[0198] It is anticipated that the aforementioned metallocene catalyst components include structural, optical, or enantiomers (racemic mixtures) or may be pure enantiomers.

[0199] As used herein, a single bridged asymmetric substituted metallocene catalyst component having racemic and / or meso isomers does not constitute at least two distinct bridged metallocene catalyst components.

[0200] The "metallocene catalyst compound," also referred to herein as a "metallocene catalyst component," may contain any combination of the above characteristics.

[0201] Metallocene compounds and catalysts are known in the art and any one or more may be used herein. Suitable metallocenes include (but are not limited to) all metallocenes disclosed and referenced in the U.S. patents listed above, as well as those in U.S. Patent Nos. 7,179,876, 7,169,864, 7,157,531, 7,129,302, 6,995,109, 6,958,306, 6,884,748, and 6,689,847, U.S. Patent Application Publication No. 2007 / 0055028, and published PCT applications Nos. WO 97 / 22635, WO 00 / 699 / 22, WO 01 / 30860, WO 01 / 30861, WO 02 / 46246, WO 02 / 50088, WO 04 / 026921, and WO All metallocenes disclosed and referenced in Patent No. 06 / 019494 are incorporated herein by reference in their entirety. Additional catalysts applicable to this document include U.S. Patent Nos. 6,309,997 and 6,265,338, U.S. Patent Application Publication No. 2006 / 019925, and those referenced in the following articles: *Chemical Review* 2000, 100, 1253, Resconi; *Chemical Review* 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.

[0202] Catalysts containing Group 15 elements

[0203] The catalyst composition may comprise one or more metallocene catalysts as described above and / or other conventional polyolefin catalysts, as well as catalysts containing Group 15 atoms as described below.

[0204] Catalysts “containing Group 15 atoms” or “group 15-containing” catalysts may comprise complexes of metal atoms from Group 3 to Group 12, wherein the metal atoms are 2 to 8 coordinating atoms, and the coordinating moiety comprises at least two and at most four Group 15 atoms. Group 15-containing catalyst components may be complexes of Group 4 metals and derived from one to four ligands such that the Group 4 metal is at least 2-coordinated, and the coordinating moiety comprises at least two nitrogen atoms. Representative Group 15-containing compounds are disclosed, for example, in WO 99 / 01460, EP A1 0 893 454, U.S. Patents 5,318,935, 5,889,128, 6,333,389B2, and 6,271,325B1.

[0205] Catalyst components containing Group 15 may include Group 4 iminophenol complexes, Group 4 bis(amide) complexes, and Group 4 pyridylamide complexes, which can activate the polymerization of olefins to any extent.

[0206] Catalyst components containing Group 15 may include HN(CH2CH2N(2,4,6-Me3phenyl))2MX2 and HN(CH2CH2N(2,3,4,5,6-Me5phenyl))2MX2, wherein M is Zr or Hf, and X is selected from F, Cl, Br, I, Me, benzyl, CH2SiMe3, and C1 to C5 alkyl or alkenyl groups.

[0207] Catalyst components containing Group 15 may include diamide compounds, such as [(2,3,4,5,6Me5C6)NCH2CH2]2NHZrBz2.

[0208] Mixed catalyst

[0209] In addition, the catalyst compound of the above type can be combined with another type of catalyst compound described herein by means of one or more activators or activation methods as described below.

[0210] This further encompasses other catalysts that can be combined with the metallocene catalyst compounds described herein. For example, see U.S. Patents 4,937,299, 4,935,474, 5,281,679, 5,359,015, 5,470,811, and 5,719,241.

[0211] Additionally, one or more metallocene catalyst compounds or catalyst systems may be used in combination with one or more conventional types of catalyst compounds or catalyst systems. Non-limiting examples of mixed catalysts and catalyst systems are described in U.S. Patents 4,159,965, 4,325,837, 4,701,432, 5,124,418, 5,077,255, 5,183,867, 5,391,660, 5,395,810, 5,691,264, 5,723,399, and 5,767,031, and PCT Publication WO 96 / 23010, published August 1, 1996.

[0212] This further encompasses two or more conventional types of transition metal catalysts that can be combined with one or more conventional types of cocatalysts. Non-limiting examples of mixed conventional types of transition metal catalysts are described, for example, in U.S. Patent Nos. 4,154,701, 4,210,559, 4,263,422, 4,672,096, 4,918,038, 5,198,400, 5,237,025, 5,408,015, and 5,420,090.

[0213] Activators and activation methods for catalyst compounds

[0214] An activator is broadly defined as any combination of reagents that increases the rate of oligomerization or polymerization of transition metal compounds into unsaturated monomers (such as olefins). It can be activated in any way sufficient to allow coordination or cationic oligomerization and / or polymerization for use in oligomerization and / or polymerization catalysis.

[0215] Alternatively, the activator can be a Lewis base, such as diethyl ether, dimethyl ether, ethanol, or methanol. Other activators that can be used include those described in WO 98 / 07515, such as tris(2,2',2″-nonafluorobiphenyl)fluoroaluminate.

