Process for polymerization of olefins and catalyst composition therefor

A process for the polymerization of alpha-olefins which comprises,

• polymerizing or copolymerizing one or more alpha-olefin monomers selected from the group consisting of ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene and styrene in the presence of a catalyst, said catalyst consisting essentially of:
• A. a titanium trichloride composition and
• B. an organoaluminum compound;
• said titanium trichloride composition (A) obtained by
• a. micro-pulverizing
• i. a titanium trichloride component prepared by reduction of titanium tetrachloride with hydrogen, silicon, metallic titanium or metallic aluminum,
• ii. in the presence of a complex of aluminum chloride or aluminum bromide with an electron-donor in an amount of from 0.005 to 0.5 mol per mol of said titanium trichloride component (i), said electron donor being selected from the group consisting of
• 1. an oxygen-containing organic compound selected from the group consisting of
• saturated aliphatic monoethers of 2-32 carbon atoms having an alkyl group,
• aromatic ethers of 7-16 carbon atoms having a saturated alkyl group of aryl group,
• halogenated mono- and diethers of 7-16 carbon atoms having at least one aromatic radical,
• saturated alkyl esters of saturated aliphatic monocarboxylic acids having an aliphatic monocarboxylic acid residual group of 1-21 carbon atoms and a saturated alkyl group of 1-16 carbon atoms, unsaturated alkyl esters of saturated aliphatic monocarboxylic acids having a saturated aliphatic monocarboxylic acid residual group of 1-8 carbon atoms and an unsaturated alkyl group of 2-12 carbon atoms, alkyl esters of unsaturated aliphatic monocarboxylic acids having an unsaturated aliphatic monocarboxylic acid residual group of 2-12 carbon atoms and a saturated or unsaturated alkyl group of 1-10 carbon atoms,
• saturated alkyl esters of aromatic monocarboxylic acids having an aromatic monocarboxylic acid residual group or 7-18 carbon atoms and a saturated alkyl group of 1-20 carbon atoms;
• saturated aliphatic monoketones having 3-20 carbon atoms,
• saturated aliphatic diketones having 4-12 carbon atoms, and
• aromatic monoketones having 7-18 carbon atoms;
• 2. a nitrogen-containing organic compound selected from the group consisting of
• saturated aliphatic primary amines having 1-18 carbon atoms,
• saturated aliphatic secondary amines having 2-24 carbon atoms,
• saturated aliphatic tertiary amines having 3-18 carbon atoms,
• aromatic amines having 6-20 carbon atoms, and
• heterocyclic amines having 5-18 carbon atoms;
• and
• 3. a phosphorus-containing organic compound selected from the group consisting of
• trialkyl phosphines having 3-21 carbon atoms,
• triaryl phosphines having 18-21 carbon atoms,
• trialkyl phosphites having 3-24 carbon atoms,
• triaryl phosphites having 18-24 carbon atoms, and
• hexaalkyl phosphoramides having 1-4 carbon atoms in each alkyl group;
• and
• b. extracting the micro-pulverized titanium trichloride component with an extracting medium comprising
• i. a solvent selected from the group consisting of saturated aliphatic hydrocarbons having 3-20 carbon atoms, aromatic hydrocarbons having 6-20 carbon atoms and halogenated aromatic hydrocarbons having 6-16 carbon atoms, and
• ii. an organic polar compound selected from the group consisting of
• 1. 0.005-10.0 mols per mol of the micro-pulverized titanium trichloride component (a) (i) to be extracted of an oxygen-containing organic polar compound selected from the group consisting of saturated aliphatic monoethers of 2-32 carbon atoms having an alkyl group, aliphatic ethers of 3-20 carbon atoms having an unsaturated aliphatic hydrocarbon group, aromatic ethers of 7-16 carbon atoms having a saturated alkyl group or aryl group, mono- or diethers having a halogen-substituted aromatic group of 7-16 carbon atoms, saturated alkyl esters of saturated aliphatic monocarboxylic acids having an aliphatic monocarboxylic acid residual group of 1-21 carbon atoms and a saturated alkyl group of 1-16 carbon atoms, unsaturated alkyl esters of saturated aliphatic monocarboxylic acids having a saturated aliphatic monocarboxylic acid residual group of 1-8 carbon atoms and an unsaturated alkyl group