Process for producing polyethylene

专利摘要:
The present invention provides, under polymerization conditions, a Ziegler-Natta type catalyst comprising ethylene and / or ethylene and one or more other olefin (s) comprising at least one internal electron donor, trimethylaluminum and Of homopolymers and copolymers of ethylene, comprising contacting with at least one external electron donor compound comprising at least one carbon-oxygen-carbon bond (COC) selected from the group consisting of compounds of Formula 3 and Formula 4 It relates to a novel manufacturing method: Formula 1 R 1 -CH 2 -O-CH 2 -R 2 Formula 2 Formula 3 R 5 -OR 6 Formula 4 R 7 -O (-R 8 -O) n -R 9 The invention also provides films and articles made from these polymers.
公开号:KR20010108287A
申请号:KR1020017011101
申请日:1999-03-03
公开日:2001-12-07
发明作者:포드랜들레이；에임즈윌리엄앨버트；둘레이케네쓰앨런；밴더빌트제프리제임스；원더스앨런조지
申请人:해리 제이. 그윈넬；이스트만 케미칼 캄파니；
IPC主号:

专利说明:

Production method of polyethylene {PROCESS FOR PRODUCING POLYETHYLENE}
[2] Polyethylene polymers are well known and are useful in many fields. In particular, linear polyethylene polymers have properties that distinguish them from other polyethylene polymers, such as branched ethylene homopolymers, commonly referred to as low density polyethylene (LDPE). Some of these features are described in US Pat. No. 4,076,698 to Anderson et al.
[3] Particularly useful polymerization media for preparing polyethylene polymers are the gas phase. Examples of such methods are U.S. Pat.Nos. 3,709,853, 4,003,712, 4,011,382, 4,302,566, 4,543,399, 4,882,400, 5,352,749 and 5,541,270, and Canadian Patents 991,798 and Belgian Patent 839,380 It can be found in the arc.
[4] Ziegler-Natta type catalyst systems for olefin polymerization are well known in the art and have been known since at least US Pat. No. 3,113,115. Subsequently, numerous patents have been issued on new or improved Ziegler-Natta type catalysts. Examples of such patent documents are U.S. Patents 3,594,330, 3,676,415, 3,644,318, 3,917,575, 4,105,847, 4,148,754, 4,256,866, 4,298,713, 4,311,752, 4,363,904, 4,481,301 And Re-licensed Patent No. 33,683.
[5] These patents disclose Ziegler-Natta type catalysts, which are widely known to typically consist of a transition metal component and a cocatalyst which is usually an organoaluminum compound. In addition to the catalyst, activators such as halogenated hydrocarbons, and activity modifiers such as electron donors are optionally used.
[6] The use of halogenated hydrocarbons with Ziegler-Natta type polymerization catalysts in the process for the production of polyethylene is disclosed in US Pat. Nos. 3,354,139 and EP 0 529 977 B1 and EP 0 703 246 A1. . As disclosed in these documents, halogenated hydrocarbons can reduce the rate of ethane formation, increase the efficiency of the catalyst, or provide other effects. Typical compounds of such halogenated hydrocarbons are saturated or unsaturated aliphatic, cycloaliphatic or aromatic hydrocarbons having 1 to 12 carbon atoms, mono- to polysubstituted with halogen. Examples of aliphatic compounds include methyl chloride, methyl bromide, methyl iodide, methylene chloride, methylene bromide, methylene iodide, chloroform, bromoform, iodoform, carbon tetrachloride, carbon tetrabromide, carbon tetraiodide, ethyl chloride, Ethyl bromide, 1,2-dichloroethane, 1,2-dibromoethane, methylchloroform, perchloroethylene and the like. Examples of the alicyclic compound include chlorocyclopropane, tetrachlorocyclopentane and the like. Examples of aromatic compounds include chlorobenzene, hexabromobenzene, benzotrichloride, and the like. These compounds can be used individually or as mixtures thereof.
[7] Also known in the process for the polymerization of olefins, in particular when Ziegler-Natta type catalysts are used, are alternatively using electron donors. Such electron donors often help to increase the efficiency of the catalyst and / or to control the stereoselectivity of the polymer when olefins other than ethylene are polymerized. When an electron donor, typically known as a Lewis base, is used during the catalyst preparation step, it is referred to as an internal electron donor. Electron donors used in steps other than during the catalyst preparation step are referred to as external electron donors. For example, an external electron donor can be added to the preformed catalyst, prepolymer and / or polymerization medium.
[8] The use of electron donors in the field of propylene polymerization is also well known and is mainly used to reduce the atactic form of the polymer and to increase the production of isotactic polymers. The use of electron donors generally improves the productivity of the catalysts making isotactic polypropylene. This is collectively shown in US Pat. No. 4,981,930.
[9] In the field of ethylene polymerization where ethylene accounts for at least about 70% by weight of the total monomers present in the polymer, electron donors are used to control the molecular weight distribution (MWD) of the polymer and the activity of the catalyst in the polymerization medium. Examples of patent documents that describe the use of internal electron donors in the preparation of linear polyethylene are described in US Pat. Nos. 3,917,575, 4,187,385, 4,256,866, 4,293,673, 4,296,223, and Re-licensed Patent 33,683. 4,302,565, 4,302,566 and 5,470,812. The use of external monoether electron donors, such as tetrahydrofuran (THF) to control molecular weight distribution, is disclosed in US Pat. No. 5,055,535, and the use of external electron donors for controlling the reactivity of catalyst particles is described in US Pat. 5,410,002.
[10] Examples of electron donors include carboxylic acids, carboxylic esters, alcohols, ethers, ketones, amines, amides, nitriles, aldehydes, thioethers, thioesters, carboxylic acid esters, organosilicon compounds including oxygen atoms, and carbon or oxygen atoms. Phosphorus compounds, arsenic compounds or antimony compounds bonded to organic groups.
[11] Summary of the Invention
[12] The polymerization process of the present invention utilizes at least one internal electron donor in a polymerization medium comprising ethylene and optionally other olefin (s) such that the molar ratio of internal electron donor to Ziegler-Natta type catalyst is from 1: 1 to about 1000: 1. A Ziegler-Natta type polymerization catalyst, trimethylaluminum (TMA) as a promoter, and at least one carbon-oxygen-carbon bond (COC) of Formula 1, Formula 2, Formula 3, and Formula 4 Introducing one or more external electron donors includes:
[13] R ¹ -CH ₂ -O-CH ₂ -R ²
[14]
[15] R ⁵ -OR ⁶
[16] R ⁷ -O (-R ⁸ -O) _n -R ⁹
[17] [Wherein,
[18] n is 1 to 30;
[19] R^OneAnd R²Is Independently saturated, containing from 1 to 30 carbon atoms and containing from 0 to 30 heteroatoms consisting of an element selected from Groups 13, 14, 15, 16 and 17 of the Periodic Table of the Elements or mixtures thereof 0-30 heteroatoms containing aliphatic or unsaturated aliphatic groups and from 1 to 30 carbon atoms and consisting of elements selected from Groups 13, 14, 15, 16 and 17 of the Periodic Table of the Elements or mixtures thereof It is selected from the group consisting of a substituted or unsubstituted aromatic group containing;
[20] R ³ and R ⁴ are connected to each other to form part of a cyclic or polycyclic structure, contain 1 to 30 carbon atoms, and an element selected from Groups 13, 14, 15, 16, and 17 of the Periodic Table of the Elements Or a saturated or unsaturated aliphatic group containing 0 to 30 heteroatoms consisting of a mixture thereof, and containing 1 to 30 carbon atoms, and containing groups 13, 14, 15, 16, and 17 of the periodic table of elements. Hydrocarbons independently selected from the group consisting of substituted or unsubstituted aromatic groups containing 0 to 30 heteroatoms consisting of an element selected from the group or a mixture thereof;
[21] R ⁵ contains 1 to 30 carbon atoms and is substituted or contains 0 to 30 heteroatoms consisting of an element selected from Groups 13, 14, 15, 16 and 17 of the Periodic Table of the Elements or mixtures thereof Unsubstituted aromatic groups;
[22] R ⁶ , R ⁷ , R ⁸ and R ⁹ independently contain 1 to 30 carbon atoms and consist of an element selected from Groups 13, 14, 15, 16 and 17 of the Periodic Table of the Elements or mixtures thereof Saturated or unsaturated aliphatic groups containing 0 to 30 heteroatoms, and elements selected from Groups 13, 14, 15, 16, and 17 of the Periodic Table of Elements or their It is selected from the group consisting of substituted or unsubstituted aromatic groups containing 0 to 30 heteroatoms consisting of a mixture of.
[23] In addition, mixtures of compounds of Formula 1, Formula 2, Formula 3 and Formula 4 can be used as the external electron donor herein.
[24] Optionally, halogenated hydrocarbon compounds can be used in the polymerization medium. External electron donors and / or TMAs as defined herein can be added to the polymerization medium in any manner. External electron donors and / or TMAs as defined herein may be added to the catalyst just prior to addition to the polymerization medium, or may be added to the polymerization medium in any manner known in the art, separate from the catalyst. For example, an external electron donor as defined herein may optionally be premixed with a TMA promoter.
[25] When using a gas phase fluidized bed process in the polymerization of ethylene, it may be advantageous to add an external electron donor as defined herein before to a heat removal means, for example a heat exchanger, to slow down the rate at which the heat removal means is blocked. .
[26] All matters mentioned herein for the elements of the periodic table refer to the periodic table of the elements as disclosed in Chemical and Engineering News , 63 (5), 27, 1985. The periodic table of elements is disclosed in Groups 1 to 18.
[1] The present invention relates to a polymerization process for producing polyethylene and to films made of polyethylene.
[27] We have found an improved method of making polyethylene. The method comprises a Ziegler-Natta catalyst, a trimethylaluminum (TMA) promoter comprising at least one internal electron donor such that the molar ratio of the internal metal donor to the Ziegler-Natta catalyst is from 1: 1 to about 1000: 1. The use of certain combinations of one or more external electron donor compounds comprising at least one carbon-oxygen-carbon bond (COC) of Formula 1, Formula 2, Formula 3, and Formula 4 is:
[28] Formula 1
[29] R ¹ -CH ₂ -O-CH ₂ -R ²
[30] Formula 2
[31]
[32] Formula 3
[33] R ⁵ -OR ⁶
[34] Formula 4
[35] R ⁷ -O (-R ⁸ -O) _n -R ⁹
[36] [Wherein,
[37] n is 1 to 30;
[38] R^OneAnd R²Is Independently saturated, containing from 1 to 30 carbon atoms and containing from 0 to 30 heteroatoms consisting of an element selected from Groups 13, 14, 15, 16 and 17 of the Periodic Table of the Elements or mixtures thereof 0-30 heteroatoms containing aliphatic or unsaturated aliphatic groups and from 1 to 30 carbon atoms and consisting of elements selected from Groups 13, 14, 15, 16 and 17 of the Periodic Table of the Elements or mixtures thereof It is selected from the group consisting of a substituted or unsubstituted aromatic group containing;
[39] R ³ and R ⁴ are connected to each other to form part of a cyclic or polycyclic structure, contain 1 to 30 carbon atoms, and an element selected from Groups 13, 14, 15, 16, and 17 of the Periodic Table of the Elements Or a saturated or unsaturated aliphatic group containing 0 to 30 heteroatoms consisting of a mixture thereof, and containing 1 to 30 carbon atoms, and containing groups 13, 14, 15, 16, and 17 of the periodic table of elements. Hydrocarbons independently selected from the group consisting of substituted or unsubstituted aromatic groups containing 0 to 30 heteroatoms consisting of an element selected from the group or a mixture thereof;
[40] R ⁵ contains 1 to 30 carbon atoms and is substituted or contains 0 to 30 heteroatoms consisting of an element selected from Groups 13, 14, 15, 16 and 17 of the Periodic Table of the Elements or mixtures thereof Unsubstituted aromatic groups;
[41] R ⁶ , R ⁷ , R ⁸ and R ⁹ independently contain 1 to 30 carbon atoms and consist of an element selected from Groups 13, 14, 15, 16 and 17 of the Periodic Table of the Elements or mixtures thereof Saturated or unsaturated aliphatic groups containing 0 to 30 heteroatoms, and elements selected from Groups 13, 14, 15, 16, and 17 of the Periodic Table of Elements or their It is selected from the group consisting of substituted or unsubstituted aromatic groups containing 0 to 30 heteroatoms consisting of a mixture of.
[42] In addition, mixtures of compounds of Formula 1, Formula 2, Formula 3 and Formula 4 can be used as the external electron donor herein.
[43] Examples of R ¹ and R ² groups suitable for use herein include hydrogen, C _1-30 alkyl, C _2-30 alkenyl, C _4-30 dienyl, C _3-30 cycloalkyl, C _{3-30 cycloal} Kenyl, C _{4-30 cyclodienyl} , C _6-30 aryl, C _7-30 aralkyl and C _7-30 alkaryl. Another example is a hydrocarbon containing 1 to 30 carbon atoms and 0 to 30 heteroatoms consisting of an element selected from Groups 13, 14, 15, 16 and 17 of the Periodic Table of the Elements or mixtures thereof And include, for example, a mixture of B _1-30 borohydrocarbon, Si _1-30 silahydrocarbon, P _{1-30 phosphahydrocarbon} , S _1-30 thiahydrocarbon, Cl _1-30 chlorohydrocarbon, and halogens Halogenated hydrocarbons are included.
[44] Examples of R ³ and R ⁴ hydrocarbon groups suitable for use herein include C _1-30 alkyl, C _2-30 alkenyl, C _4-30 dienyl, C _3-30 cycloalkyl, C _3-30 cycloalkenyl , C _{4-30 cyclodienyl} , C _6-30 aryl, C _7-30 aralkyl and C _7-30 alkaryl, wherein R ³ and R ⁴ are linked to each other to form part of a cyclic or polycyclic structure. Form. Another example is a hydrocarbon containing 1 to 30 carbon atoms and 0 to 30 heteroatoms consisting of an element selected from Groups 13, 14, 15, 16 and 17 of the Periodic Table of the Elements or mixtures thereof And include, for example, a mixture of B _1-30 borohydrocarbon, Si _1-30 silahydrocarbon, P _{1-30 phosphahydrocarbon} , S _1-30 thiahydrocarbon, Cl _1-30 chlorohydrocarbon, and halogens Halogenated hydrocarbons are included, wherein R ³ and R ⁴ are connected to each other to form part of a cyclic or polycyclic structure.
[45] Examples of R ⁵ groups suitable for use herein include C _6-30 aryl and C _7-30 aralkyl. Another example is a substitution containing from 1 to 30 carbon atoms and containing from 0 to 30 heteroatoms consisting of an element selected from Groups 13, 14, 15, 16 and 17 of the Periodic Table of the Elements or mixtures thereof Aromatic hydrocarbons, which may be substituted or unsubstituted, include, for example, B _1-30 borohydrocarbon, Si _1-30 silahydrocarbon, P _{1-30 phosphahydrocarbon} , S _1-30 thiahydrocarbon, Cl _1-30 chlorohydrocarbon and Halogenated hydrocarbons comprising a mixture of halogens are included.
[46] Examples of R ⁶ , R ⁷ , R ⁸ and R ⁹ groups suitable for use herein include C _1-30 alkyl, C _2-30 alkenyl, C _4-30 dienyl, C _3-30 cycloalkyl, C _{3 -30} cycloalkenyl, C _{4-30 cyclodienyl} , C _6-30 aryl, C _7-30 aralkyl and C _7-30 alkaryl. Another example is a hydrocarbon containing 1 to 30 carbon atoms and 0 to 30 heteroatoms consisting of an element selected from Groups 13, 14, 15, 16 and 17 of the Periodic Table of the Elements or mixtures thereof And include, for example, a mixture of B _1-30 borohydrocarbon, Si _1-30 silahydrocarbon, P _{1-30 phosphahydrocarbon} , S _1-30 thiahydrocarbon, Cl _1-30 chlorohydrocarbon, and halogens Halogenated hydrocarbons are included.
[47] Exemplary compounds of Formula 1, R ¹ -CH ₂ -O-CH ₂ -R ² , which may be used herein, are compounds comprising one COC bond, for example, alkyl, alkenyl, dietenyl, and aryl substitutions. Included compounds. Specific examples are dimethyl ether, diethyl ether, dipropyl ether, dibutyl ether, dipentyl ether, diisoamyl ether, dihexyl ether, dioctyl ether, dibenzyl ether, diallyl ether, allyl methyl ether, allyl ethyl ether , Allyl benzyl ether, benzyl methyl ether, benzyl ethyl ether, butyl methyl ether, butyl ethyl ether, isoamyl methyl ether, isoamyl ethyl ether, isoamyl propyl ether, isoamyl butyl ether and the like. Examples of hydrocarbons of formula (I) containing heteroatoms of groups 13, 14, 15, 16, and 17 of the periodic table of the elements include bis (trimethylsilylmethyl) ether, trimethylsilylmethyl methyl ether, bis (2,2, 2-trifluoroethyl) ether, benzyl 3-bromopropyl ether, benzyl 3-bromo-2-chloropropyl ether, benzyl chloromethyl ether, butyl 2-chloroethyl ether, chloromethyl methyl ether, chloromethyl ethyl ether , Dimethyl 2-methoxyethyl borate, dimethyl methoxymethyl borate, dimethoxy-2-methoxyethylborane, diphenyl-2-methoxyethylphosphine, diphenylmethoxymethylphosphine, 2- (2-thi Yl) ethyl ethyl ether, 2- (2-thienyl) ethyl methyl ether, 2- (3-thienyl) ethyl ethyl ether, 2- (3-thienyl) ethyl methyl ether, 2- (2-methoxymethyl ) -1,3,2-dioxaphospholane, 1- (2-methoxyethyl) pyrrole, 1- (2-methoxyethyl) pyrazole, 1- (2-methoxyethyl) imidazole, 2- (2-methoxyethyl) pyridine and the like.
[48] Formula 2, which may be used herein Examples of the compound of include cyclic compounds in which R ³ and R ⁴ are connected to form a cyclic or polycyclic structure, for example, ethylene oxide, propylene oxide, 1,2-epoxybutane, 2,3-epoxybutane , 1,2-epoxybut-3-ene, cyclopentene oxide, trimethylene oxide, styrene oxide, 3,3-dimethyloxetane, furan, 2,3-dihydrofuran, 2,5-dihydrofuran, tetra Hydrofuran, 2-methyltetrahydrofuran, 2,5-dimethyltetrahydrofuran, 4,5-dihydro-2-methylfuran, 2-methylfuran, 2-ethylfuran, 2-3-butylfuran, 2 , 5-dimethylfuran, 2,3-dimethylfuran, 1,2-pyran, 1,4-pyran, tetrahydropyran, 3-methyltetrahydropyran, oxocan, 2,3-benzofuran, 2,3- Dihydrobenzofuran, 2-methylbenzofuran, phthalan, dibenzofuran, genten, chroman, isochroman and the like. Still other examples include cyclic compounds comprising one or more COC bonds, for example 2,5-dimethoxyfuran, 2-methoxyfuran, 3-methoxyfuran, 2-methoxytetrahydropyran, 3 -Methoxytetrahydropyran, 1,3-dioxolane, 2-methyl-1,3-dioxolane, 2,2-dimethyl-1,3-dioxolane, 2-ethyl-2-methyl-1,3- Dioxolane, 2,2-tetramethylene-1,3-dioxolane, 2,2-pentamethylene-1,3-dioxolane, 2-vinyl-1,3-dioxolane, 2-methoxy-1,3 Dioxolane, 1,4-dioxaspiro [4.4] non-6-ene, 1,4,9,12-tetraoxadispiro (4.2.4.2) tetradecane, 1,3-dioxane, 1,4 Dioxane, 4-methyl-1,3-dioxane, 1,3,5-trioxane, 2,4,8,10-tetraoxaspiro (5.5) undecane, 12-crown-4, 15-crown -5, cis-4,7-dihydro-1,3-dioxepin, 1,7-dioxaspiro (5.5) undecane, 3,4-epoxytetrahydrofuran, 2,2-dimethyl-4-vinyl -1,3-dioxolane and the like. Examples of hydrocarbons of formula (2) containing heteroatoms of Groups 13, 14, 15, 16 and 17 of the Periodic Table of the Elements include epichlorohydrin, 3-bromofuran, 2-chloromethyl-1,3- Dioxolane, 4-chlorotetrahydropyran, tri-2-furylphosphine, 1-furfurylpyrrole, dimethyl 3-furylmethyl borate, 2-trimethylsilylfuran, 3-trimethylsilylfuran, 2-trimethylsilyl-1, 3-dioxolane, 2- (3-thienyl) -1,3-dioxolane, 2-bromochloromethyl-1,3-dioxolane, oxazole, 1,3,4-oxadiazole, 3, 4-dichloro-1,2-epoxybutane, 3,4-dibromo-1,2-epoxybutane and the like.
[49] Examples of compounds of Formula 3, R ⁵ -OR ^{6 that} can be used herein include compounds comprising one COC bond, including, for example, alkyl, alkenyl, dietenyl and aryl substituted aromatic compounds. . Specific examples include diphenyl ether, bis (2-tolyl) ether, bis (3-tolyl) ether, bis (1-naphthyl) ether, bis (2-naphthyl) ether, allyl phenyl ether, allyl 2-tolyl ether , Allyl 3-tolyl ether, allyl 1-naphthyl ether, allyl 2-naphthyl ether, benzyl phenyl ether, benzyl 2-tolyl ether, benzyl 3-tolyl ether, benzyl 1-naphthyl ether, benzyl 2-naphthyl ether , Ethyl phenyl ether, ethyl 2-tolyl ether, ethyl 3-tolyl ether, ethyl 1-naphthyl ether, ethyl 2-naphthyl ether, methyl phenyl ether, methyl 2-tolyl ether, methyl 3-tolyl ether, methyl 1- Naphthyl ether, methyl 2-naphthyl ether, and the like. Another example of a hydrocarbon of formula (3) containing heteroatoms of Groups 13, 14, 15, 16 and 17 of the Periodic Table of the Elements is 2-ethoxy-1-methylpyrrole, 3-methoxy-1-methyl Pyrrole, 2-ethoxythiophene, 3-methoxythiophene, 3-methoxy-1-methylpyrazole, 4-methoxy-1-methylpyrazole, 5-methoxy-1-methylpyrazole, 2-meth Methoxy-1-methylimidazole, 4-methoxy-1-methylimidazole, 5-methoxy-1-methylimidazole, 3-methoxy-1-phenylpyrazole, 4-methoxy-1 -Phenylpyrazole, 5-methoxy-1-phenylpyrazole, 2-methoxy-1-phenylimidazole, 4-methoxy-1-phenylimidazole, 5-methoxy-1-phenylimida Sol, 4-methoxy-1-methyl-1,2,3-triazole, 5-methoxy-1-methyl-1,2,3-triazole, 4-methoxy-1-phenyl-1,2 , 3-triazole, 5-methoxy-1-phenyl-1,2,3-triazole, 3-methoxy-1-methyl-1,2,4-triazole, 5-methoxy-1-methyl -1,2,4-triazole, 3-methoxy-1-phenyl-1,2,4-triazole, 5-methoxy-1-phenyl-1,2,4-triazole, 5-methoxy -1-methyltetrazole, 5- Methoxy-1-phenyltetrazole, 3-methoxyisoxazole, 4-methoxyisoxazole, 5-methoxyisoxazole, 2-methoxyoxazole, 4-methoxyoxazole, 5-methoxyoxazole , 3-methoxy-1,2,4-oxadiazole, 5-methoxy-1,2,4-oxadiazole, 2-methoxy-1,3,4-oxadiazole, 3-methoxy Isothiazole, 4-methoxyisothiazole, 5-methoxyisothiazole, 2-methoxythiazole, 4-methoxythiazole, 5-methoxythiazole, 2-methoxypyridine, 3-methoxypyridine, 4-methoxypyridine, 3-methoxypyridazine, 4-methoxypyridazine, 2-methoxypyrimidine, 4-methoxypyrimidine, 5-methoxypyrimidine, 2-methoxypyrazine, 3-methoxy Methoxy-1,2,4-triazine, 5-methoxy-1,2,4-triazine, 6-methoxy-1,2,4-triazine, 2-methoxy-1,3,5- Triazines and the like.