[0216] Combinations of activators can be used. For example, aluminum oxanes and ionized activators can be used in combination, see, for example, EP-B1 0 573 120, WO 94 / 07928 and WO 95 / 14044, and U.S. Patents 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'-bisphenyl-ditrimethylsilyl)4THF as an activator for metallocene catalyst compounds. WO 99 / 18135 describes the use of organoboron-aluminum activators. EP-B1-0 781299 describes the use of a combination of silylium salts and noncoordinate compatible anions. WO 2007 / 024773 discloses the use of an activator-support that may comprise chemically treated solid oxides, clay minerals, silicate minerals, or any combination thereof. Furthermore, it covers activation methods such as radiation (see EP-B1-0 615 981), electrochemical oxidation, etc., for the purpose of converting neutral metallocene catalyst compounds or precursors into metallocene cations capable of polymerizing olefins. Other activators or methods for activating metallocene catalyst compounds are described, for example, in U.S. Patents 5,849,852, 5,859,653, and 5,869,723 and PCT WO 98 / 32775.

[0217] Aluminoxanes can also be used as activators in catalyst compositions. Aluminoxanes are generally oligomeric compounds containing --Al(R)--O-- subunits, where R is an alkyl group. Examples of aluminoxanes include methylaluminoxane (MAO), modified methylaluminoxane (MMAO), ethylaluminoxane, and isobutylaluminoxane. Alkylaluminoxanes and modified alkylaluminoxanes are suitable as catalyst activators, especially when the ligand that can be abstracted is a halide. Mixtures of different aluminoxanes and modified aluminoxanes can also be used. For further description, see U.S. Patents 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.

[0218] Aluminoxanes can be generated by the hydrolysis of corresponding trialkylaluminum compounds. MMAO can be generated by the hydrolysis of trimethylaluminum and higher trialkylaluminum compounds (e.g., triisobutylaluminum). MMAO is generally more soluble in aliphatic solvents and more stable during storage. Various methods exist for the preparation of aluminoxanes and modified aluminoxanes, non-limiting examples of which are described in, for example, U.S. Patents 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, and 5,248. Cases No. 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 Open Case 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. Visually clear methylalumoxanes can be used. Turbid or gelled aluminoxanes can be filtered to produce a clear solution or clear aluminoxanes can be decanted from a turbid solution. Another aluminoxane is modified methylalumoxane (MMAO) co-catalyst type 3A (available under the trade name Modified Methylalumoxane type 3A from Akzo Chemicals, Inc., disclosed in U.S. Patent No. 5,041,584).

[0219] Ionized or stoichiometric activators (neutral or ionic) may also be used, such as tris(n-butylammonium tetra(pentafluorophenyl)boron, trifluorophenylboron-based metal precursors or trifluoronaphthylboron-based metal precursors, polyhalogenated heteroborane anions (see, for example, WO 98 / 43983), boric acid (see, for example, U.S. Patent No. 5,942,459), or combinations thereof. Neutral or ionic activators may be used alone or in combination with aluminoxane or modified aluminoxane activators.

[0220] Examples of neutral stoichiometric activators may include trisubstituted boron, tellurium, aluminum, gallium, and indium, or mixtures thereof. The three substituents may each be independently selected from the group consisting of alkyl, alkenyl, halogen, substituted alkyl, aryl, aryl halides, alkoxy, and halides. The three substituents may be independently selected from the group consisting of halogens, monocyclic or polycyclic (including halogen-substituted) aryl, alkyl, and alkenyl compounds, and mixtures thereof; or alkenyl having 1 to 20 carbon atoms, alkyl having 1 to 20 carbon atoms, alkoxy having 1 to 20 carbon atoms, and aryl (including substituted aryl) having 3 to 20 carbon atoms. Alternatively, the three groups may be alkyl, phenyl, naphthyl, or mixtures thereof having 1 to 4 carbon groups. The three groups may be halogenated, such as fluorinated aryl. In other illustrative examples, the neutral stoichiometric activator is trifluorophenylboron or trifluoronaphthylboron.

[0221] Ionic stoichiometric activator compounds may contain active protons, or associate with other ions of the ionized compound but not coordinate, or only loosely coordinate with some other cations. Such compounds 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 U.S. Patents 5,153,157, 5,198,401, 5,066,741, 5,206,197, 5,241,025, 5,384,299, and 5,502,124.

[0222] carrier

[0223] The above-described catalyst compound can be combined with one or more supports using one of the support methods well known in the art or described below. For example, the compound can be used in a supported form (e.g., deposited on a support, in contact with a support, incorporated into a support, adsorbed or absorbed in or on a support).

[0224] As used herein, the term "support" refers to a compound containing oxides and chlorides from Groups 2, 3, 4, 5, 13, and 14. Suitable supports include, for example, silica, magnesium oxide, titanium dioxide, zirconium oxide, montmorillonite, silicosilicates, alumina, silica-alumina, silica-chromium, silica-titanium dioxide, magnesium chloride, graphite, magnesium oxide, titanium dioxide, zirconium oxide, montmorillonite, silicosilicates, etc.

[0225] The carrier may have an average particle size in the range of about 0.1 μm to about 500 μm, or about 1 μm to about 200 μm, or about 1 μm to about 50 μm, or about 5 μm to about 50 μm.