of 2-12 carbon atoms, alkyl esters of unsaturated aliphatic monocarboxylic acids having an unsaturated aliphatic monocarboxylic acid residual group having 2-12 carbon atoms and a saturated or unsaturated alkyl group of 1-10 carbon atoms, saturated alkyl esters of aromatic monocarboxylic acids having an aromatic monocarboxylic acid residual group of 7-18 carbon atoms and a saturated alkyl group of 1-20 carbon atoms, saturated aliphatic monoalcohols having 1-18 carbon atoms, monohydric and dihydric phenols having 6-16 carbon atoms, saturated aliphatic monoketones having 3-20 carbon atoms, saturated aliphatic diketones having 4-12 carbon atoms, aromatic monoketones having 7-18 carbon atoms, aromatic monocarboxylic acids having 7-18 carbon atoms, saturated aliphatic carboxylic acid halides having 2-12 carbon atoms and aromatic carboxylic acid halides having 7-15 carbon atoms;
• 2. 0.005-0.5 moles per mol of the micro-pulverized titanium trichloride component (a) (i) to be extracted of a nitrogen-containing organic polar compound selected from the group consisting of saturated aliphatic secondary amines having 2-24 carbon atoms, saturated aliphatic tertiary amines having 3-18 carbon atoms, aromatic amines having 6-20 carbon atoms, heterocyclic amines having 5-18 carbon atoms, aromatic monoisocyanates having 7-11 carbon atoms and aromatic azo compounds having 12-20 carbon atoms which may have a hydrocarbon group or halogen atom as a substituent;
• and
• 3. 0.01-15 parts by weight per part by weight of the micro-pulverized titanium trichloride component (a) (i) to be extracted of a silicon-containing organic polar compound selected from the group consisting of tetrahydrocarbylsilanes of 4-50 carbon atoms having a substituent selected from a saturated alkyl group and an aryl group, tetrahydrocarbylsilanes of 5-28 carbon atoms having an unsaturated alkyl group, alkyl hydrogenosilanes of 1-30 carbon atoms having an Si-H bond, aryl hydrogenosilanes of up to 30 carbon atoms having an Si-H bond, alkyl halogenosilanes of 3-30 carbon atoms having an Si-halogen bond, aryl halogenosilanes of 6-30 carbon atoms having an Si-halogen bond, trialkylsilyl amines of 3-18 carbon atoms, triaryl silyl amines of up to 30 carbon atoms, alkoxysilanes of 4-20 carbon atoms having an Si-O-C bond, aryloxy silanes of 6-40 carbon atoms having an Si-O-C bond, alkyl silyl esters or aryl silyl esters of aliphatic mono- or aromatic monocarboxylic acids composed of trialkyl silanols having 3-10 carbon atoms, alkylaryl silanols having 8-20 carbon atoms or triarylsilanols having 18-30 carbon atoms and aliphatic monocarboxylic acids having 1-10 carbon atoms or aromatic monocarboxylic acids having 7-11 carbon atoms, trialkyl silicon isocyanates having 3-10 carbon atoms, dialkyl aryl silicon isocyanates having 8-15 carbon atoms, triaryl silicon isocyanates having 18-30 carbon atoms, polysilmethylenes of the formula CH.sub.3 SiCH.sub.2 [(CH.sub.3).sub.2 SiCH.sub.2 ].sub.x Si(CH.sub.3).sub.3 wherein x is an integer of 1-10, linear polyalkyl polysilanes having 6-80 carbon atoms, polyaryl polysilanes of up to 80 carbon atoms, polyalkyl cyclopolysilanes having 12-120 carbon atoms, organopolysiloxanes of the formula R(R'R"SiO).sub.x SiR.sub.3, wherein R, R' and R" which may be the same or different, represent an alkyl group having 1-4 carbon atoms, an aryl group having 6-8 carbon atoms, with the proviso that R" can also be hydrogen, and x is an integer of 1-1000;
• .alpha.,.omega.-dihaloalkylpolysiloxanes of the formula X(R.sub.2 SiO).sub.x SiR.sub.2 X, wherein R and x are as defined above, and X is a halogen atom;
• alkyl cyclopolysiloxanes of the formula (R"HSiO).sub.y, wherein R"is an alkyl group having 1-4 carbon atoms, and y is an integer of 3-8, alkyl cyclopolysiloxanes of the general formula (R"".sub.2 SiO).sub.z, wherein R"" is an alkyl group having 1-4 carbon atoms and z is an integer of 3-9, aryl cyclopolysiloxanes of the formula (Q.sub.2 SiO).sub.p, wherein Q is an aryl group having 6-8 carbon atoms and p is an integer of 3-6, alkyl polysilazanes of 6-50 carbon atoms having an Si-N-Si bond and a molecular weight of not more than 1000, and aryl polysilazanes of 6-50 carbon atoms having an Si-N-Si bond and a molecular weight of not more than 1000.

