US4983561A
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Process for producing solid catalyst for use in polymerization of olefins
Assignee: Sumitomo Chemical Co Ltd
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Filing: 1989-09-12
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Granted: 1991-01-08
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Expires: 2009-09-12
Abstract
Abstract A process for producing a trivalent titanium compound-containing solid catalyst for use in the polymerization of olefins which comprises treating, with an ester compound, a solid product obtained by reducing a titanium compound represented by the following general formula: ##STR1## (R 1 represents hydrocarbon group having 1 to 20 carbon atoms, X represents halogen atom, and n represents a number satisfying 0<n≦4) with an organomagnesium compound in the presence of an organic silicon compound having Si--O bond, and thereafter treating it with a mixture of an ester compound and titanium tetrachloride.
Inventors
- 👤 Toshio Sasaki
- 👤 Eiji Sogabe
- 👤 Takeshi Ebara
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-01 22:46
CPC Classifications
C; C08; C08F; C08F10/00; C08F110/00; C08F110/04; C08F110/06; C08F210/00; C08F210/16
Claims Analysis
Total Claims: 38
Claim 1
Independent Claim
216 words
A process for producing a trivalent titanium compound-containing solid catalyst for use in the polymerization of olefins which comprises treating, with a mono- or poly-valent carboxylic ester selected from the group consisting of aliphatic carboxylic esters, olefinic carboxylic esters, alicyclic carboxylic esters and aromatic carboxylic esters, a solid product obtained by reducing a titanium compound represented by the following general formula, Ti(OR.sup.1).sub.n X.sub.4-n wherein R 1 represents hydrocarbon group having 1 to 20 carbon atoms, X represents halogen atom, and n represents a number satisfying 0<n≦4 with an organomagnesium compound in the presence of an organic silicon compound having Si--O bond which has any of the general formulae, Si(OR.sup.3).sub.m R.sup.4.sub.4-m, R.sup.5 (R.sup.6.sub.2 SiO).sub.p SiR.sup.7.sub.3, and R.sup.8.sub.2 SiO).sub.q wherein R 3 represents hydrocarbon group having 1 to 20 carbon atoms; R 4 , R 5 , R 6 , R 7 and R 8 each represents hydrocarbon group having 1 to 20 carbon atoms or hydrogen atom; m represents a number satisfying 0<m≦4; p represents an integer of 1 to 1,000; and q represents an integer of 2 to 1,000 to obtain an ester-treated solid product, and treating the ester-treated solid product with a mixture of the same mono- or poly-valent carboxylic ester as used in the step of producing the ester-treated solid product and titanium tetrachloride.
Claim 2
Dependent Claim
216 words
A process for producing a trivalent titanium compound-containing solid catalyst for use in the polymerization of olefins which comprises treating, with a mono- or poly-valent carboxylic ester selected from the group consisting of aliphatic carboxylic esters, olefinic carboxylic esters, alicyclic carboxylic esters and aromatic carboxylic esters, a solid product obtained by reducing a titanium compound represented by the following general formula, Ti(OR.sup.1).sub.n X.sub.4-n wherein R 1 represents hydrocarbon group having 1 to 20 carbon atoms, X represents halogen atom, and n represents a number satisfying 0<n≦4 with an organomagnesium compound in the presence of an organic silicon compound having Si--O bond which has any of the general formulae, Si(OR.sup.3).sub.m R.sup.4.sub.4-m, R.sup.5 (R.sup.6.sub.2 SiO).sub.p SiR.sup.7.sub.3, and R.sup.8.sub.2 SiO).sub.q wherein R 3 represents hydrocarbon group having 1 to 20 carbon atoms; R 4 , R 5 , R 6 , R 7 and R 8 each represents hydrocarbon group having 1 to 20 carbon atoms or hydrogen atom; m represents a number satisfying 0<m≦4; p represents an integer of 1 to 1,000; and q represents an integer of 2 to 1,000 to obtain an ester-treated solid product, and treating the ester-treated solid product with a mixture of the same mono- or poly-valent carboxylic ester as used in the step of producing the ester-treated solid product and titanium tetrachloride.
Claim 3
Dependent Claim
57 words
A process according to claim 1, wherein the step of treating the ester-treated solid product includes the step of selecting as the mixture a mixture of a mono- or poly-valent carboxylic ester selected from the group consisting of aliphatic carboxylic esters, olefinic carboxylic esters, alicyclic carboxylic esters and aromatic carboxylic esters, a dialkyl ether, and titanium tetrachloride.
Claim 4
Dependent Claim
42 words
A process according to claim 1, wherein R 1 in the titanium compound represented by the general formula Ti(OR 1 ) n X 4-n is alkyl groups having 2 to 18 carbon atoms and aryl groups having 6 to 18 carbon atoms.