[0226] The average pore size of the carrier can be approximately To date or about To date or To date Within the range.

[0227] The surface area of ​​the carrier can be approximately 10m² 2 / g to approximately 700m 2 / g, or about 50m 2 / g to approximately 500m 2 / g, or approximately 100mg 2 / g to approximately 400m 2 Within the range of / g.

[0228] The pore volume of the carrier can range from about 0.1 cc / g to about 4.0 cc / g, or from about 0.5 cc / g to about 3.5 cc / g, or from about 0.8 cc / g to about 3.0 cc / g.

[0229] The surface area of ​​the carrier (e.g., inorganic oxide) can be approximately 10 μm. 2 / g to approximately 700m 2 Within the range of [value missing] g, the pore volume ranges from approximately 0.1 cc / g to approximately 4.0 cc / g, and the average particle size ranges from approximately 1 μm to approximately 500 μm. Alternatively, the surface area of ​​the support can be approximately 50 m². 2 / g to approximately 500m 2 Within the range of / g, the pore volume is approximately 0.5 cc / g to approximately 3.5 cc / g, and the average particle size is approximately 10 μm to approximately 200 μm. The surface area of ​​the support can be approximately 100 m². 2 / g to approximately 400m 2 Within the range of / g, the pore volume is from about 0.8cc / g to about 3.0cc / g, and the average particle size is from about 5μm to about 100μm.

[0230] The catalyst compound can be supported together with the activator on the same or separate support, or the activator can be used in an unsupported form or deposited on a different support than the supported catalyst compound.

[0231] Various other methods exist in the art for supporting polymerization catalyst compounds. For example, the catalyst compound may contain polymer-bound ligands, as described, for example, in U.S. Patent Nos. 5,473,202 and 5,770,755; the catalyst may be spray-dried, as described, for example, in U.S. Patent No. 5,648,310; the support used with the catalyst may be functionalized, as described in European Publication EP-A-0 802 203; or at least one substituent or leaving group may be selected, as described in U.S. Patent No. 5,688,880.

[0232] Catalyst composition

[0233] The catalyst compositions disclosed herein may comprise at least one supported polymerization catalyst, wherein the supported polymerization catalyst is modified with, treated with, or contacted with at least one aliphatic amine, and wherein said aliphatic amine is substantially free of particulate inorganic material. When used in this context, the term "substantially free of" means that the aliphatic amine contains less than 2% by weight, or less than 1% by weight, or less than 0.5% by weight, or 0% by weight of particulate inorganic material.

[0234] At least one aliphatic amine may be substantially free of particulate inorganic oxides. For example, the aliphatic amine may be substantially free of particulate silica or particulate alumina. The aliphatic amine may contain less than 2% by weight, or less than 1% by weight, or less than 0.5% by weight, or 0% by weight of particulate inorganic oxides, particulate silica, or particulate alumina.

[0235] The catalyst composition may be in a substantially dry solid form or in a slurry form suitable for liquid media.

[0236] When the catalyst composition is in substantially dry solid form, at least one aliphatic amine may be present in the catalyst composition in an amount of up to about 20% by weight, or up to about 10% by weight, or up to 5% by weight, or up to 2% by weight, or up to 1% by weight, based on the total weight of the catalyst composition.

[0237] As used herein, fatty amines can be nitrogen derivatives of fatty acids, alkenes, or alcohols that can be prepared from natural sources, fats, and oils, or from petrochemical feedstocks. Commercially available fatty amines can be mixtures of carbon chains or from about C8 to about C98. 40的 Composed of specific chain lengths.

[0238] As used herein, at least one fatty amine can be represented by the following formula:

[0239] (R1) x N(R2OH) y

[0240] in

[0241] R1 is a hydrocarbon group having 8 to 40 carbon atoms;

[0242] R2 is a divalent hydrocarbon group having 1 to 8 carbon atoms;

[0243] as well as

[0244] The value of x is 1 or 2 and x + y = 3.

[0245] R1 can be a hydrocarbon group having 14 to 26 carbon atoms, and R2 can be methylene, ethylene, n-propylene, n-butylene, or isopropylene. A non-limiting example of an aliphatic amine is octadecylbis(2-hydroxyethyl)amine.

[0246] Supported polymerization catalysts may comprise a support, an activator, and one or more catalyst compounds containing titanium, zirconium, or hafnium atoms. The catalyst compound may comprise:

[0247] (pentamethylcyclopentadienyl)(propylcyclopentadienyl)MX2

[0248] (tetramethylcyclopentadienyl)(propylcyclopentadienyl)MX2

[0249] (tetramethylcyclopentadienyl)(butylcyclopentadienyl)MX2

[0250] Me2Si(indene)2MX2,

[0251] Me2Si(tetrahydroindenyl)2MX2,

[0252] (n-propylcyclopentadienyl)2MX2

[0253] (n-Butylcyclopentadienyl)2MX2

[0254] (1-Methyl, 3-Butylcyclopentadienyl)2MX2,

[0255] HN(CH2CH2N(2,4,6-Me3phenyl))2MX2,

[0256] HN(CH2CH2N(2,3,4,5,6-Me5phenyl))2MX2,

[0257] (propylcyclopentadienyl)(tetramethylcyclopentadienyl)MX2

[0258] (Butylcyclopentadienyl)2MX2

[0259] (propylcyclopentadienyl)2MX2, and mixtures thereof,

[0260] Where M is Zr or Hf, and X is selected from F, Cl, Br, I, Me, benzyl, CH2SiMe3, and C1 to C5 alkyl or alkenyl groups.

