Supported nonmetallocene catalysts, preparation and use thereof

Patent metadata

Field	Value
Publication number	US-9334339-B2
Application number	US-201414299973-A
Country	US
Kind code	B2
Filing date	Jun 9, 2014
Priority date	Jun 8, 2013
Publication date	May 10, 2016
Grant date	May 10, 2016

Abstract

Disclosed is a supported nonmetallocene catalyst and preparation thereof. The supported nonmetallocene catalyst is characterized by a high catalyst activity for olefin polymerization and a significant monomer effect. Further disclosed is use of the supported nonmetallocene catalyst in olefin homopolymerization/copolymerization. The polymer produced therewith is characterized by superior particle morphology, a high bulk density, and/or a narrow molecular weight distribution.

First claim

We claim:

1. A process for producing a supported nonmetallocene catalyst, comprising the steps of: dissolving a magnesium compound in a first solvent in the presence of an alcohol to obtain a magnesium compound solution; obtaining a Mg-containing carrier by (1) mixing a porous carrier with the magnesium compound solution to obtain a first slurry, and drying the first slurry, or introducing into the first slurry a precipitating agent to obtain a Mg-containing carrier, or (2) drying the magnesium compound solution, or introducing into the magnesium compound solution a precipitating agent to obtain a Mg-containing carrier; contacting the Mg-containing carrier with a silicon compound represented by the following formula (X) and a chemical treating agent selected from the group consisting of a Group IVB metal compound, to obtain a modified Mg-containing carrier;
Si(OR) m X 4-m   (X)

wherein each R may be identical to or different from one another, each independently selected from a C 1 -C 8 straight chain or branched alkyl, m is 0, 1, 2, 3, or 4, each X may be identical to or different from one another, each independently selected from a halogen atom,
and, contacting the modified Mg-containing carrier with a nonmetallocene complex in the presence of a second solvent, to obtain the supported nonmetallocene catalyst,
optionally further comprising the step of pre-contacting the Mg-containing carrier with an assistant chemical treating agent selected from the group consisting of an aluminoxane, an alkylaluminum and any combination thereof, before contacting the Mg-containing carrier with the silicon compound and the chemical treating agent.

2. The process according to claim 1 , wherein the porous carrier is one or more selected from the group consisting of olefin homopolymers or copolymers, vinyl alcohol homopolymers or copolymers, cyclodextrins, polyesters or co-polyesters, polyamides or co-polyamides, vinyl chloride homopolymers or copolymers, acrylic ester homopolymers or copolymers, methacrylic ester homopolymers or copolymers, styrene homopolymers or copolymers, partly crosslinked products of these homopolymers or copolymers, refractory oxides or refractory composite oxides of a Group IIA, IIIA, IVA or IVB metal in the Periodic Table of Elements, clay, molecular sieve, mica, montmorillonite, bentonite and kieselguhr, the porous carrier being optionally thermally activated and/or chemically activated by the Group IVB metal compound, while the magnesium compound is one or more selected from the group consisting of a magnesium halide, an alkoxy magnesium halide, an alkoxy magnesium, an alkyl magnesium, an alkyl magnesium halide and an alkyl alkoxy magnesium.

3. The process according to claim 1 , wherein the first solvent is one or more selected from the group consisting of a C 6-12 aromatic hydrocarbon and tetrahydrofuran, the second solvent is one or more selected from the group consisting of a C 6-12 aromatic hydrocarbon, dichloromethane and tetrahydrofuran, and the alcohol is one or more selected from the group consisting of an aliphatic alcohol, wherein the alcohol is optionally substituted by a substituent selected from the group consisting of a halogen atom and a C 1-6 alkoxy group.