A catalyst composition consisting essentially of

• A. a titanium trichloride composition and
• B. an organoaluminum compound;
• said titanium trichloride composition (A) obtained by
• a. micro-pulverizing
• i. a titanium trichloride component prepared by reduction of titanium tetrachloride with hydrgen, silicon, metallic titanium or metallic aluminum,
• ii. in the presence of a complex of aluminum chloride or aluminum bromide with an electron-donor in an amount of from 0.005 to 0.5 mol per mol of said titanium trichloride component (i) said electron-donor being selected from the group consisting of
• 1. an oxygen-containing organic compound selected from the group consisting of
• saturated aliphatic monoethers of 2-32 carbon atoms having an alkyl group,
• aromatic ethers of 7-16 carbon atoms having a saturated alkyl group or aryl group,
• halogenated mono- and diethers of 7-16 carbon atoms having at least one aromatic radical
• saturated alkyl esters of saturated aliphatic monocarboxylic acids having an aliphatic monocarboxylic acid residual group of 1-21 carbon atoms and a saturated alkyl group of 1-16 carbon atoms,
• unsaturated alkyl esters of saturated aliphatic monocarboxylic acids having a saturated aliphatic monocarboxylic acid residual group of 1-8 carbon atoms and an unsaturated alkyl group of 2-12 carbon atoms;
• alkyl esters of unsaturated aliphatic monocarboxylic acids having an unsaturated aliphatic monocarboxylic acid residual group of 2-12 carbon atoms and a saturated or unsaturated alkyl group of 1-10 carbon atoms,
• saturated alkyl esters of aromatic monocarboxylic acids having an aromatic monocarboxylic acid residual group of 7-18 carbon atoms and a saturated alkyl group of 1-20 carbon atoms, saturated aliphatic monoketones having 3-20 carbon atoms,
• saturated aliphatic diketones having 4-12 carbon atoms, and
• aromatic monoketone having 7-18 carbon atoms;
• 2. a nitrogen-containing organic compound selected from the group consisting of
• saturated aliphatic primary amines having 1-18 carbon atoms,
• saturated aliphatic secondary amines having 2-24 carbon atoms,
• saturated aliphatic tertiary amines having 3-18 carbon atoms,
• aromatic amines having 6-20 carbon atoms, and heterocyclic amines having 5-18 carbon atoms;
• and
• 3. a phosphorus-containing organic compound selected from the group consisting of
• trialkyl phosphines having 3-21 carbon atoms,
• triaryl phosphines having 18-21 carbon atoms,
• trialkyl phosphites having 3-24 carbon atoms,
• triaryl phosphites having 18-.gtoreq.carbon atoms, and
• hexaalkyl phosphoramides having 1-4 carbon atoms in each alkyl group;
• iii. and in the copresence of a polysiloxane, and
• b. extracting the micro-pulverized titanium trichloride component with a solvent selected from the group consisting of saturated aliphatic hydrocarbons, aromatic hydrocarbons and halogenated aromatic hydrocarbons.