[50] Examples of compounds of Formula 4, R ⁷ -O (-R ⁸ -O) _n -R ⁹ compounds, wherein n is from 1 to 30, which include one or more COC bonds that can be used herein are alkyl, alkenyl , Dienyl and aryl substituted compounds. Specific examples include dimethoxymethane, 1,1-dimethoxyethane, 1,1,1-trimethoxyethane, 1,1,1-triethoxyethane, 1,1,2-trimethoxyethane, 1, 1-dimethoxypropane, 1,2-dimethoxypropane, 2,2-dimethoxypropane, 1,3-dimethoxypropane, 1,1,3-trimethoxypropane, 1,4-dimethoxybutane, 1 , 2-dimethoxybenzene, 1,3-dimethoxybenzene, 1,4-dimethoxybenzene, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol divinyl ether, ethylene glycol diphenyl ether, ethylene glycol dicyclo Pentyl ether, ethylene glycol tert-butyl methyl ether, ethylene glycol tert-butyl ethyl ether, di (ethylene glycol) dimethyl ether, di (ethylene glycol) diethyl ether, di (ethylene glycol) dibutyl ether, di (ethylene Glycol) tert-butyl methyl ether, tri (ethylene glycol) dimethyl ether, tri (ethylene glycol) diethyl ether, tet La (ethylene glycol) dimethyl ether, tetra (ethylene glycol) diethyl ether, 2- (2-ethylhexyl) -1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, 2-butyl -1,3-dimethoxypropane, 2-tert-butyl-1,3-dimethoxypropane, 2-3-butyl-1,3-dimethoxypropane, 2-cyclohexyl-1,3-dimethoxy Propane, 2-phenyl-1,3-dimethoxypropane, 2-cumyl-1,3-dimethoxypropane, 2- (2-phenylethyl) -1,3-dimethoxypropane, 2- (2-cyclohexyl Ethyl) -1,3-dimethoxypropane, 2- (p-chlorophenyl) -1,3-dimethoxypropane, 2- (p-fluorophenyl) -1,3-dimethoxypropane, 2- (di Phenylmethyl) -1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-dimethoxypropane, 2,2-dipropyl- 1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-dibutyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3 Dimethoxypropane, 2-methyl-2-ethyl-1,3-dimethoxypropane, 2-methyl-2-propyl-1,3-dimethoxypropane, 2-methyl-2-butyl-1,3-dimethoxypropane, 2-methyl-2-benzyl-1,3-dimethoxypropane, 2- Methyl-2-methylcyclohexyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2-bis (2-cyclohexylmethyl) -1,3 Dimethoxypropane and the like. Another example of a compound of Formula 4 containing heteroatoms of Groups 13, 14, 15, 16 and 17 of the Periodic Table of the Elements is ethylene glycol bis (trimethylsilylmethyl) ether, di (ethylene glycol) methyl trimethylsilyl Ethers, tris (2-methoxyethyl) borate, ethylene glycol chloromethyl bromomethyl ether and the like.
[51] Preferred examples for use herein as external electron donors include dimethyl ether, diethyl ether, dipropyl ether, dibutyl ether, diisoamyl ether, dibenzyl ether, butyl methyl ether, butyl ethyl ether, chloromethyl methyl ether, trimethyl Silylmethyl methyl ether, bis (trimethylsilylmethyl) ether, bis (2,2,2-trifluoroethyl) ether, ethylene oxide, propylene oxide, 1,2-epoxybutane, cyclopentene oxide, epichlorohydrin, Furan, 2,3-dihydrofuran, 2,5-dihydrofuran, tetrahydrofuran, 2-methyltetrahydrofuran, 2,5-dimethyltetrahydrofuran, 2-methylfuran, 2,5-dimethylfuran, Tetrahydropyran, 1,2-epoxybut-3-ene, styrene oxide, 2-ethylfuran, oxazole, 1,3,4-oxadiazole, 3,4-dichloro-1,2-epoxybutane, 3 , 4-dibromo-1,2-epoxybutane, dimethoxymethane , 1,1-dimethoxyethane, 1,1,1-trimethoxymethane, 1,1,1-trimethoxyethane, 1,1,2-trimethoxyethane, 1,1-dimethoxypropane, 1,2-dimethoxypropane, 2,2-dimethoxypropane, 1,3-dimethoxypropane, 1,1,3-trimethoxypropane, 1,4-dimethoxybutane, 1,2-dimethoxybenzene , 1,3-dimethoxybenzene, 1,4-dimethoxybenzene, ethylene glycol dimethyl ether, di (ethylene glycol) dimethyl ether, di (ethylene glycol) diethyl ether, di (ethylene glycol) dibutyl ether, di ( Ethylene glycol) tert-butyl methyl ether, tri (ethylene glycol) dimethyl ether, tri (ethylene glycol) diethyl ether, tetra (ethylene glycol) dimethyl ether, 2,2-dienyl-1,3-dimethoxypropane, 2-methyl-2-ethyl-1,3-dimethoxypropane, 2-methoxyfuran, 3-methoxyfuran, 1,3-dioxolane, 2-methyl-1,3-dioxolane, 2,2- Dimethyl-1,3-dioxolane, 2-ethyl-2-methyl-1,3-dioxolane, 2,2-tetramethylene-1,3-di Oxolane, 2,2-pentamethylene-1,3-dioxolane, 1,3-dioxane, 1,4-dioxane, 4-methyl-1,3-dioxane, 1,3,5-trioxane And 3,4-epoxytetrahydrofuran.
[52] Most preferred examples for use as external electron donors herein include tetrahydrofuran, diethyl ether, dipropyl, methyl propyl ether, dibutyl ether, dioctyl ether, trimethylene oxide and tetrahydropyran.
[53] The polymerization process of the invention can be carried out using any suitable method. For example, a polymerization process can be used which is carried out in a suspension medium, a solution medium, a supercritical medium or a gaseous medium. All of these polymerization methods are well known in the art.
[54] Particularly preferred processes for preparing polyethylene polymers according to the invention are preferably gas phase polymerization processes using fluidized bed reactors. Typical forms of fluidized bed reactors and means for operating the reactors are well known and described in US Pat. Nos. 3,709,853, 4,003,712, 4,011,382, 4,012,573, 4,302,566, 4,543,399, 4,882,400, 5,352,749, 5,541,270, and Canadian Patent 991,798, and Belgian Patent 839,380. These patent documents disclose a gas phase polymerization process in which the polymerization medium is mechanically stirred or flowed by continuous flow of gaseous monomers and diluents. The entire contents of these patent documents are incorporated herein by reference.
[55] In general, the polymerization process of the invention can be carried out in a continuous gas phase process such as a fluidized bed process. Fluidized bed reactors for use in the method of the invention typically comprise a reaction zone and a so-called deceleration zone. The reaction zone comprises a layer of the resulting polymer particles, the resulting polymer particles and a small amount of catalyst particles suspended by a continuous flow of gaseous monomer and diluent to remove the heat of polymerization therethrough. Optionally, by cooling and compressing a portion of the recycled gas, a liquid may be prepared that increases the heat removal capacity of the circulating gas stream when it is returned to the reaction zone. Appropriate gas flow rates can be determined immediately by simple experiments. The rate of introduction of the gaseous monomer into the circulating gas stream is the same as the rate of recovery of the polymer product in particulate form and the monomers bound thereto from the reactor, so that the composition of the gas passing through the reactor is essentially steady within the reaction zone. It is adjusted to maintain the composition of the gas. The gas exiting the reaction zone passes through a deceleration zone where trapped particles are removed. More finely collected particles and dust can be removed in cyclones and / or fine filters. The gas is passed through a heat exchanger to remove heat of polymerization, compressed in a compressor, and then returned to the reaction zone.
[56] More specifically, the reaction temperature of the fluidized bed process herein is about 30 ° C to about 110 ° C. In general, the reactor temperature is the highest temperature that can be raised in consideration of the sintering temperature of the polymer product in the reactor.
[57] The process of the invention is suitable for preparing homopolymers of ethylene and / or copolymers of ethylene and one or more other olefins, terpolymers and the like. Preferably the olefin is an alpha-olefin. For example, the olefin may contain 3 to 16 carbon atoms. Particularly preferred compounds for preparing herein using the process of the invention are linear polyethylenes. Such linear polyethylenes are preferably linear homopolymers of ethylene, and linear copolymers of ethylene and one or more alpha-olefins, where the ethylene content accounts for at least about 70% by weight of the total monomers. Examples of alpha-olefins that can be used herein include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4-methylpent-1-ene, 1-decene, 1-dodecene , 1-hexadecene and the like. 1,3-hexadiene, 1,4-hexadiene, cyclopentadiene, dicyclopentadiene, 4-vinylcyclohex-1-ene, 1,5-cyclooctadiene, 5-vinylidene-2-nor Polyenes such as bonene and 5-vinyl-2-norbornene, and olefins formed in situ in the polymerization medium can also be used herein. When olefins are formed in situ in the polymerization medium, linear polyethylene with long chain branches can be produced.
[58] The polymerization reaction of the present invention is carried out in the presence of a Ziegler-Natta catalyst. In the process of the invention, the catalyst can be introduced in any manner known in the art. For example, in the process of the invention, the catalyst can be introduced directly into the polymerization medium in the form of a solution, slurry, or anhydrous free flowing powder. The catalyst can also be used in the form of inactivated catalysts or in the form of prepolymers prepared by contacting the catalyst with one or more olefins in the presence of a promoter. The Ziegler-Natta catalyst used in the present invention comprises one or more internal electron donors.