4. The process according to claim 1 , wherein the nonmetallocene complex is one or more selected from the group consisting of the compounds having the following structure,

wherein,
q is 0 or 1;
d is 1;
m is 1, 2 or 3;
M is a central metal atom selected from the group consisting of a Group III to XI metal atom in the Periodic Table of Elements;
n is 1, 2, 3 or 4, depending on the valence of the central metal atom M;
X is selected from the group consisting of a halogen atom, a hydrogen atom, a C 1 -C 30 hydrocarbyl, a substituted C 1 -C 30 hydrocarbyl, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, a boron-containing group, an aluminium-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, and a tin-containing group, when multiple X's exist, the X's may be the same as or different from one another, and may form a bond or a ring with one another;
A is selected from the group consisting of an oxygen atom, a sulfur atom, a selenium atom,

—NR 23 R 24 , —N(O)R 25 R 26 ,

—PR 28 R 29 , P(O)R 30 OR 31 , a sulfone group, a sulfoxide group and —Se(O)R 39 , wherein N, O, S, Se and P each represents a coordination atom;
B is selected from the group consisting of a nitrogen atom, a nitrogen-containing group, a phosphorus-containing group and a C 1 -C 30 hydrocarbyl;
D is selected from the group consisting of a nitrogen atom, an oxygen atom, a sulfur atom, a selenium atom, a phosphorus atom, a nitrogen-containing group, a phosphorus-containing group, a C 1 -C 30 hydrocarbyl, a sulfone group or a sulfoxide group,

and —P(O)R 32 OR 33 , wherein N, O, S, Se and P each represents a coordination atom;
E is selected from the group consisting of a nitrogen-containing group, an oxygen-containing group, a sulfur-containing group, a selenium-containing group, a phosphorus-containing group and a cyano group, wherein N, O, S, Se and P each represents a coordination atom;
G is selected from the group consisting of a C 1 -C 30 hydrocarbylene group, a substituted C 1 -C 30 hydrocarbylene group and an inert functional group;
→ represents a single bond or a double bond;
— represents a covalent bond or an ionic bond;
--- represents a coordination bond, a covalent bond or an ionic bond;
R′ to R 3 , R 22 to R 33 and R 39 are each independently selected from the group consisting of a hydrogen atom, a C 1 -C 30 hydrocarbyl, a substituted C 1 -C 30 hydrocarbyl and an inert functional group, wherein these groups may be identical to or different from one another, and any adjacent groups may form a bond or a ring with one another.

5. The process according to claim 1 , wherein ratio of the magnesium compound to the first solvent is 1 mol 75-400 ml, ratio by molar of the magnesium compound (based on Mg) to the alcohol is 1:0.02-4.00, ratio by weight of the magnesium compound (on a solid basis) to the porous carrier is 1:0.1-20, ratio by volume of the precipitating agent to the first solvent is 1:0.2-5, ratio by molar of the Mg-containing carrier (based on Mg) to the silicon compound (based on Si) is 1:0.01-1, ratio by molar of the Mg-containing carrier (based on Mg) to the chemical treating agent (based on the Group IVB metal) is 1:0.01-1, ratio by molar of the Mg-containing carrier (based on Mg) to the nonmetallocene complex is 1:0.01-1, and ratio by molar of the Mg-containing carrier (based on Mg) to the assistant chemical treating agent (based on Al) is 1:0-1.0.

6. The process according to claim 1 , wherein the precipitating agent is one or more selected from the group consisting of pentane, hexane, heptane, octane, nonane, decane, cyclohexane, cyclopentane, cycloheptane, cyclodecane, cyclononane, dichloromethane, dichloro hexane, dichloro heptane, trichloro methane, trichloro ethane, trichloro butane, dibromo methane, dibromo ethane, dibromo heptane, tribromo methane, tribromo ethane, tribromo butane, chlorinated cyclopentane, chlorinated cyclohexane, chlorinated cycloheptane, chlorinated cyclooctane, chlorinated cyclononane, chlorinated cyclodecane, b

Assignees

• China Petroleum & Chemical
• Sinopec Yangzi Petrochemical

Inventors

• Li Chuanfeng
• Ren Hongping
• Kan Lin
• Guo Feng
• Wang Wenrui
• Yi Yuming
• Chen Shaohui
• Bai Jiye

Classifications

• C08F10/02 Primary

  Ethene · CPC title

• C08F2500/18

  Bulk density · CPC title

• C08F210/16

  Copolymers of ethene with alpha-alkenes, e.g. EP rubbers · CPC title

• C08F110/02

  Ethene · CPC title

• C08F4/02

  Carriers therefor · CPC title