[0261] Supported polymerization catalysts may comprise two or more catalyst compounds containing titanium, zirconium, or hafnium atoms. The two or more catalyst compounds may comprise one or more metallocene compounds and one or more compounds containing Group 15 metals. The metallocene compounds may include:

[0262] (pentamethylcyclopentadienyl)(propylcyclopentadienyl)MX2

[0263] (tetramethylcyclopentadienyl)(propylcyclopentadienyl)MX2

[0264] (tetramethylcyclopentadienyl)(butylcyclopentadienyl)MX2

[0265] Me2Si(indene)2MX2,

[0266] Me2Si(tetrahydroindenyl)2MX2,

[0267] (n-propylcyclopentadienyl)2MX2

[0268] (n-Butylcyclopentadienyl)2MX2

[0269] (1-Methyl, 3-Butylcyclopentadienyl)2MX2,

[0270] (propylcyclopentadienyl)(tetramethylcyclopentadienyl)MX2

[0271] (Butylcyclopentadienyl)2MX2

[0272] (propylcyclopentadienyl)2MX2, and mixtures thereof,

[0273] Where M is Zr or Hf, and X is selected from F, Cl, Br, I, Me, benzyl, CH2SiMe3, and C1 to C5 alkyl or alkenyl groups.

[0274] Compounds containing Group 15 metals may include:

[0275] HN(CH2CH2N(2,4,6-Me3phenyl))2MX2 or

[0276] HN(CH2CH2N(2,3,4,5,6-Me5phenyl))2MX2, wherein M is Zr or Hf, and X is selected from F, Cl, Br, I, Me, benzyl, CH2SiMe3, and C1 to C5 alkyl or alkenyl groups.

[0277] Supported polymerization catalysts may contain two catalyst compounds selected from:

[0278] (pentamethylcyclopentadienyl)(propylcyclopentadienyl)MX2

[0279] (tetramethylcyclopentadienyl)(propylcyclopentadienyl)MX2

[0280] (tetramethylcyclopentadienyl)(butylcyclopentadienyl)MX2

[0281] Me2Si(indene)2MX2,

[0282] Me2Si(tetrahydroindenyl)2MX2,

[0283] (n-propylcyclopentadienyl)2MX2

[0284] (n-Butylcyclopentadienyl)2MX2

[0285] (1-Methyl, 3-Butylcyclopentadienyl)2MX2,

[0286] (propylcyclopentadienyl)(tetramethylcyclopentadienyl)MX2

[0287] (Butylcyclopentadienyl)2MX2 or

[0288] (propylcyclopentadienyl)2MX2, and

[0289] HN(CH2CH2N(2,4,6-Me3phenyl))2MX2 or

[0290] HN(CH2CH2N(2,3,4,5,6-Me5phenyl))2MX2,

[0291] Where M is Zr or Hf, and X is selected from the group consisting of: F, Cl, Br, I, Me, benzyl, CH2SiMe3, and C1 to C5 alkyl or alkenyl groups.

[0292] The catalyst composition may also be in the form of a slurry of at least one liquid medium. Non-limiting examples of liquid mediums include mineral oils, aromatic hydrocarbons, or aliphatic hydrocarbons.

[0293] The catalyst composition may be in the form of a slurry of one or more liquid mediators, the liquid mediators being present in an amount of about 1% to about 60% by weight of the total slurry. The catalyst composition may be present in the slurry, preferably in an amount of more than or equal to about 1%, 2%, 4%, 6%, 10%, 15%, 20%, 25%, 30%, 40%, or 50% by weight of the total slurry.

[0294] When a liquid medium is present, the catalyst composition may contain at least one aliphatic amine in an amount greater than or equal to about 0.01 wt%, or 0.05 wt%, or 0.1 wt%, or 0.2 wt%, or 0.5 wt%, or 1 wt%, or 2 wt%, or 3 wt%, or 4 wt%, or 5 wt%, or 6 wt%, or 7 wt%, or 8 wt%, or 10 wt%, based on the total weight of the catalyst composition including the liquid medium.

[0295] Method for preparing catalyst compositions

[0296] Methods for preparing catalyst compositions may involve contacting one or more supported catalysts with at least one aliphatic amine that is substantially free of particulate inorganic material. Contact may also refer to combination, blending, mixing, modification, etc. Contact may be carried out in the presence or absence of a suitable liquid medium.

[0297] Supported catalysts can be in substantially dry and / or free-flowing form or in slurry form in a suitable liquid medium.

[0298] At least one aliphatic amine may be in dry form or dissolved in a suitable liquid medium or formed into a slurry prior to contact with one or more supported catalysts. The slurry may be a suspension, dispersion, or emulsion of the aliphatic amine in the liquid medium.