[59] When preparing a Ziegler-Natta type catalyst as used herein, one or more internal electron donors are introduced. Any internal electron donor known in the art can be used. Internal electron donors are introduced such that the molar ratio of internal electron donor to Ziegler-Natta type catalyst is from 1: 1 to about 1000: 1.
[60] Ziegler-Natta catalysts are well known in the industry. The simplest form of Ziegler-Natta catalysts consists of transition metal compounds and organometallic promoter compounds. Metals of transition metal compounds are described in Group 4, 5, 6, 7, 8, 9 and 10 of the Periodic Table of the Elements as disclosed in Chemical and Engineering News , 63 (5), 27, 1985. Metal. In the periodic table, metals are divided into groups 1 to 18. Examples of such transition metals include titanium, zirconium, vanadium, chromium, manganese, iron, cobalt, nickel, and mixtures thereof. In a preferred embodiment, the transition metal is selected from the group consisting of titanium, zirconium, vanadium and chromium, and in a more preferred embodiment, the transition metal is titanium. Ziegler-Natta catalysts may optionally include magnesium and chlorine. Catalysts comprising such magnesium and chlorine can be prepared by any method known in the art.
[61] Any internal electron donor can be used to prepare the Ziegler-Natta catalyst. Examples of internal electron donors include hydrocarbons containing 1 to 50 carbon atoms and 0 to 30 heteroatoms consisting of an element selected from Groups 14, 15, 16 and 17 of the Periodic Table of the Elements or mixtures thereof. Included. Examples of suitable internal electron donor compounds include, for example, ethers, thioethers, amines, esters, thioesters, amides, anhydrides, acid halides, aldehydes, ketones, alcohols, nitriles, phosphines, silanes, carboxylic acids, and the like. .
[62] Examples of ethers useful as internal electron donors include dimethyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dipentyl ether, dihexyl ether, dioctyl ether, diisoamyl ether, di-tertiary -Butyl ether, diphenyl ether, dibenzyl ether, divinyl ether, diallyl ether, dicyclopropyl ether, dicyclopentyl ether, dicyclohexyl ether, bis (2,2,2-trifluoroethyl) ether, Allyl methyl ether, allyl ethyl ether, allyl cyclohexyl ether, allyl phenyl ether, allyl benzyl ether, allyl 2-tolyl ether, allyl 3-tolyl ether, allyl 4-tolyl ether, benzyl methyl ether, benzyl ethyl ether, benzyl isoamyl Ether, benzyl chloromethyl ether, benzyl cyclohexyl ether, benzyl phenyl ether, benzyl 1-naphthyl ether, benzyl 2-naphthyl ether, butyl methyl Tert, butyl ethyl ether, secondary-butyl methyl ether, tert-butyl methyl ether, butyl cyclopentyl ether, butyl 2-chloroethyl ether, cyclopentyl methyl ether, cyclohexyl ethyl ether, cyclohexyl vinyl ether, tertiary- Amyl methyl ether, secondary-butyl ethyl ether, tert-butyl ethyl ether, tert-amyl ethyl ether, cyclododecyl methyl ether, bis (2-cyclopenten-l-yl) ether, 1-methoxy-1 , 3-cyclohexadiene, 1-methoxy-1,4-cyclohexadiene, chloromethyl methyl ether, chloromethyl ethyl ether, bis (2-tolyl) ether, trimethylsilylmethyl methyl ether, trimethylene oxide, 3, 3-dimethyloxetane, furan, 2,3-dihydrofuran, 2,5-dihydrofuran, tetrahydrofuran, 2-methyltetrahydrofuran, 2,5-dimethyltetrahydrofuran, 4,5-dihydro 2-methylfuran, 2-methylfuran, 2,5-dimethylfuran Lan, 3-bromofuran, 2,3-benzofuran, 2-methylbenzofuran, dibenzofuran, isobenzofuran, genten, 1,2-pyran, 1,4-pyran, tetrahydropyran, 3-methyl Tetrahydropyran, 4-chlorotetrahydropyran, chromman, isochroman, oxocan, 1,1-dimethoxyethane, 1,1,1-trimethoxyethane, 1,1,2-trimethoxyethane , 1,1-dimethoxypropane, 1,2-dimethoxypropane, 2,2-dimethoxypropane, 1,3-dimethoxypropane, 1,1,3-trimethoxypropane, 1,4-dimethoxy Butane, 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, 1,4-dimethoxybenzene, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol divinyl ether, ethylene glycol diphenyl ether, ethylene Glycol tert-butyl methyl ether, ethylene glycol tert-butyl ethyl ether, di (ethylene glycol) dimethyl ether, di (ethylene glycol) diethyl ether, di (ethylene glycol) dibutyl ether, (Ethylene glycol) tert-butyl methyl ether, tri (ethylene glycol) dimethyl ether, tri (ethylene glycol) diethyl ether, tetra (ethylene glycol) dimethyl ether, tetra (ethylene glycol) diethyl ether, 2,5-dimeth Methoxyfuran, 2-methoxyfuran, 3-methoxyfuran, 2-methoxytetrahydropyran, 3-methoxytetrahydropyran, 1,3-dioxolane, 2-methyl-1,3-dioxolane, 2 , 2-dimethyl-1,3-dioxolane, 2-ethyl-2-methyl-1,3-dioxolane, 2,2-tetramethylene-1,3-dioxolane, 2,2-pentamethylene-1, 3-dioxolane, 2-vinyl-1,3-dioxolane, 2-chloromethyl-1,3-dioxolane, 2-methoxy-1,3-dioxolane, 1,4-dioxaspiro [4.4] Non-6-ene, 1,4,9,12-tetraoxadispiro (4.2.4.2) tetradecane, 1,3-dioxane, 1,4-dioxane, 4-methyl-1,3-dioxane , 1,3,5-trioxane, 2,4,8,10-tetraoxaspiro (5.5) undecane, 12-crown-4, 15-crown-5, cis-4,7-dihydro-1, 3-dioxepin, 2- (2-ethylhexyl) -1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, 2-butyl-1,3-dimethoxypropane, 2-tert-butyl-1,3-dimethoxypropane, 2 -Tert-butyl-1,3-dimethoxypropane, 2-cyclohexyl-1,3-dimethoxypropane, 2-phenyl-1,3-dimethoxypropane, 2-cumyl-1,3-dimethoxypropane , 2- (2-phenylethyl) -1,3-dimethoxypropane, 2- (2-cyclohexylethyl) -1,3-dimethoxypropane, 2- (p-chlorophenyl) -1,3-dimeth Oxypropane, 2- (p-fluorophenyl) -1,3-dimethoxypropane, 2- (diphenylmethyl) -1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethic Oxypropane, 2,2-diethyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2 , 2-dibutyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2-methyl-2-ethyl-1,3-dimethoxypropane, 2-methyl- 2-propyl-1,3-dimethoxypropane, 2-methyl-2-butyl-1,3-dimethoxypropane, 2-methyl-2-benzyl-1,3- Methoxypropane, 2-methyl-2-methylcyclohexyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2-bis (2-cyclohexyl Methyl) -1,3-dimethoxypropane and the like.
[63] Examples of thioethers useful as internal electron donors include dimethyl sulfide, diethyl sulfide, dipropyl sulfide, diisopropyl sulfide, dibutyl sulfide, dipentyl sulfide, dihexyl sulfide, dioctyl sulfide, Diisoamyl sulfide, di-tert-butyl sulfide, diphenyl sulfide, dibenzyl sulfide, divinyl sulfide, diallyl sulfide, dipropargyl sulfide, dicyclopropyl sulfide, dicyclopentyl Sulfide, dicyclohexyl sulfide, allyl methyl sulfide, allyl ethyl sulfide, allyl cyclohexyl sulfide, allyl phenyl sulfide, allyl benzyl sulfide, allyl 2-tolyl sulfide, allyl 3-tolyl sulfide, benzyl Methyl sulfide, benzyl ethyl sulfide, benzyl isoamyl sulfide, benzyl chloromethyl sulfide, benzyl cyclohexyl sulfide, benzyl phenyl sulfide, benzyl 1-naphthyl sulfide, benzyl 2-naphthyl sulfide, butyl methyl Sulfide, butyl ethyl sulfide, secondary-part Methyl sulfide, tert-butyl methyl sulfide, butyl cyclopentyl sulfide, butyl 2-chloroethyl sulfide, cyclopentyl methyl sulfide, cyclohexyl ethyl sulfide, cyclohexyl vinyl sulfide, tert-amyl methyl sulfide Feed, secondary-butyl ethyl sulfide, tert-butyl ethyl sulfide, tert-amyl ethyl sulfide, cyclododecyl methyl sulfide, bis (2-cyclopenten-l-yl) sulfide, 1-methyl Thio-1,3-cyclohexadiene, 1-methylthio-1,4-cyclohexadiene, chloromethyl methyl sulfide, chloromethyl ethyl sulfide, bis (2-tolyl) sulfide, trimethylsilylmethyl methyl sulfide , Trimethylene sulfide, thiophene, 2,3-dihydrothiophene, 2,5-dihydrothiophene, tetrahydrothiophene, 2-methyltetrahydrothiophene, 2,5-dimethyltetrahydrothiophene, 4,5-dihydro-2-methylthiophene, 2-methylthiophene, 2,5-dimethylthiophene, 3-bromothiophene, 2,3-benzo Offen, 2-methylbenzothiophene, dibenzothiophene, isobenzothiophene, 1,1-bis (methylthio) ethane, 1,1,1-tris (methylthio) ethane, 1,1,2-tris (Methylthio) ethane, 1,1-bis (methylthio) propane, 1,2-bis (methylthio) propane, 2,2-bis (methylthio) propane, 1,3-bis (methylthio) propane, 1,1,3-tris (methylthio) propane, 1,4-bis (methylthio) butane, 1,2-bis (methylthio) benzene, 1,3-bis (methylthio) benzene, 1,4- Bis (methylthio) benzene, ethylene glycol dimethyl sulfide, ethylene glycol diethyl sulfide, ethylene glycol divinyl sulfide, ethylene glycol diphenyl sulfide, ethylene glycol tert-butyl methyl sulfide, ethylene glycol tert-butyl Ethyl sulfide, 2,5-bis (methylthio) thiophene, 2-methylthiothiophene, 3-methylthiothiophene, 2-methylthiotetrahydropyran, 3-methylthiotetrahydropyran, 1,3- Dithiolane, 2-methyl-1,3-dithiolane, 2,2-dimethyl-1,3-dithiol , 2-ethyl-2-methyl-1,3-dithiolane, 2,2-tetramethylene-1,3-dithiolane, 2,2-pentamethylene-1,3-dithiolane, 2-vinyl-1, 3-dithiolane, 2-chloromethyl-1,3-dithiolane, 2-methylthio-1,3-dithiolane, 1,3-dithiane, 1,4-dithiane, 4-methyl-1,3 -Dithiane, 1,3,5-trithione, 2- (2-ethylhexyl) -1,3-bis (methylthio) propane, 2-isopropyl-1,3-bis (methylthio) propane, 2 -Butyl-1,3-bis (methylthio) propane, 2-tert-butyl-1,3-bis (methylthio) propane, 2-3-butyl-1,3-bis (methylthio) propane, 2-cyclohexyl-1,3-bis (methylthio) propane, 2-phenyl-1,3-bis (methylthio) propane, 2-cumyl-1,3-bis (methylthio) propane, 2- (2 -Phenylethyl) -1,3-bis (methylthio) propane, 2- (2-cyclohexylethyl) -1,3-bis (methylthio) propane, 2- (p-chlorophenyl) -1,3- Bis (methylthio) propane, 2- (p-fluorophenyl) -1,3-bis (methylthio) propane, 2- (diphenylmethyl) -1,3-bis (methylthio) propane, 2,2 Dicyclohexyl-1 , 3-bis (methylthio) propane, 2,2-diethyl-1,3-bis (methylthio) propane, 2,2-dipropyl-1,3-bis (methylthio) propane, 2,2- Diisopropyl-1,3-bis (methylthio) propane, 2,2-dibutyl-1,3-bis (methylthio) propane, 2,2-diisobutyl-1,3-bis (methylthio) Propane, 2-methyl-2-ethyl-1,3-bis (methylthio) propane, 2-methyl-2-propyl-1,3-bis (methylthio) propane, 2-methyl-2-butyl-1, 3-bis (methylthio) propane, 2-methyl-2-benzyl-1,3-bis (methylthio) propane, 2-methyl-2-methylcyclohexyl-1,3-bis (methylthio) propane, 2 -Isopropyl-2-isopentyl-1,3-bis (methylthio) propane, 2,2-bis (2-cyclohexylmethyl) -1,3-bis (methylthio) propane and the like.