A catalyst composition consisting essentially of:

• A. a titanium trichloride composition and
• B. an organoluminum compound;
• said titanium trichloride composition (A) obtained by
• a. micro-pulverizing
• i. a titanium tichloride component prepared by reduction of titanium tetrachloride with hydrogen, silicon, metallic titanium or metallic aluminum,
• ii. in the presence of a complex of aluminum chloride or aluminum bromide with an electron-donor in an amount of from 0.005 to 0.5 mol per mol of said titanium trichloride component (i), said electron donor being selected from the group consisting of
• 1. an oxygen-containing organic compound selected from the group consisting of
• saturated aliphatic monoethers of 2-32 carbon atoms having an alkyl group,
• aromatic ethers of 7-16 carbon atoms having a saturated alkyl group of aryl group,
• halogenated mono- and diethers of 7-16 carbon atoms having at least one aromatic radical,
• saturated alkyl esters of saturated aliphatic monocarboxylic acids having an aliphatic monocarboxylic acid residual group of 1-21 carbon atoms and a saturated alkyl group of 1-16 carbon atoms,
• unsaturated alkyl esters of saturated aliphatic monocarboxylic acids having a saturated aliphatic monocarboxylic acid residual group of 1-8 carbon atoms and an unsaturated alkyl group of 2-12 carbon atoms, alkyl esters of unsaturated aliphatic monocarboxylic acids having an unsaturated aliphatic monocarboxylic acid residual group of 2-12 carbon atoms and a saturated or unsaturated alkyl group of 1-10 carbon atoms,
• saturated alkyl esters of aromatic monocarboxylic acids having an aromatic monocarboxylic acid residual group of 7-18 carbon atoms and a saturated alkyl group of 1-20 carbon atoms;
• saturated aliphatic monoketones having 3-20 carbon atoms,
• saturated aliphatic diketones having 4-12 carbon atoms, and
• aromatic monoketones having 7-18 carbon atoms;
• 2. a nitrogen-containing organic compound selected from the group consisting of
• saturated aliphatic primary amines having 1-18 carbon atoms,
• saturated aliphatic secondary amines having 2-24 carbon atoms,
• saturated aliphatic tertiary amines having 3-18 carbon atoms,
• aromatic amines having 6-20 carbon atoms, and heterocyclic amines having 5-18 carbon atoms;
• and
• 3. a phosphorous-containing organic compound selected from the group consisting of
• trialkyl phosphines having 3-21 carbon atoms,
• triaryl phosphines having 18-21 carbon atoms,
• trialkyl phosphites having 3-24 carbon atoms, triaryl phosphites having 18-24 carbon atoms, and hexaalkyl phosphoramides having 1-4 carbon atoms in each alkyl group;
• and
• b. extracting the micro-pulverized titanium trichloride component with an extracting medium comprising
• i. a solvent selected from the group consisting of saturated aliphatic hydrocarbons having 3-20 carbon atoms, aromatic hydrocarbons having 6-20 carbon atoms and halogenated aromatic hydrocarbons having 6-16 carbon atoms, and
• ii. an organic polar compound selected from the group consisting of
• 1. 0.005-10.0 mols per mol of the micro-pulverized titanium trichloride component (a) (i) to be extracted of an oxygen-containing organic polar compound selected from the group consisting of saturated aliphatic monoethers of 2-32 carbon atoms having an alkyl group, aliphatic ethers of 3-20 carbon atoms having an unsaturated aliphatic hydrocarbon group, aromatic ethers of 7-16 carbon atoms having a saturated alkyl group or aryl group, mono- or diethers having a halogen-substituted aromatic group of 7-16 carbon atoms, saturated alkyl esters of saturated aliphatic monocarboxylic acids having an aliphatic monocarboxylic acid residual group of 1-21 carbon atoms and a saturated alkyl group of 1-16 carbon atoms, unsaturated alkyl esters of saturated aliphatic monocarboxylic acids having a saturated aliphatic monocarboxylic acid residual group of 1-8 carbon atoms and an unsaturated alkyl group of 2-12 carbon atoms, alkyl esters of unsaturated aliphatic monocarboxylic acids having an unsaturated aliphatic monocarboxylic acid residual group having 2-12 carbon atoms