[0299] Supported catalysts and aliphatic amines can be combined in the presence of a liquid, for example, mineral oil, toluene, hexane, isobutane, or mixtures thereof. In one method, the aliphatic amine can be dissolved in a suitable liquid, such as an aromatic hydrocarbon, and subsequently combined with a supported catalyst that has been slurried in a suitable liquid. The suitable liquid can be an aromatic hydrocarbon, such as toluene.

[0300] The method may include the following steps:

[0301] A slurry of a catalyst composition is formed in at least one liquid medium by contacting at least one supported catalyst with at least one fatty amine.

[0302] The method may also include the following steps:

[0303] a) Combining at least one supported catalyst with a liquid medium to form a slurry; and

[0304] b) Combining at least one fatty amine with the slurry formed in (a) to form a slurry of the catalyst composition in the liquid medium.

[0305] The method may also include the following steps:

[0306] a) Combining at least one fatty amine with a liquid mediator; and

[0307] b) Combining at least one supported catalyst with the mixture formed in a) to form a slurry of the catalyst composition in the liquid medium.

[0308] In another method, the supported catalyst can be substantially dry, pre-formed, substantially dry, and / or free-flowing. The pre-formed supported catalyst can be contacted with at least one aliphatic amine. The aliphatic amine can be in a solution or slurry or in a dry state. When the aliphatic amine is in a dry state, it can be contacted with the supported catalyst in a rotary mixer (most preferably a tilting mixer) or in a fluidized bed mixing process under a nitrogen atmosphere, wherein both the supported catalyst and the aliphatic amine are in a solid state, i.e., both are substantially dry.

[0309] Non-limiting examples of mixing devices for combining solid supported catalysts and aliphatic amines include belt mixers, static mixers, double cone mixers, drum mixers, drum rollers, dehydrators, fluidized beds, spiral mixers, and conical screw mixers.

[0310] The fatty amine is in contact with the supported catalyst for a period of time so that a significant portion of the supported catalyst is tightly mixed with and / or substantially in contact with the fatty amine.

[0311] The contact time between aliphatic amines and supported catalysts can vary depending on one or more of the following conditions: temperature and pressure, type of mixing equipment, amount of components to be combined, and even the mechanism by which the polymerization catalyst / aliphatic amine combination is introduced into the reactor.

[0312] The supported catalyst can be in contact with aliphatic amines for a period of time ranging from one second to about 24 hours, or from about one minute to about 12 hours, or from about one minute to about 5 hours, or from about two minutes to about two hours.

[0313] At least one supported catalyst and at least one aliphatic amine can be spray-dried or spray-condensed. The resulting spray-dried powder can then be formulated into a slurry in a suitable liquid medium. Those skilled in the art will be familiar with various spray-drying techniques known in the field.

[0314] The aliphatic amine may be heated to provide a free-flowing liquid before contact with one or more supported catalysts. The temperature required to melt the aliphatic amine will depend on its melting point. The temperature may be greater than 20°C, or 30°C, or 40°C, or 50°C, or 60°C, or 70°C, or 80°C, or 90°C, or 100°C, or 110°C, or 120°C, or 130°C.

[0315] The aliphatic amine may be dried, i.e., subjected to a process to reduce its moisture content, before contact with one or more supported catalysts. The drying temperature may be greater than 20°C, or 30°C, or 40°C, or 50°C, or 60°C, or 70°C, or 80°C, or 90°C, or 100°C, or 110°C, or 120°C, or 130°C.

[0316] One or more supported catalysts can be contacted with aliphatic amines at high temperatures. The contact temperature can be greater than 20°C, or 30°C, or 40°C, or 50°C, or 60°C, or 70°C, or 80°C, or 90°C, or 100°C, or 110°C, or 120°C, or 130°C.

[0317] Supported catalysts can be contacted with aliphatic amines in an inert gas atmosphere, such as nitrogen. Combinations of polymerization catalysts with aliphatic amines can also be carried out in the presence of olefins, solvents, hydrogen, etc.

[0318] Residual solvent can be removed by drying the catalyst composition. The catalyst composition can be dried at high temperatures, such as above 20°C, or 30°C, or 40°C, or 50°C, or 60°C, or 70°C, or 80°C, or 90°C, or 100°C, or 110°C, or 120°C, or 130°C. The drying temperature can be below 90°C, or 80°C, or 70°C, or 60°C, or 50°C, or 40°C.

[0319] The drying of the catalyst composition can also be carried out under vacuum conditions. Alternatively, drying can be promoted by purging or spraying the solid or slurry with nitrogen.

[0320] Those skilled in the art will recognize that, depending on the catalyst system and aliphatic amine used, certain temperature and pressure conditions will be required to prevent, for example, loss of catalyst system activity.

[0321] Additional continuous additives / auxiliaries

[0322] One or more additional continuous additives may also be required to, for example, help regulate the electrostatic level in the polymerization reactor. Continuous additives may be used as part of the catalyst composition or introduced directly into the reactor independently of the catalyst composition. Continuous additives may be supported on inorganic oxides of the supported catalyst compositions described herein.