[64] Examples of amines useful as internal electron donors include methylamine, ethylamine, propylamine, isopropylamine, butylamine, isobutylamine, amylamine, isoamylamine, octylamine, cyclohexylamine, aniline, dimethylamine, diethyl Amine, dipropylamine, diisopropylamine, dibutylamine, diisobutylamine, diamylamine, diisoamamine, dioctylamine, dicyclohexylamine, trimethylamine, triethylamine, tripropylamine, tri Isopropylamine, tributylamine, triisobutylamine, triamylamine, triisoamylamine, trioctylamine, tricyclohexylamine, N-methylaniline, N-ethylaniline, N-propylaniline, N-isopropyl Aniline, N-butylaniline, N-isobutylaniline, N-amylaniline, N-isoamaniline, N-octylaniline, N-cyclohexylaniline, N, N-dimethylaniline, N, N-diethylaniline, N, N-dipropylaniline, N, N-diiso Propylaniline, N, N-dibutylaniline, N, N-diisobutylaniline, N, N-diamylaniline, N, N-diisoamaniline, N, N-dioctylaniline, N, N-di Cyclohexylaniline, azetidine, 1-methylazetidine, 1-ethylazetidine, 1-propylazetidine, 1-isopropylazetidine, 1-butylazetidine, 1-isobutylazetidine, 1-amylazetidine , 1-isoamylazetidine, pyrrolidine, 1-methylpyrrolidine, 1-ethylpyrrolidine, 1-propylpyrrolidine, 1-isopropylpyrrolidine, 1-butylpyrrolidine, 1- Isobutylpyrrolidine, 1-amylpyrrolidine, 1-isoamylpyrrolidine, 1-octylpyrrolidine, 1-cyclohexylpyrrolidine, 1-phenylpyrrolidine, piperidine, 1-methyl Piperidine, 1-ethylpiperidine, 1-propylpiperidine, 1-isopropylpiperidine, 1-butylpiperidine, 1-isobutylpiperidine, 1-amylpiperidine, 1- Isoamylpiperidine, 1-octylpiperidine, 1-cyclohexylpiperidine, 1-phenylpiperidine, piperazine, 1-methylpiperazine, 1-ethylpiperazine, 1-propylpiperazine, 1-isopropyl piperazine, 1-butylpiperazine, 1-isobutylpiperazine, 1-amylpiperazine, 1-isoamylpiperazine , 1-octylpiperazine, 1-cyclohexylpiperazine, 1-phenylpiperazine, 1,4-dimethylpiperazine, 1,4-diethylpiperazine, 1,4-dipropylpiperazine, 1,4 -Diisopropylpiperazine, 1,4-dibutylpiperazine, 1,4-diisobutylpiperazine, 1,4-diamilpiperazine, 1,4-diisoamylpiperazine, 1,4-di Octylpiperazine, 1,4-dicyclohexylpiperazine, 1,4-diphenylpiperazine, and the like.
[65] Examples of esters useful as internal electron donors include methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, butyl acetate, isopropyl acetate, isobutyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, ethyl valeric Latex, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl pivalate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, isobutyl benzoate, isopropyl benzoate, Octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl 2-methylbenzoate, ethyl 2-methylbenzoate, propyl 2-methylbenzoate, isopropyl 2-methylbenzoate, butyl 2-methyl Benzoate, isobutyl 2-meth Tylbenzoate, octyl 2-methylbenzoate, cyclohexyl 2-methylbenzoate, phenyl 2-methylbenzoate, benzyl 2-methylbenzoate, methyl 3-methylbenzoate, ethyl 3-methylbenzoate, propyl 3- Methylbenzoate, isopropyl 3-methylbenzoate, butyl 3-methylbenzoate, isobutyl 3-methylbenzoate, octyl 3-methylbenzoate, cyclohexyl 3-methylbenzoate, phenyl 3-methylbenzoate, benzyl 3-methylbenzoate, methyl 4-methylbenzoate, ethyl 4-methylbenzoate, propyl 4-methylbenzoate, isopropyl 4-methylbenzoate, butyl 4-methylbenzoate, isobutyl 4-methylbenzoate, Octyl 4-methylbenzoate, cyclohexyl 4-methylbenzoate, phenyl 4-methylbenzoate, benzyl 4-methylbenzoate, methyl o-chlorobenzoate, ethyl o-chlorobenzoate, propyl o-chlorobenzoate, Isopropyl o-chlorobene Et, butyl o-chlorobenzoate, isobutyl o-chlorobenzoate, amyl o-chlorobenzoate, isoamyl o-chlorobenzoate, octyl o-chlorobenzoate, cyclohexyl o-chlorobenzoate, phenyl o- Chlorobenzoate, benzyl o-chlorobenzoate, methyl m-chlorobenzoate, ethyl m-chlorobenzoate, propyl m-chlorobenzoate, isopropyl m-chlorobenzoate, butyl m-chlorobenzoate, isobutyl m -Chlorobenzoate, amyl m-chlorobenzoate, isoamyl m-chlorobenzoate, octyl m-chlorobenzoate, cyclohexyl m-chlorobenzoate, phenyl m-chlorobenzoate, benzyl m-chlorobenzoate, methyl p-chlorobenzoate, ethyl p-chlorobenzoate, propyl p-chlorobenzoate, isopropyl p-chlorobenzoate, butyl p-chlorobenzoate, isobutyl p-chlorobenzoate, Amyl p-chlorobenzoate, isoamyl p-chlorobenzoate, octyl p-chlorobenzoate, cyclohexyl p-chlorobenzoate, phenyl p-chlorobenzoate, benzyl p-chlorobenzoate, dimethyl maleate, dimethyl phthalate , Diethyl phthalate, dipropyl phthalate, dibutyl phthalate, diisobutyl phthalate, methyl ethyl phthalate, methyl propyl phthalate, methyl butyl phthalate, methyl isobutyl phthalate, ethyl propyl phthalate, ethyl butyl phthalate, ethyl isobutyl phthalate, propyl butyl Phthalate, propyl isobutyl phthalate, dimethyl terephthalate, diethyl terephthalate, dipropyl terephthalate, dibutyl terephthalate, diisobutyl terephthalate, methyl ethyl terephthalate, methyl propyl terephthalate, methyl butyl terephthalate, methyl Isobutyl terephthalate, ethyl propyl terephthalate, ethyl butyl terephthalate, ethyl isobutyl terephthalate, propyl butyl terephthalate, propyl isobutyl terephthalate, dimethyl isophthalate, diethyl isophthalate, dipropyl isophthalate, dibutyl isophthalate , Diisobutyl isophthalate, methyl ethyl isophthalate, methyl propyl isophthalate, methyl butyl isophthalate, methyl isobutyl isophthalate, ethyl propyl isophthalate, ethyl butyl isophthalate, ethyl isobutyl isophthalate, propyl butyl isophthalate, propyl Isobutyl isophthalate and the like.
[66] Examples of thioesters useful as internal electron donors include methyl thiol acetate, ethyl thiol acetate, propyl thiol acetate, isopropyl thiol acetate, butyl thiol acetate, isobutyl thiol acetate, amyl thiol acetate, isoamyl thiol acetate, octyl thiol acetate, cyclocyclo Hexyl thiol acetate, phenyl thiol acetate, 2-chloroethyl thiol acetate, 3-chloropropyl thiol acetate, methyl thiobenzoate, ethyl thiobenzoate, propyl thiobenzoate, isopropyl thiobenzoate, butyl thiobenzoate, isobutyl Thiobenzoate, amyl thiobenzoate, isoamyl thiobenzoate, octyl thiobenzoate, cyclohexyl thiobenzoate, phenyl thiobenzoate, 2-chloroethyl thiobenzoate, 3-chloropropyl thiobenzoate and the like. .
[67] Examples of amides useful as internal electron donors include formamide, acetamide, propionamide, isobutyramide, trimethylacetamide, hexanoamide, octadecanamide, cyclohexanecarboxamide, 1-adamatanecarboxamide, acrylamide, Methacrylamide, 2-fluoroacetamide, 2-chloroacetamide, 2-bromoacetamide, 2,2-dichloroacetamide, 2,2-trifluoroacetamide, 2,2,2-trichloro Acetamide, 2-chloropropionamide, benzamide, N-methylformamide, N-ethylformamide, N-propylformamide, N-butylformamide, N-isobutylformamide, N-amylformamide, N -Cyclohexylformamide, formanilide, N-methylacetamide, N-ethylacetamide, N-propylacetamide, N-butylacetamide, N-isobutylacetamide, N-amylacetamide, N- Cyclohexyl acetamide, acetanilide, N-methylpropionamide, N-ethylpropionamide, N-propylpionamide, N-butylpropionamide, N-isobutylpropionamide, N-amylpropionamide, N-cyclohexylpropion Amide, N-phenylpropionamide, N-methylisobutyramide, N-methyltrimethylacetamide, N-methylhexanoamide, N-methyloctadecanamide, N-methylacrylamide, N-methylmethacrylamide, N -Methyl-2-fluoroacetamide, N-methyl-2-chloroacetamide, N-methyl-2-bromoacetamide, N-methyl-2,2-dichloroacetamide, N-methyl-2,2 , 2-trifluoroacetamide, N-methyl-2,2,2-trichloroacetamide, N-methyl-2-chloropropionamide, N, N-dimethylformamide, N, N-diethylformamide , N, N-diisopropylformamide, N, N-dibutylformamide, N-methylformanilide, N, N-dimeth Tylacetamide, N, N-diethylacetamide, N, N-diisopropylacetamide, N, N-dibutylacetamide, N-methylacetanilide, N, N-dimethylpropionamide, N, N- Diethylpropionamide, N, N-diisopropylpropionamide, N, N-dibutylpropionamide, N, N-dimethylisobutyramide, N, N-dimethyltrimethylacetamide, N, N-dimethylhexanoamide , N, N-dimethyloctadecanamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N, N-dimethyl-2-fluoroacetamide, N, N-dimethyl-2-chloroacet Amide, N, N-dimethyl-2-bromoacetamide, N, N-dimethyl-2,2-dichloroacetamide, N, N-dimethyl-2,2,2-trifluoroacetamide, N, N -Diethyl-2,2,2-trifluoroacetamide, N, N-diisopropyl-2,2,2-trichloroacetamide, N, N-dibutyl-2,2,2-trifluoro Loacetamide, N, N-dimethyl-2,2,2-trichloro Acetamide, N, N-diethyl-2,2,2-trichloroacetamide, N, N-diisopropyl-2,2,2-trichloroacetamide, N, N-dibutyl-2,2 , 2-trichloroacetamide, N, N-dimethyl-2-chloropropionamide, 1-acetylazetidine, 1-acetylpyrrolidine, 1-acetylpiperidine, 1-acetylpiperazine, 1-acetylpipepe Lazine, 1,4-diacetylpiperazine and the like.
[68] Examples of anhydrides useful as internal electron donors include acetic anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride, valeric anhydride, trimethylacetic anhydride, hexanoic anhydride, heptanoic anhydride, decanoic anhydride, lauric anhydride, myristic acid Anhydride, palmitic anhydride, stearic anhydride, docosanone anhydride, crotonic anhydride, methacrylic anhydride, oleic anhydride, linoleic anhydride, chloroacetic anhydride, iodiacetic anhydride, dichloroacetic anhydride, trifluoroacetic anhydride, chlorodiacetic anhydride Fluoroacetic anhydride, trichloroacetic anhydride, pentafluoropropionic anhydride, heptafluorobutyric anhydride, succinic anhydride, methyl succinic anhydride, 2,2-dimethylsuccinic anhydride, itaconic anhydride, maleic anhydride, glutaric anhydride, Digly Cholic anhydride, benzoic anhydride, phenylsuccinic anhydride, phenylmaleic anhydride, homophthalic anhydride, isotonic anhydride, phthalic anhydride, tetrafluorophthalic anhydride, tetrabromophthalic anhydride and the like.
[69] Examples of acid halides useful as internal electron donors include acetyl chloride, acetyl bromide, chloroacetyl chloride, dichloroacetyl chloride, trichloroacetyl chloride, trifluoroacetyl chloride, tribromoacetyl chloride, propionyl chloride, propionyl bromide, buty Reyl chloride, isobutyryl chloride, trimethylacetyl chloride, 3-cyclopentylpropionyl chloride, 2-chloropropionyl chloride, 3-chloropropionyl chloride, tert-butylacetyl chloride, isovaleryl chloride, hexanoyl chloride, Heptanoyl chloride, decanoyl chloride, lauroyl chloride, myristoyl chloride, palmitoyl chloride, stearoyl chloride, oreoyl chloride, cyclopentanecarbonyl chloride, jade Reyl chloride, malonyl dichloride, succinyl chloride glutaryl dichloride, adipoyl chloride, pimeilyl chloride, subboroyl chloride, azeolayl chloride, sebacoyl chloride, dodecanediol dichloride, methoxyacetyl chloride, ace Oxyacetyl chloride and the like.
[70] Examples of aldehydes useful as internal electron donors include formaldehyde, acetalaldehyde, propionaldehyde, isobutyraldehyde, trimethylacetaldehyde, butyraldehyde, 2-methylbutyraldehyde, valeraldehyde, isovaleraldehyde, hexanal, 2-ethyl Hexanal, heptaldehyde, decyl aldehyde, crotonaldehyde, acrolein, methacrolein, 2-ethylcrolein, chloroacetaldehyde, iodine acetaldehyde, dichloroacetaldehyde, trifluoroacetaldehyde, chlorodifluoroacetaldehyde Aldehydes, pentafluoropropionaldehyde, heptafluorobutyraldehyde, phenylacetaldehyde, benzaldehyde, o-tolualdehyde, m-tolualdehyde, p-tolualdehyde, trans-cinnaaldehyde, Trans-2-nitrocinnamaldehyde, 2-bromobenzaldehyde, 2-chlorobenzaldehyde, 3-chlorobenzaldehyde, 4-chlorobenzaldehyde and the like.