Claim 5
Dependent Claim
35 words
A process according to claim 3, wherein R 1 in the titanium compound represented by the general formula Ti(OR 1 ) n X 4-n is straight chain alkyl groups having 2 to 18 carbon atoms.
Claim 6
Dependent Claim
27 words
A process according to claim 1, wherein the value of n in the titanium compound represented by general formula Ti(OR 1 ) n X 4-n is 2≦n≦4.
Claim 7
Dependent Claim
13 words
A process according to claim 5, wherein the value of n is 4.
Claim 8
Dependent Claim
82 words
A process according to claim 1, wherein the organomagnesium compound is Grignard compounds represented by general formula R 9 MgX (R 9 represents hydrocarbon group having 1 to 20 carbon atoms and X represents halogen atom), dialkylmagnesium compounds or diarylmagnesium compounds represented by general formula R 10 R 11 Mg (R 10 and R 11 each represents hydrocarbon group having 1 to 20 carbon atoms), among which R 9 , R 10 and R 11 are identical or different from one another.
Claim 9
Dependent Claim
29 words
A process according to claim 1, wherein the organic silicone compound is alkoxYsilane compounds represented by general formula Si(OR 3 ) m R 4 4-m wherein m satisfies 1≦m≦4.
Claim 10
Dependent Claim
15 words
A process according to claim 8, wherein the alkoxysilane compound is tetraalkoxysilane compounds satisfying m=4.
Claim 11
Dependent Claim
39 words
A process according to claim 1, wherein the ether compound is diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, diisoamyl ether, dineopentyl ether, dihexyl ether, dioctyl ether, methyl butyl ether, methyl isoamyl ether, or ethyl isobutyl ether.
Claim 12
Dependent Claim
16 words
A process according to claim 10, wherein the ether compound is dibutyl ether or diisoamyl ether.
Claim 13
Dependent Claim
23 words
A process according to claim 1, wherein the organomagnesium compound is added to a mixture of titanium compound and an organic silicone compound.
Claim 14
Dependent Claim
25 words
A process according to claim 12, wherein the titanium compound and organic silicone compound are used after disolving or diluting them with an appropriate solvent.
Claim 15
Dependent Claim
19 words
A process according to claim 13, wherein the solvent is aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, or ether compounds.
Claim 16
Dependent Claim
21 words
A process according to claim 1, wherein the reduction is carried out at a temperature ranging from -50° to 70° C.
Claim 17
Dependent Claim
50 words
A process according to claim 1, wherein the reduction is carried out in the presence of a porous material having a pore volume of 0.3 ml/g or more as measured at a pore radius of 200 to 2,000 angstroms and having a mean particle diameter of 5 to 300 microns.
Claim 18
Dependent Claim
16 words
A process according to claim 16, wherein the porous material is inorganic oxide or organic polymer.
Claim 19
Dependent Claim
46 words
A process according to claim 17, wherein the porous inorganic oxide is SiO 2 , Al 2 O 3 , MgO, TiO 2 , ZrO 2 , SiO 2 .Al 2 O 3 , MgO.Al 2 O 3 or MgO.SiO 2 .Al 2 O 3 .
Claim 20
Dependent Claim
29 words
A process according to claim 17, wherein the porous organic polymer is polystyrene type, polyacrylic ester type, polymethacrylic ester type, polyacrylonitrile type, polyvinyl chloride type or polyolefin type polymers.
Claim 21
Dependent Claim
38 words
A process according to claim 1, wherein the amount of organic silicon compound is in the range of 1 to 50 as expressed in terms of atomic ratio of silicon atom to titanium atom (Si/Ti) in titanium compound.
Claim 22
Dependent Claim
41 words
A process according to claim 1, wherein the amount of the organomagnesium compound is in the range of 0.1 to 10 as expressed in terms of atomic ratio of the sum of titanium atom and silicon atom to magnesium atom (Ti+Si/Mg).
Claim 23
Dependent Claim
32 words
A process according to claim 1, wherein the amount of ester compound for treating the solid product is 0.1 to 50 moles per one mole of titanium atom in the solid product.
Claim 24
Dependent Claim
37 words
A process according to claim 1, wherein the amount of ester compound for treating the solid product is used in an amount of 0.01 to 1.0 mole per one mole of magnesium atom in the solid product.
Claim 25
Dependent Claim
22 words
A process according to claim 1, wherein the solid product is treated with the ester compound in the presence of a diluent.
Claim 26
Dependent Claim
19 words
A process according to claim 24, wherein the diluent is aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons or halogenated hydrocarbons.
Claim 27
Dependent Claim
21 words
A process according to claim 24, wherein the amount of diluent is 0.1-1000 ml per one gram of the solid product.