[0323] Non-limiting examples of continuous additives include amide-hydrocarbon or ethoxylated amide compounds, such as those described as “surface modifiers” in WO96 / 11961; carboxylic acid ester compounds, such as aryl-carboxylic acid esters and long-chain hydrocarbon carboxylic acid esters, as well as fatty acid-metal complexes; alcohols, ethers, sulfate ester compounds, metal oxides, and other compounds known in the art. Some specific examples of continuous additives include 1,2-diether organic compounds, magnesium oxide, ARMOSTAT 310, ATMER 163, ATMER AS-990 and other glycerides, ethoxylated amines (e.g., N,N-bis(2-hydroxyethyl)octadecylamine), alkyl sulfonates and alkoxylated fatty acid esters; STADIS 450 and 425, KEROSTAT CE4009 and KEROSTAT CE 5009, chromium salts of N-oleyl-o-aminobenzoic acid, Medialan acid and calcium salts of di-tert-butylphenol; POLYFLO 130, TOLAD 511 (olefin-acrylonitrile copolymer and polymeric polyamine), EDENOL D32, aluminum stearate, sorbitol monooleate, glyceryl monostearate, methyl methyl benzoate, dimethyl maleate, dimethyl transbutenedioate, triethylamine, 3,3-diphenyl-3-(imidazol-1-yl)-propyne, etc.

[0324] Any of the aforementioned additional continuous additives may be used alone or in combination as additional continuous additives.

[0325] Other additional continuous additives used in the embodiments disclosed herein are well known to those skilled in the art. Regardless of which additional continuous additives are used, care should be taken in selecting appropriate additional continuous additives to avoid introducing poisons into the reactor. Furthermore, in the selected embodiments, the minimum amount of additional continuous additive necessary to bring the static charge within the desired range should be used.

[0326] Additional continuous additives may be added to the reactor in combination of two or more of the listed additional continuous additives. Additional continuous additives may be added to the reactor in solution or slurry (e.g., a slurry containing mineral oil) form, and may be added to the reactor as a separate feed stream or may be combined with other feeds prior to addition to the reactor. For example, additional continuous additives may be combined with a catalyst or catalyst slurry prior to feeding a combined catalyst-static control agent mixture into the reactor.

[0327] The additional continuous additive may be added to the reactor in amounts ranging from about 0.05 ppmw to about 200 ppmw, or from about 2 ppmw to about 100 ppmw, or from about 2 ppmw to about 50 ppmw, depending on the polymer productivity. The additional continuous additive may also be added to the reactor in amounts of about 2 ppmw or greater, depending on the polymer productivity.

[0328] Method using catalyst composition

[0329] Those skilled in the art will recognize that, depending on the olefin polymerization composition used, certain temperature and pressure conditions will be required to prevent, for example, the catalyst system from losing its activity.

[0330] The catalyst composition disclosed above can be directly introduced into the polymerization reactor. The catalyst can be in the form of a slurry suitable for liquid media or in the form of a dry powder.

[0331] It should be understood that the accurate introduction method can vary depending on one or more of the following conditions: temperature and pressure, type of mixing equipment, and amount of components to be combined.

[0332] Polymerization process

[0333] The polymerization process may include solution, gas phase, slurry phase, and high-pressure processes, or combinations thereof. In illustrative embodiments, gas-phase or slurry-phase polymerization of one or more olefins (at least one of which is ethylene or propylene) is provided. Optionally, the reactor is a gas-phase fluidized bed polymerization reactor.

[0334] The catalyst composition described above is suitable for any prepolymerization and / or polymerization process over a wide range of temperatures and pressures. Temperatures can range from -60°C to about 280°C, 50°C to about 200°C, 60°C to 120°C, 70°C to 100°C, or 80°C to 95°C.

[0335] The process of the present invention is applicable to solution, high-pressure, slurry, or gas-phase polymerization processes of one or more olefin monomers having 2 to 30 carbon atoms, preferably 2 to 12 carbon atoms, and more preferably 2 to 8 carbon atoms. The process is particularly well-suited for the polymerization of two or more olefins or comonomers, such as ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, etc.

[0336] Other olefins that can be used in the process of this invention include olefinic unsaturated monomers, dienes having 4 to 18 carbon atoms, conjugated or non-conjugated dienes, polyenes, vinyl monomers, and cycloolefins. Available monomers may include (but are not limited to) norbornene, norbornadiene, isobutylene, isoprene, vinylbenzocyclobutane, styrene, alkyl-substituted styrene, ethylidene norbornene, dicyclopentadiene, and cyclopentene. In an illustrative embodiment of the process of this invention, an ethylene copolymer is produced wherein a comonomer having at least one α-olefin having 4 to 15 carbon atoms, preferably 4 to 12 carbon atoms, and most preferably 4 to 8 carbon atoms, is polymerized with ethylene in a gas-phase process. In another embodiment of the process of this invention, ethylene or propylene is polymerized with at least two different comonomers (optionally, one of which may be a diene) to form a terpolymer.

[0337] The present invention relates to polymerization processes, particularly gas-phase or slurry-phase processes, for polymerizing propylene alone or with one or more other monomers including ethylene and / or other olefins having 4 to 12 carbon atoms. The polymerization process may involve contacting ethylene and optionally α-olefins with one or more catalyst compositions as described above in a reactor under polymerization conditions to produce an ethylene polymer or copolymer.