[71] Examples of ketones useful as internal electron donors include acetone, 2-butanone, 3-methyl-2-butanone, pinacolon, 2-petanone, 3-pentanone, 3-methyl-2-pentanone, 4-methyl 2-pentanone, 2-methyl-3-pentanone, 4,4-dimethyl-2-pentanone, 2,4-dimethyl-3-pentanone, 2,2,4,4-tetramethyl-3- Pentanone, 2-hexanone, 3-hexanone, 5-methyl-2-hexanone, 2-methyl-3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-methyl- 3-heptanone, 5-methyl-3-heptanone, 2,6-dimethyl-4-heptanone, 2-octanone, 3-octanone, 4-octanone, acetophenone, benzophenone, mesityl oxide, Hexafluoroacetone, perfluoro-2-butanone, 1,1,1-trichloroacetone and the like.
[72] Examples of alcohols useful as internal electron donors include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, hexanol, heptanol, octanol, dodecanol, octadecyl alcohol, 2-ethylhexyl alcohol, benzyl alcohol, cumyl alcohol, Oleyl alcohol, diphenyl methanol, triphenyl methanol, phenol, cresol, ethylphenol, propylphenol, cumylphenol, naphthol, cyclopentanol, cyclohexanol and the like.
[73] Examples of nitriles useful as internal electron donors include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, valeronitrile, isovaleronitrile, trimethylacetonitrile, hexanenitrile, heptanenitrile, heptyl cyanide, octyl cyanide Amide, undecanenitrile, malononitrile, succinonitrile, glutaronitrile, adiponitrile, sebaconitrile, allyl cyanide, acrylonitrile, crotononitrile, methacrylonitrile, fumaronitrile, tetracyano Ethylene, cyclopentanecarbonitrile, cyclohexanecarbonitrile, dichloroacetonitrile, fluoroacetonitrile, trichloroacetonitrile, benzonitrile, benzyl cyanide, 2-methylbenzyl cyanide, 2-chlorobenzonitrile, 3-chlorobenzo Nitrile, 4-chlorobenzonitrile, o-tolunitrile, m-tolunitrile, p-tolunitrile and the like.
[74] Examples of phosphines useful as internal electron donors include trimethylphosphine, triethylphosphine, trimethyl phosphite, triethyl phosphite, hexamethylphosphorus triamide, hexamethylphosphoramide, tripiperidinophosphine oxide, triphenyl Phosphine, tri-p-tolylphosphine, tri-m-tolylphosphine, tri-o-tolylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, isopropyldiphenylphosphine, allyldiphenylphosphine Pin, cyclohexyldiphenylphosphine, benzyldiphenylphosphine, di-tert-butyl dimethylphosphoramide, di-tert-butyl diethylphosphoramidite, di-tert-butyl diisopropylphosphor Amidite, diallyl diisopropylphosphoramidite, and the like.
[75] Examples of silanes useful as internal electron donors include tetramethyl orthosilicate, tetraethyl orthosilicate, tetrapropyl orthosilicate, tetrabutyl orthosilicate, trichloromethoxysilane, trichloroethoxysilane, trichloropropoxysilane, trichloroisopro Foxysilane, Trichlorobutoxysilane, Trichloroisobutoxysilane, Dichlorodimethoxysilane, Dichlorodiethoxysilane, Dichlorodipropoxysilane, Dichlorodiisoprooxysilane, Dichlorodibutoxysilane, Dichlorodiisobutoxysilane, Chloro Trimethoxysilane, chlorotriethoxysilane, chlorotripropoxysilane, chlorotriisopropoxysilane, chlorotributoxysilane, chlorotriisobutoxysilane, dimethylmethoxysilane, diethylmethoxysilane, dipropylmethoxy Methoxysilane, diisopropylmethoxysilane, dibutylmethoxysilane , Diisobutylmethoxysilane, dipentylmethoxysilane, dicyclopentylmethoxysilane, dihexylmethoxysilane, dicyclohexylmethoxysilane, diphenylmethoxysilane, dimethylethoxysilane, diethylethoxysilane, di Propylethoxysilane, diisopropylethoxysilane, dibutylethoxysilane, diisobutylethoxysilane, dipentylethoxysilane, dicyclopentylethoxysilane, dihexylethoxysilane, dicyclohexylethoxysilane Diphenylethoxysilane, trimethylmethoxysilane, triethylmethoxysilane, tripropylmethoxysilane, triisopropylmethoxysilane, tributylmethoxysilane, triisobutylmethoxysilane, tripentylmethoxysilane, Tricyclopentylmethoxysilane, trihexylmethoxysilane, tricyclohexylmethoxysilane, triphenylmethoxysilane, trimethylethoxysilane, triethylethoxysilane, tripropylethoxysilane, triisopropylethoxysil Column, tributylethoxysilane, triisobutylethoxysilane, tripentylethoxysilane, tricyclopentylethoxysilane, trihexylethoxysilane, tricyclohexylethoxysilane, triphenylethoxysilane, dimethyldimethoxy Silane, diethyldimethoxysilane, dipropyldimethoxysilane, diisopropyldimethoxysilane, dibutyldimethoxysilane, diisobutyldimethoxysilane, dipentyldimethoxysilane, dicyclopentyldimethoxysilane, dihexyldimeth Methoxysilane, dicyclohexyldimethoxysilane, diphenyldimethoxysilane, dimethyl diethoxysilane, diethyl diethoxysilane, dipropyl diethoxysilane, diisopropyl diethoxysilane, dibutyl diethoxysilane, diisobutyl die Methoxysilane, dipentyl diethoxysilane, dicyclopentyl diethoxysilane, dihexyl diethoxysilane, dicyclohexyl diethoxysilane, diphenyl diethoxysilane, cyclopentyl methyl dimethoxysil Cyclopentylethyldimethoxysilane, cyclopentylpropyldimethoxysilane, cyclopentylmethyldiethoxysilane, cyclopentylethyldiethoxysilane, cyclopentylpropyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane, Cyclohexylpropyldimethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyldiethoxysilane, cyclohexylpropyldiethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, vinyltrimethoxysilane, propyltrimethoxy Silane, isopropyltrimethoxysilane, butyltrimethoxysilane, isobutyltrimethoxysilane, tert-butyltrimethoxysilane, phenyltrimethoxysilane, norbornanetrimethoxysilane, methyltriethoxysilane, Ethyltriethoxysilane, vinyltriethoxysilane, propyltriethoxysilane, isopropyltriethoxysilane, butyltriethoxysil Column, isobutyltriethoxysilane, tert-butyltriethoxysilane, phenyltriethoxysilane, norbornanetriethoxysilane, 2,3-dimethyl-2- (trimethoxysilyl) butane, 2,3- Dimethyl-2- (triethoxysilyl) butane, 2,3-dimethyl-2- (tripropoxysilyl) butane, 2,3-dimethyl-2- (triisopropoxysilyl) butane, 2,3-dimethyl -2- (trimethoxysilyl) pentane, 2,3-dimethyl- (2-triethoxysilyl) pentane, 2,3-dimethyl-2- (tripropoxysilyl) pentane, 2,3-dimethyl-2 -(Triisopropoxysilyl) pentane, 2-methyl-3-ethyl-2- (trimethoxysilyl) pentane, 2-methyl-3-ethyl-2- (triethoxysilyl) pentane, 2-methyl- 3-ethyl-2- (tripropoxysilyl) pentane, 2-methyl-3-ethyl-2- (triisopropoxysilyl) pentane, 2,3,4-trimethyl-2- (trimethoxysilyl) pentane , 2,3,4-trimethyl-2- (triethoxysilyl) pentane, 2,3,4-trimethyl-2- (tripropoxysilyl) pentane, 2,3,4-trimethyl-2- (triiso Propoxysilyl) pentane, 2,3-dimethyl-2- (trimeth) Methoxysilyl) hexane, 2,3-dimethyl-2- (triethoxysilyl) hexane, 2,3-dimethyl-2- (tripropoxysilyl) hexane, 2,3-dimethyl-2- (triisopropoxy Silyl) hexane, 2,4-dimethyl-3-ethyl-2- (trimethoxysilyl) pentane, 2,4-dimethyl-3-ethyl-2- (triethoxysilyl) pentane, 2,4-dimethyl- 3-ethyl-2- (tripropoxysilyl) pentane, 2,4-dimethyl-3-ethyl-2- (triisopropoxysilyl) pentane, 2,4-dimethyl-3-isopropyl-2- (tri Methoxysilyl) pentane, 2,4-dimethyl-3-isopropyl-2- (triethoxysilyl) pentane, 2,4-dimethyl-3-isopropyl-2- (tripropoxysilyl) pentane, 2, 4-dimethyl-3-isopropyl-2- (triisopropoxysilyl) pentane, hexamethyldisiloxane, 1,1,1,3,3,3-hexamethyldisilazane and the like.
[76] Examples of carboxylic acids useful as internal electron donors include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, Eicosanoic acid, heneic acid, heptaconic acid, isobutyric acid, 2-ethylbutyric acid, trimethylacetic acid, 2-methylbutyric acid, 2,2-dimethylbutyric acid, oxalic acid, malonic acid, methylmalonic acid, ethylmalonic acid, butyl mal Lonic acid, dimethylmalonic acid, succinic acid, 2-methylsuccinic acid, 2,2-dimethylsuccinic acid, 2-ethyl-2-methylsuccinic acid, 2,3-dimethylsuccinic acid, glutaric acid, 2-methylglutaric acid, 3-methyl Glutaric acid, 2,2-dimethylglutaric acid, 2,3-dimethylglutaric acid, 3,3-dimethylglutaric acid, acrylic acid, methacrylic acid, crotonic acid, vinylacetic acid, tiglic acid, 6-heptenic acid, Citronellic Acid, Chloroacetic Acid, Dichloroacetic Acid, Trichloroacetic Acid, Fluoroacetic Acid, Diple Oroacetic acid, difluoroacetic acid, chlorodifluoroacetic acid, benzoic acid, o-toluic acid, m-toluic acid, p-toluic acid, 2-fluorobenzoic acid, 3-fluorobenzoic acid, 4-fluorobenzoic acid, 2 Ethoxybenzoic acid, 3-ethoxybenzoic acid, 4-ethoxybenzoic acid, 2-methoxybenzoic acid, 3-methoxybenzoic acid, 4-methoxybenzoic acid, 2-ethylbenzoic acid, 3-ethylbenzoic acid, 4-ethylbenzoic acid, 4-vinylbenzoic acid, 2-propylbenzoic acid, 2-isopropylbenzoic acid, 2-butylbenzoic acid, 2-isobutylbenzoic acid, 2-3-butylbenzoic acid and the like.
[77] Mixtures of two or more such compounds can be used herein as internal electron donors.
[78] The promoter added to the polymerization medium of the present invention is trimethylaluminum (TMA).
[79] When using the prepolymer form of the catalyst, the organometallic promoter compounds used to prepare the prepolymer include metals of Groups 1, 2, 11, 12, 13 and 14 of the Periodic Table of Elements described above. It may be any organometallic compound. Examples of such metals include lithium, magnesium, copper, zinc, boron, silicon and the like. However, when using prepolymers, TMA is still used as promoter in the polymerization medium.
[80] The catalyst system may include other conventional components in addition to the internal electron donor, the transition metal component, the external electron donor and the TMA promoter component as defined herein. For example, any magnesium compound, any halogen hydrocarbon (s), etc., known in the art may be added.
[81] Ziegler-Natta catalysts can be prepared by any method known in the art. This catalyst may be in the form of a solution, slurry or anhydrous free flowing powder. The amount of Ziegler-Natta catalyst used is sufficient to produce the desired amount of polyethylene.
[82] In carrying out the polymerization process of the invention, TMA is added to the polymerization medium in an amount sufficient to produce the desired polyethylene. Preferably, the TMA is introduced such that the molar ratio of the transition metal component of the TMA to the Ziegler-Natta catalyst is from about 1: 1 to about 100: 1. In a more preferred embodiment, the molar ratio of TMA to transition metal component is from about 1: 1 to about 50: 1.