and a saturated or unsaturated alkyl group of 1-10 carbon atoms, saturated alkyl esters of aromatic monocarboxylic acids having an aromatic monocarboxylic acid residual group of 7-18 carbon atoms and a saturated alkyl group of 1-20 carbon atoms, saturated aliphatic monoalcohols having 1-18 carbon atoms, monohydric and dihydric phenols having 6-16 carbon atoms, saturated aliphatic monoketones having 3-20 carbon atoms, saturated aliphatic diketones having 4-12 carbon atoms, aromatic monoketones having 7-18 carbon atoms, aromatic monocarboxylic acids having 7-18 carbon atoms, saturated aliphatic carboxylic acid halides having 2-12 carbon atoms and aromatic carboxylic acid halides having 7-15 carbon atoms;
• 2. 0.005-0.5 moles per mol of the micro-pulverized titanium trichloride component (a) (i) to be extracted of a nitrogen-containing organic polar compound selected from the group consisting of saturated aliphatic secondary amines having 2-24 carbon atoms, saturated aliphatic tertiary amines having 3-18 carbon atoms, aromatic amines having 6-20 carbon atoms, heterocyclic amines having 5-18 carbon atoms, aromatic monoisocyanates having 7-11 carbon atoms and aromatic azo compounds having 12-20 carbon atoms which may have a hydrocarbon group or halogen atom as a substituent;
• and
• 3. 0.0l-15 parts by weight per part by weight of the micro-pulverized titanium trichloride component (a) (i) to be extracted of a silicon-containing organic polar compound selected from the group consisting of tetrahydrocarbylsilanes of 4-50 carbon atoms having a substituent selected from a saturated alkyl group and an aryl group, tetrahydrocarbylsilanes of 5-28 carbon atoms having an unsaturated alkyl group, alkyl hydrogenosilanes of 1-30 carbon atoms having an Si-H bond, aryl hydrogenosilanes of up to 30 carbon atoms having an Si-H bond, alkyl halogenosilanes of 3-30 carbon atoms having an Si-halogen bond, aryl halogenosilanes of 6-30 carbon atoms having an Si-halogen bond, trialkylsilyl amines of 3-18 carbon atoms, triaryl silyl amines of up to 30 carbon atoms, alkoxysilanes of 4-20 carbon atoms having an Si-O-C bond, aryloxy silanes of 6-40 carbon atoms having an Si-O-C bond, alkyl silyl esters or aryl silyl esters of aliphatic mono- or aromatic monocarboxylic acids composed of trialkyl silanols having 3-10 carbon atoms, alkylaryl silanols having 8-20 carbon atoms or triarylsilanols having 18-30 carbon atoms and aliphatic monocarboxylic acids having 1-10 carbon atoms or aromatic monocarboxylic acids having 7-11 carbon atoms, trialkyl silicon isocyanates having 3-10 carbon atoms, dialkyl aryl silicon isocyanates having 8-15 carbon atoms, triaryl silicon isocyanates having 18-30 carbon atoms, polysilmethylenes of the formula CH.sub.3 SiCH.sub.2 [(CH.sub.3).sub.2 SiCH.sub.2 ].sub.x Si(CH.sub.3).sub.3 wherein x is an integer of 1-10, linear polyalkyl polysilanes having 6-80 carbon atoms, polyaryl polysilanes of up to 80 carbon atoms, polyalkyl cyclopolysilanes having 12-120 carbon atoms, organopolysiloxanes of the formula R(R'R"SiO).sub.x SiR.sub.3, wherein R, R' and R" which may be the same or different, represent an alkyl group having 1-4 carbon atoms, an aryl group having 6-8 carbon atoms, with the proviso that R" can also be hydrogen, and x is an integer of 1-1000;
• .alpha., .omega.-dihaloalkylpolysiloxanes of the formula X(R.sub.2 SiO).sub.x SiR.sub.2 X, wherein R and x are as defined above, and X is a halogen atom;
• alkyl cyclopolysiloxanes of the formula (R"HSiO).sub.y, wherein R" is an alkyl group having 1-4 carbon atoms, and y is an integer of 3-8, alkyl cyclopolysiloxanes of the general formula (R"".sub.2 SiO).sub.z, wherein R"" is an alkyl group having 1-4 carbon atoms and z is an integer of 3-9, aryl cyclopolysiloxanes of the formula (Q.sub.2 SiO).sub.p, wherein Q is an aryl group having 6-8 carbon atoms and p is an integer of 3-6, alkyl polysilazanes of 6-50 carbon atoms having an Si-N-Si bond and a molecular weight of not more than 1000, and aryl polysilazanes of 6-50 carbon atoms having an Si-N-Si bond and a molecular weight of not more than 1000.