[0338] Suitable gas-phase polymerization methods are described, for example, in U.S. Patents 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, 5,668,228, 5,627,242, 5,665,818, and 5,677,375, and European Publications EP-A-0 794 200, EP-A-0 802 202, EP-A2 0 891 990, and EP-B-634 421.

[0339] Slurry polymerization processes are generally used at pressures ranging from about 1 atmosphere to about 50 atmospheres and even higher, and at temperatures ranging from 0°C to about 120°C. In slurry polymerization, a suspension of solid, particulate polymer is formed in a liquid polymerization diluent medium containing ethylene and comonomers, typically hydrogen, and a catalyst. The suspension, including the diluent, is removed from the reactor intermittently or continuously, whereby volatile components separate from the polymer and are optionally recycled back to the reactor after distillation. The liquid diluent used in the polymerization medium is typically an alkane having 3 to 7 carbon atoms, preferably a branched alkane. The medium used should be liquid and relatively inert under polymerization conditions. When propane is used as the medium, the process must be operated above the critical temperature and pressure of the reaction diluent. Hexane or isobutane is preferably used as the medium.

[0340] Preferred polymerization processes are referred to as particle-form polymerization, or slurry methods, in which the temperature is maintained below the temperature at which the polymer becomes a solution. Such techniques are well known in the art and are described, for example, in U.S. Patent No. 3,248,179. Other slurry processes include those using loop reactors and those using multiple stirred reactors in series, parallel, or a combination thereof. Non-limiting examples of slurry processes include continuous loop or stirred tank processes. Furthermore, other examples of slurry processes are described in U.S. Patent No. 4,613,484. Examples of solution processes are described in U.S. Patent Nos. 4,271,060, 5,001,205, 5,236,998, and 5,589,555.

[0341] Example

[0342] It should be understood that although the invention has been described in conjunction with specific embodiments thereof, the foregoing description is intended to be illustrative and not to limit the scope of the invention. Other aspects, advantages, and modifications will be apparent to those skilled in the art to which this invention pertains. Therefore, the following examples are set forth to provide those skilled in the art with a complete disclosure and description of how the disclosed compositions are prepared and used, and the following examples are not intended to limit the scope of the invention.

[0343] Catalyst composition

[0344] Catalyst C-1 (Comparative)In a nitrogen glove box, 8 ml of toluene and 6.18 g of a 30 wt% MAO toluene solution (Albemarle Corporation, Baton Rouge, La.) were combined, followed by the addition of 0.136 g of bis(1,3-methyl-n-butylcyclopentadienyl)zirconium dichloride, and the mixture was stirred for 15 minutes at ambient temperature. Subsequently, 5 g of Davison 948 silica, pre-dehydrated at 600 °C, was added, and the slurry was stirred for 30 minutes at ambient temperature. A slurry prepared from 0.036 g of AS990 (90 wt% ethoxylated stearamide and 10% syloid silica manufactured by Univation Technologies LLC, USA) in 2.0 ml of toluene was added to the mixture and stirred for 5 minutes. The composition was then dried to a free-flowing solid by purging with nitrogen at 70 °C.

[0345] Catalyst A (In this invention) In a nitrogen glove box, 8 ml of toluene and 6.18 g of a 30 wt% MAO toluene solution (Albemarle Corporation, Baton Rouge, La.) were combined, followed by the addition of 0.136 g of bis(1,3-methyl-n-butylcyclopentadienyl)zirconium dichloride, and the mixture was stirred for 15 minutes at ambient temperature. Subsequently, 5 g of Davison 948 silica, pre-dehydrated at 600 °C, was added, and the slurry was stirred for 30 minutes at ambient temperature. 0.032 g of Varonic S202 (ethoxylated stearamide, manufactured by Evonik Goldschmidt Corporation), pre-dissolved in 2.0 ml of toluene, was added to the mixture and stirred for 5 minutes. The composition was then dried to a free-flowing solid by purging with nitrogen at 70 °C.

[0346] Catalyst C-2 (Comparative) In a nitrogen glove box, 8 ml of toluene and 6.18 g of a 30 wt% MAO toluene solution were combined, followed by the addition of 0.123 g of dimethylsilyl bis(tetrahydroindene)zirconium dichloride, and the mixture was stirred for 15 minutes at ambient temperature. Subsequently, 5 g of PQ ES70 silica, pre-dehydrated at 600 °C, was added, and the slurry was stirred for 30 minutes at ambient temperature. A slurry prepared from AS990 (0.144 g) in 2.0 ml of toluene was added to the mixture and stirred for 5 minutes. The composition was then dried to a free-flowing solid by purging with nitrogen at 70 °C.

[0347] Catalyst B (in this invention)In a nitrogen glove box, 8 ml of toluene and 6.18 g of a 30 wt% MAO toluene solution were combined, followed by the addition of 0.123 g of dimethylsilyl bis(tetrahydroindene)zirconium dichloride, and the mixture was stirred for 15 minutes at ambient temperature. 5 g of PQ ES70 silica, pre-dehydrated at 600 °C, was added, and the slurry was stirred for 30 minutes at ambient temperature. Varonic S202 (0.130 g) pre-dissolved in 2.0 ml of toluene was added to the mixture, and the mixture was stirred for 5 minutes. The composition was then dried to a free-flowing solid by purging with nitrogen at 70 °C.