[83] In carrying out the polymerization process of the invention, the external electron donor is added in any manner. For example, external electron donors can be added to the preformed catalyst, the prepolymer during the prepolymerization stage, the preformed prepolymer and / or the polymerization medium. External electron donors may optionally be premixed with the TMA promoter. The external electron donor is added in an amount sufficient to produce the desired polyethylene. It is preferred to introduce an external electron donor such that the molar ratio of the external electron donor to the transition metal component of the Ziegler-Natta catalyst is from about 0.01: 1 to about 100: 1. In a more preferred embodiment, the molar ratio of external electron donor to transition metal component is from about 0.1: 1 to about 50: 1.
[84] When carrying out the polymerization process of the invention, other conventional additives can generally be used to polymerize the olefins in the process. Specifically, any of the above-mentioned halogenated hydrocarbons, preferably chloroform can be added. The molar ratio of halogenated hydrocarbons to the transition metal component of the Ziegler-Natta catalyst is preferably from about 0.001: 1 to about 1: 1.
[85] The molecular weight of the polyethylenes produced by the present invention can be controlled in any known manner, for example using hydrogen. Control of the molecular weight can be confirmed by an increase in the melt index (I ₂ ) of the polymer as the molar ratio of hydrogen to ethylene in the polymerization medium is increased.
[86] The polyethylene of the present invention may be made into a film by any technique known in the art. For example, the films can be made by well known cast film technology, blown film technology and extrusion coating technology.
[87] In addition, polyethylene can be made into other products, such as molded articles, using well known techniques.
[88] The invention will be more readily understood by reference to the following examples. Of course, those skilled in the art will readily appreciate that there are many other forms of the invention as long as the invention is fully disclosed, and therefore the following examples are merely illustrative and are intended to limit the scope of the invention in any way. It will be understood.
[89] Polymerization method
[90] The polymerization method used in the examples was carried out in a fluidized bed reactor for gas phase polymerization, consisting of a vertical cylinder of 0.9 m diameter and 6 m height and placed on a deceleration chamber. The reactor is equipped at its bottom with an external line for the fluidization grid and recycle gas, which connects the bottom of the reactor to the top of the reduction chamber below the fluidization grid. The recycle line is equipped with heat transfer means such as a compressor for circulating gas and a heat exchanger. In particular, the lines for supplying ethylene, other olefins (e.g. 1-butene, 1-pentene and 1-hexene), hydrogen and nitrogen, the main components of the gas phase reaction mixture passing through the fluidized bed are recycle lines. Were supplied. The reactor included a fluidized bed composed of polyethylene powder consisting of particles having a weight-average diameter of about 0.5 mm to about 1.4 mm on the fluidization grid. The gas phase reaction mixture comprising ethylene, olefin comonomer, hydrogen, nitrogen and small amounts of other components was passed through the fluidized bed at an elevated fluidization rate ranging from about 1.8 feet to about 2.0 feet per second under a pressure of about 290 psig to about 300 psig. .
[91] In addition, in each of the examples below, a Ziegler-Natta catalyst comprising an internal electron donor was intermittently introduced into the reactor. The catalyst included magnesium, chlorine, titanium and internal electron donors. The rate at which the catalyst was introduced into the reactor was adjusted for each particular set of conditions to obtain the desired rate of production. During the polymerization, trimethylaluminum (TMA) solution in n-hexane was continuously introduced into the gas phase reaction mixture recycle line disposed in the lower part of the heat transfer means. The TMA feed rate is expressed as the molar ratio of TMA to titanium (TMA / Ti) and is defined as the ratio of the TMA feed rate (moles of TMA per hour) to the catalyst feed rate (moles of titanium per hour). At the same time, a solution of chloroform (CHCl ₃ ) in n-hexane at a concentration of about 0.5% by weight was continuously introduced into the gas phase reaction mixture recycle line. The CHCl ₃ feed rate is expressed as the molar ratio of CHCl ₃ to titanium (CHCl ₃ / Ti) and is defined as the ratio of CHCl ₃ feed rate (moles of CHCl ₃ per hour) to catalyst feed rate (moles of titanium per hour).
[92] The feed rate of an external electron donor (eED) is expressed as the mole ratio of eED to titanium (eED / Ti), and is the ratio of the eED feed rate (eED moles per hour) to catalyst feed rate (moles of titanium per hour) Is defined.
[93] The productivity (manufacturability) of the catalyst is the ratio of pounds of polyethylene produced per pound of catalyst to be added to the reactor. The activity of the catalyst is expressed in grams of polyethylene per millimolar of titanium per ethylene pressure bar.
[94] Example 1
[95] Preparation of Linear Low Density Polyethylene (LLDPE) Using TMA as Cocatalyst, THF as External Electron Donor, and Ziegler-Natta Catalysts Containing THF as Internal Electron Donor
[96] A Ziegler-Natta type catalyst comprising magnesium, titanium, chlorine and THF (tetrahydrofuran) as internal electron donor was added to the polymerization medium described above comprising ethylene, 1-hexene, hydrogen and nitrogen. TMA was added in an amount sufficient to activate the Ziegler-Natta catalyst. THF was added to the polymerization as an external electron donor. Linear polyethylene was obtained.
[97] Example 2
[98] Preparation of LLDPE Using TMA as Cocatalyst, Dibutyl Ether as External Electron Donor, and Ziegler-Natta Catalysts Containing Dibutylphthalate as Internal Electron Donor
[99] The method of Example 1 was followed except that dibutyl ether was added as the external electron donor and the Ziegler-Natta catalyst included dibutylphthalate as the internal electron donor. Linear polyethylene was obtained.
[100] Example 3
[101] Preparation of LLDPE Using TMA as Cocatalyst, Methyl Phenyl Ether as External Electron Donor, and Ziegler-Natta Catalysts Containing Tetraethylorthosilicate as Internal Electron Donor
[102] The method of Example 1 was followed except that methyl phenyl ether was added as the external electron donor and the Ziegler-Natta catalyst included tetraethylorthosilicate as the internal electron donor. Linear polyethylene was obtained.
[103] Example 4
[104] Preparation of LLDPE Using TMA as Cocatalyst, 1,3-dimethoxypropane as External Electron Donor, and Ziegler-Natta Catalysts Containing Ethanol as Internal Electron Donor
[105] The method of Example 1 was followed except that 1,3-dimethoxypropane was added as the external electron donor and the Ziegler-Natta catalyst included ethanol as the internal electron donor. Linear polyethylene was obtained.
[106] Example 5
[107] Preparation of LLDPE Using Ziegler-Natta Catalysts Using TMA as Cocatalyst, THF as External Electron Donor, and N, N-dimethylformamide as Internal Electron Donor
[108] The method of Example 1 was followed except that the Ziegler-Natta catalyst included N, N-dimethylformamide as internal electron donor. Linear polyethylene was obtained.
[109] Example 6
[110] Preparation of LLDPE Using TMA as Cocatalyst, Tert-Butyl Methyl Ether as External Electron Donor, and Ziegler-Natta Catalysts Containing Hexamethylphosphorus Triamide as Internal Electron Donor
[111] The method of Example 1 was followed except that tert-butyl methyl ether was added as the external electron donor and the Ziegler-Natta catalyst included hexamethylphosphorus triamide as the internal electron donor. Linear polyethylene was obtained.
[112] Example 7
[113] Preparation of LLDPE Using TMA as Cocatalyst, Tert-Butyl Methyl Ether as External Electron Donor, and Ziegler-Natta Catalysts Containing N, N-diisopropylaniline as Internal Electron Donor
[114] The method of Example 1 was followed except that tert-butyl methyl ether was added as the external electron donor and the Ziegler-Natta catalyst included N, N-diisopropylaniline as the internal electron donor. Linear polyethylene was obtained.
[115] Example 8
[116] Preparation of LLDPE Using TMA as Cocatalyst, Diethyl Ether as External Electron Donor, and Ziegler-Natta Catalyst Containing Trifluoroacetaldehyde as Internal Electron Donor
[117] The method of Example 1 was followed except that diethyl ether was added as the external electron donor and the Ziegler-Natta catalyst included trifluoroacetaldehyde as the internal electron donor. Linear polyethylene was obtained.
[118] Example 9
[119] Preparation of LLDPE Using TMA as Cocatalyst, Diisopropyl Ether as External Electron Donor, Ziegler-Natta Catalysts Containing Pinacolone as Internal Electron Donor
[120] The method of Example 1 was followed except that diisopropyl ether was added as the external electron donor and the Ziegler-Natta catalyst included pinacolon as the internal electron donor. Linear polyethylene was obtained.
[121] Example 10
[122] Preparation of LLDPE Using TMA as Cocatalyst, THF as External Electron Donor, and Ziegler-Natta Catalysts Containing Acetonitrile as Internal Electron Donor
[123] The method of Example 1 was followed except that THF was added as the external electron donor and the Ziegler-Natta catalyst included acetonitrile as the internal electron donor. Linear polyethylene was obtained.
[124] Films made of the polyethylene of the present invention can be readily prepared by any method known for producing films.
[125] Articles such as shaped articles can also be made from the polyethylene of the present invention.
[126] It should be clearly understood that the embodiments of the invention disclosed herein are illustrative only and are not intended to limit the scope of the invention. The invention includes all modifications within the scope of the following claims.