Claim 28
Dependent Claim
26 words
A process according to claim 1, wherein the solid product is treated with the ester compound at -50° to 150° C. for 10 minutes or more.
Claim 29
Dependent Claim
25 words
A process according to claim 27, wherein the solid product is treated with the ester compound at 0°-120° C. for 30 minutes to 3 hours.
Claim 30
Dependent Claim
27 words
A process according to claim 1, wherein the ester-treated solid product is treated with a mixture of an ester compound and titanium tetrachloride in a slurry state.
Claim 31
Dependent Claim
22 words
A process according to claim 29, wherein a solvent used for slurry is aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons or halogenated hydrocarbons.
Claim 32
Dependent Claim
18 words
A process according to claim 29, wherein a concentration of slurry is 0.05-0.7 g.solid per ml of solvent.
Claim 33
Dependent Claim
24 words
A process according to claim 29, wherein the treatment is carried out at a temperature of 30°-150° C. for 30 minutes to 6 hours.
Claim 34
Dependent Claim
36 words
A process according to claim 1, the amount of the ester compound in the mixture for treating the ester-treated solid product is 0.02 to 30moles per one mole of titanium atom in the ester-treated solid product.
Claim 35
Dependent Claim
37 words
A process according to claim 1, wherein the amount of titanium tetrachloride in the mixture for treating the ester-treated solid product is 1 to 1,000 moles per one mole of titanium atom in the ester-treated solid product.
Claim 36
Dependent Claim
230 words
A trivalent titanium compound-containing solid catalyst for use in the polymerization of olefins which is produced by treating, with a mono- or poly-valent carboxylic ester selected from the group consisting of aliphatic carboxylic esters, olefinic carboxylic esters, alicyclic carboxylic esters and aromatic carboxylic esters, a solid product obtained by reducing a titanium compound represented by the following general formula, Ti(OR.sup.1).sub.n X.sub.4-n wherein R 1 represents hydrocarbon group having 1 to 20 carbon atoms, X represents halogen atom, and n represents a number satisfying 0<n≦4, with an organomagnesium compound in the presence of an organic silicon compound having Si--O bond which has any of the general formulae, Si(OR 3 ) m R 4 4-m , R 5 (R 6 2 SiO) p SiR 7 3 , and R 8 2 SiO) q wherein R 3 represents hydrocarbon group having 1 to 20 carbon atoms; R 4 , R 5 , R 6 , R 7 and R 8 each represents hydrocarbon group having 1 to 20 carbon atoms or hydrogen atom; m represents a number satisfying 0<m≦4; p represents an integer of 1 to 1,000; and q represents an integer of 2 to 1,000 to obtain an ester-treated solid product, and treating the ester-treated solid product with a mixture of the same mono- or poly-valent carboxylic ester as used in the step of producing the ester-treated solid product and titanium tetrachloride.
Claim 37
Dependent Claim
230 words
A trivalent titanium compound-containing solid catalyst for use in the polymerization of olefins which is produced by treating, with a mono- or poly-valent carboxylic ester selected from the group consisting of aliphatic carboxylic esters, olefinic carboxylic esters, alicyclic carboxylic esters and aromatic carboxylic esters, a solid product obtained by reducing a titanium compound represented by the following general formula, Ti(OR.sup.1).sub.n X.sub.4-n wherein R 1 represents hydrocarbon group having 1 to 20 carbon atoms, X represents halogen atom, and n represents a number satisfying 0<n≦4, with an organomagnesium compound in the presence of an organic silicon compound having Si--O bond which has any of the general formulae, Si(OR 3 ) m R 4 4-m , R 5 (R 6 2 SiO) p SiR 7 3 , and R 8 2 SiO) q wherein R 3 represents hydrocarbon group having 1 to 20 carbon atoms; R 4 , R 5 , R 6 , R 7 and R 8 each represents hydrocarbon group having 1 to 20 carbon atoms or hydrogen atom; m represents a number satisfying 0<m≦4; p represents an integer of 1 to 1,000; and q represents an integer of 2 to 1,000 to obtain an ester-treated solid product, and treating the ester-treated solid product with a mixture of the same mono- or poly-valent carboxylic ester as used in the step of producing the ester-treated solid product and titanium tetrachloride.
Claim 38
Dependent Claim
61 words
A trivalent titanium compound-containing solid catalyst according to claim 35, wherein the step of treating the ester-treated solid product includes the step of selecting as the mixture a mixture of a mono- or poly-valent carboxylic ester selected from the group consisting of aliphatic carboxylic esters, olefinic carboxylic esters, alicyclic carboxylic esters and aromatic carboxylic esters, a dialkyl ether, and titanium tetrachloride.
References Cited (Backward Citations)
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