[0348] Catalyst compositions D and C-3 were prepared in the same manner as compositions A and C-1, except that bis(n-propyl-cyclopentadienyl)zirconium dichloride was used instead of bis(1,3-methyl-n-butylcyclopentadienyl)zirconium dichloride.

[0349] Laboratory polymerization

[0350] A 0.20 mmol solution of triisobutylaluminum (TIBAL) in hexane was charged into a 2-liter high-pressure reactor under nitrogen purging, followed by the addition of 1-hexene comonomer (20 ml of catalyst B and catalyst C-2, or 60 ml of catalysts A, D, C-1, and C-3) and 800 ml of isobutane diluent. The reactor contents were heated to 80°C, and then 100 mg of the catalyst composition, 3 mg of aluminum distearate, and ethylene were simultaneously introduced into the reactor to establish a total reactor pressure of 325 psi. The reactor temperature was maintained at 85°C, and polymerization was allowed to proceed for 40 minutes. After 40 minutes, the reactor was cooled, ethylene and isobutane were drained, and the polymer was dried and weighed to obtain the yield. The results are summarized in Table 1.

[0351]

[0352] The results indicate that the catalyst productivity was not affected by the source of the fatty amine.

[0353] Continuous pilot-scale polymerization

[0354] Supported catalysts similar to compositions A, B, C-1, and C-2 were tested in a continuous pilot-scale gas-phase fluidized bed reactor with an inner diameter of 0.6 m and a bed height of 4.4 m. The fluidized bed consisted of polymer particles, and a gaseous feed stream of ethylene and hydrogen, along with liquid 1-hexene, was introduced into the recirculation gas line below the reactor bed. Individual flow rates of ethylene, hydrogen, and 1-hexene were controlled to maintain a fixed composition target. The ethylene concentration was controlled to maintain a constant ethylene partial pressure. Hydrogen was controlled to maintain a constant hydrogen to ethylene molar ratio. The concentrations of all gases were measured by online gas chromatography to ensure a relatively constant composition in the recirculation gas stream. The reaction bed of growing polymer particles was maintained in a fluidized state by continuously flowing the supplementary feed and recirculation gas through the reaction zone. This was achieved using an apparent gas velocity of approximately 0.7 m / s. The reactor was operated at a total pressure of 2200 kPa. The bed was maintained at a constant height by evacuating a portion of the fluidized bed at a rate equal to the rate of granular product formation. The polymer production rate is in the range of 60-70 kg / h. The product is semi-continuously removed into a fixed-volume chamber through a series of valves. This product is purified to remove entrained hydrocarbons and treated with a small stream of moist nitrogen to passivate any trace amounts of residual catalyst.

[0355] Table 2 below, based on a mass balance method, shows that catalyst compositions A and B of the present invention produce improved productivity compared to comparative catalyst compositions C1 and C2. Furthermore, reactor shell temperature and static measurements indicate that the catalyst compositions of the present invention perform well without process interference.

[0356]

[0357] For the sake of brevity, this article only explicitly discloses certain ranges. However, a range from any lower bound can be combined with any upper bound to enumerate a range that is not explicitly enumerated, and a range from any lower bound can be combined with any other lower bound to enumerate a range that is not explicitly enumerated, and in the same way, a range from any upper bound can be combined with any other upper bound to enumerate a range that is not explicitly enumerated.

[0358] All referenced documents are fully incorporated herein by way of all permissions, in which such incorporation is permitted and, to some extent, the disclosures are consistent with the description of the invention.

Claims

1. A method for manufacturing a catalyst composition, the method comprising the step of: contacting at least one supported catalyst with at least one aliphatic amine, wherein the aliphatic amine comprises less than 2% by weight of particulate inorganic material, and wherein the at least one aliphatic amine is represented by the following formula: (R1) x N(R2OH) y in R1 is a hydrocarbon group having 9 to 40 carbon atoms; R2 is a divalent hydrocarbon group having 1 to 8 carbon atoms; as well as The value of x is 1 or 2 and x + y = 3. When the catalyst composition is in substantially dry solid form, the at least one aliphatic amine is present in the catalyst composition in an amount of up to 1% by weight of the total weight of the catalyst composition.

2. The method according to claim 1, wherein the method comprises the following steps: At least one supported catalyst is contacted with at least one fatty amine in at least one liquid medium to form a slurry of the catalyst composition in the liquid medium.

3. The method according to claim 2, wherein the method comprises the following steps: a) Combining at least one supported catalyst with a liquid medium to form a slurry; and b) Add at least one fatty amine to the slurry to form a slurry of the catalyst composition in the liquid medium.

4. The method according to claim 2, wherein the method comprises the following steps: a) Combining at least one fatty amine with a liquid mediator; and b) Combining at least one supported catalyst with the mixture formed in a) to form a slurry of the catalyst composition in the liquid medium.

5. The method according to any one of claims 2 to 4, wherein the liquid medium is an aromatic hydrocarbon.

6. The method according to any one of claims 2 to 5, wherein the method further comprises the step of drying the slurry to provide a substantially free-flowing powder.

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