权利要求:
Claims (27)
[1" claim-type="Currently amended] Under polymerization conditions, a Ziegler-Natta type catalyst comprising ethylene and / or ethylene and one or more other olefin (s) comprising one or more internal electron donors, wherein the internal electron donor is an internal electron donor to a Ziegler-Natta One or more selected from the group consisting of trimethylaluminum and a compound represented by the following Chemical Formula 1, Chemical Formula 2, Chemical Formula 3 and Chemical Formula 4, wherein the molar ratio of the transition metal compound of the catalyst is 1: 1 to about 1000: 1. Process for the polymerization of ethylene and / or ethylene and one or more other olefin (s) comprising contacting at least one external electron donor compound comprising a carbon-oxygen-carbon bond (COC):
Formula 1
R ¹ -CH ₂ -O-CH ₂ -R ²
Formula 2

Formula 3
R ⁵ -OR ⁶
Formula 4
R ⁷ -O (-R ⁸ -O) _n -R ⁹
Where
n is 1 to 30;
R^OneAnd R²Is Independently saturated, containing from 1 to 30 carbon atoms and containing from 0 to 30 heteroatoms consisting of an element selected from Groups 13, 14, 15, 16 and 17 of the Periodic Table of the Elements or mixtures thereof 0-30 heteroatoms containing aliphatic or unsaturated aliphatic groups and from 1 to 30 carbon atoms and consisting of elements selected from Groups 13, 14, 15, 16 and 17 of the Periodic Table of the Elements or mixtures thereof It is selected from the group consisting of a substituted or unsubstituted aromatic group containing;
R ³ and R ⁴ are connected to each other to form part of a cyclic or polycyclic structure, contain 1 to 30 carbon atoms, and an element selected from Groups 13, 14, 15, 16, and 17 of the Periodic Table of the Elements Or a saturated or unsaturated aliphatic group containing 0 to 30 heteroatoms consisting of a mixture thereof, and containing 1 to 30 carbon atoms, and containing groups 13, 14, 15, 16, and 17 of the periodic table of elements. Hydrocarbons independently selected from the group consisting of substituted or unsubstituted aromatic groups containing 0 to 30 heteroatoms consisting of an element selected from the group or a mixture thereof;
R ⁵ contains 1 to 30 carbon atoms and is substituted or contains 0 to 30 heteroatoms consisting of an element selected from Groups 13, 14, 15, 16 and 17 of the Periodic Table of the Elements or mixtures thereof Unsubstituted aromatic groups;
R ⁶ , R ⁷ , R ⁸ and R ⁹ independently contain 1 to 30 carbon atoms and consist of an element selected from Groups 13, 14, 15, 16 and 17 of the Periodic Table of the Elements or mixtures thereof Saturated or unsaturated aliphatic groups containing 0 to 30 heteroatoms, and elements selected from Groups 13, 14, 15, 16, and 17 of the Periodic Table of Elements or their It is selected from the group consisting of substituted or unsubstituted aromatic groups containing 0 to 30 heteroatoms consisting of a mixture of.
[2" claim-type="Currently amended] The method of claim 1,
At least one internal electron donor is selected from the group consisting of ethers, thioethers, amines, esters, thioesters, amides, anhydrides, acid halides, aldehydes, ketones, alcohols, nitriles, phosphines, silanes and carboxylic acids.
[3" claim-type="Currently amended] The method of claim 2,
At least one internal electron donor is selected from the group consisting of ethers, esters, alcohols and silanes.
[4" claim-type="Currently amended] The method of claim 1,
At least one external electron donor compound is selected from the group consisting of tetrahydrofuran, diethyl ether, dipropyl ether, methyl propyl ether, dibutyl ether, dioctyl ether, trimethylene oxide and tetrahydropyran.
[5" claim-type="Currently amended] The method of claim 1,
Further comprising halogenated hydrocarbons.
[6" claim-type="Currently amended] The method of claim 5,
The halogenated hydrocarbon is chloroform.
[7" claim-type="Currently amended] The method of claim 1,
And wherein the Ziegler-Natta type catalyst comprises a transition metal compound which is a metal selected from metals of Groups 4, 5, 6, 7, 8, 9 and 10 of the Periodic Table of Elements as defined herein.
[8" claim-type="Currently amended] The method of claim 7, wherein
The metal of the transition metal compound is selected from the group consisting of titanium, zirconium, vanadium and chromium.
[9" claim-type="Currently amended] The method of claim 8,
The metal of the transition metal compound is titanium.
[10" claim-type="Currently amended] The method of claim 1,
The Ziegler-Natta catalyst further comprises magnesium and chlorine.
[11" claim-type="Currently amended] The method of claim 7, wherein
The Ziegler-Natta catalyst further comprises magnesium and chlorine.
[12" claim-type="Currently amended] The method of claim 5,
Adding a halogenated hydrocarbon such that the molar ratio of halogenated hydrocarbon to Ziegler-Natta catalyst is from about 0.001: 1 to about 1: 1.
[13" claim-type="Currently amended] The method of claim 1,
Trimethylaluminum is added such that the molar ratio of trimethylaluminum to Ziegler-Natta catalyst is from about 1: 1 to about 100: 1.
[14" claim-type="Currently amended] The method of claim 13,
Wherein the molar ratio of the transition metal component of the trimethylaluminum to the Ziegler-Natta type catalyst ranges from about 1: 1 to about 50: 1.
[15" claim-type="Currently amended] The method of claim 1,
A method of adding an external electron donor compound such that the molar ratio of the external electron donor compound to the transition metal component of the Ziegler-Natta catalyst is from about 0.01: 1 to about 100: 1.
[16" claim-type="Currently amended] The method of claim 15,
Wherein the molar ratio of the external electron donor compound to the transition metal component of the Ziegler-Natta type catalyst is in the range of about 0.1: 1 to about 50: 1.
[17" claim-type="Currently amended] The method of claim 1,
The polymerization conditions are gaseous.
[18" claim-type="Currently amended] The method of claim 1,
The polymerization conditions are in solution phase.
[19" claim-type="Currently amended] The method of claim 1,
The polymerization conditions are slurry.
[20" claim-type="Currently amended] The method of claim 1,
At least one other olefin (s) is an olefin having 3 to 16 carbon atoms.
[21" claim-type="Currently amended] The method of claim 20,
At least one other olefin (s) is selected from the group consisting of 1-octene, 1-hexene, 4-methylpent-1-ene, 1-pentene, 1-butene and propylene.
[22" claim-type="Currently amended] The method of claim 1,
And wherein the copolymer prepared by polymerizing ethylene and one or more other olefin (s) comprises ethylene in an amount of at least about 70% by weight of the copolymer.
[23" claim-type="Currently amended] The method of claim 1,
And wherein the Ziegler-Natta catalyst comprises titanium, magnesium and chlorine.
[24" claim-type="Currently amended] The method of claim 23, wherein
Further comprising halogenated hydrocarbons.
[25" claim-type="Currently amended] The method of claim 23, wherein
The polymerization conditions are gaseous.
[26" claim-type="Currently amended] A film made of polyethylene prepared according to claim 1.
[27" claim-type="Currently amended] A product made of polyethylene prepared according to claim 1.

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同族专利:

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公开号 | 公开日

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CN1348472A|2002-05-08|

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CN1168748C|2004-09-29|

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DE69933139T2|2007-09-13|

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EP1159315B1|2006-09-06|

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KR100582313B1|2006-05-22|

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JP2002538244A|2002-11-12|

---

DE69933139D1|2006-10-19|

---

EP1159315A1|2001-12-05|

---

WO2000052068A1|2000-09-08|

引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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法律状态:
1999-03-03|Application filed by 해리 제이. 그윈넬, 이스트만 케미칼 캄파니

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1999-03-03|Priority to PCT/US1999/004766

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2001-12-07|Publication of KR20010108287A

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2006-05-22|Application granted

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2006-05-22|Publication of KR100582313B1

优先权:

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申请号 | 申请日 | 专利标题

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PCT/US1999/004766|WO2000052068A1|1999-03-03|1999-03-03|Process for producing polyethylene|