Catalyst composition for olefin polymerization and application of same

Patent metadata

Field	Value
Publication number	US-9822196-B2
Application number	US-201415025698-A
Country	US
Kind code	B2
Filing date	Sep 28, 2014
Priority date	Sep 30, 2013
Publication date	Nov 21, 2017
Grant date	Nov 21, 2017

Abstract

The present disclosure discloses a catalyst composition for olefin polymerization, comprising the following components: a): a solid catalyst component containing magnesium, titanium, halogens, and at least one internal electron donor having a lone pair of electrons; b): an aluminum alkyl compound; and c): an external electron donor containing a first external electron donor C1, which is a malonate compound. In the present disclosure, a catalyst composition having an external electron donor that contains a malonate compound is used in olefin polymerization, in particular propene polymerization, and can significantly improve catalytic activity and hydrogen response of the catalyst and expand molecular weight distribution of polymers, which facilitates development of different polymers.

First claim

The invention claimed is:

1. A catalyst composition for olefin polymerization, comprising the following components:
a): a solid catalyst component containing magnesium, titanium, halogens, and at least one internal electron donor having a lone pair of electrons;
b): an aluminum alkyl compound; and
c): an external electron donor containing a first external electron donor C1, which is a malonate compound and a second external electron donor C2 selected from the group consisting of silane, diether, and amine compounds,
wherein the internal electron donor is selected from the group of compounds containing the atom of O, N, P, or S.

2. The catalyst composition of claim 1 , wherein the malonate compound has a general formula as shown in Formula (I):

wherein R 9 is a substituted or non-substituted C 1 to C 20 hydrocarbyl group, and R 7 and R 8 , identical with or different from each other, are selected from the group consisting of hydrogen, halogens, and substituted or non-substituted C 1 to C 20 hydrocarbyl groups.

3. The catalyst composition according to claim 2 , wherein R 9 is selected from the group consisting of substituted or non-substituted C 1 to C 10 straight-chain alkyl groups, C 3 to C 10 branched-chain alkyl groups, C 3 to C 10 cycloalkyl groups, C 6 to C 10 aryl groups, C 7 to C 10 alkaryl groups, and C 7 to C 10 aralkyl groups; and
wherein, R 7 and R 8 , identical with or different from each other, are selected from the group consisting of hydrogen, halogens, and substituted or non-substituted C 1 to C 10 alkyl groups, C 1 to C 10 alkylene groups, C 3 to C 10 cycloalkyl groups, C 6 to C 10 aryl groups, and C 7 to C 10 alkaryl or aralkyl groups.

4. The catalyst composition of claim 1 , wherein the malonate compound is at least one selected from the group consisting of diethyl malonate, di-n-propyl malonate, diisopropyl malonate, di-n-butyl malonate, diisobutyl malonate, diethyl methylmalonate, di-n-propyl methylmalonate, di-iso-propyl methylmalonate, di-n-butyl methylmalonate, di-iso-butyl methylmalonate, di-tert-butyl methylmalonate, diethyl ethylmalonate, di-n-propyl ethylmalonate, di-iso-propyl ethylmalonate, di-n-butyl ethylmalonate, di-iso-butyl ethylmalonate, di-tert-butyl ethylmalonate, diethyl n-propylmalonate, di-n-propyl n-propylmalonate, di-iso-propyl n-propylmalonate, di-n-butyl n-propylmalonate, di-iso-butyl n-propylmalonate, di-tert-butyl n-propylmalonate, diethyl isopropylmalonate, di-n-propyl isopropylmalonate, di-iso-propyl isopropylmalonate, di-n-butyl isopropylmalonate, di-iso-butyl isopropylmalonate, di-tert-butyl isopropylmalonate, diethyl phenylmalonate, di-n-propyl phenylmalonate, di-iso-propyl phenylmalonate, di-n-butyl phenylmalonate, di-iso-butyl phenylmalonate, di-tert-butyl phenylmalonate, diethyl benzylmalonate, di-n-propyl benzylmalonate, di-iso-propyl benzylmalonate, di-n-butyl benzylmalonate, di-iso-butyl benzylmalonate, di-tert-butyl benzylmalonate, diethyl dimethylmalonate, diethyl diethylmalonate, diethyl methylethylmalonate, diethyl methyl-n-butylmalonate, diethyl methylisobutylmalonate, diethyl methyl-n-propylmalonate, diethyl methylisopropylmalonate, diethyl di-n-propyl-malonate, diethyl di-n-butyl-malonate, diethyl di-iso-propyl-malonate, diethyl di-iso-butyl-malonate, and diethyl di-allyl-malonate.

5. The catalyst composition of claim 1 , wherein the internal electron donor in solid catalyst component a) is selected from the group consisting of ether, ester, phenolic ether, phenolic ester, and ketone compounds.

6. The catalyst composition of claim 5 , wherein the internal electron donor in solid catalyst component a) is selected from the group consisting of diol ester compounds, succinate compounds, phthalate compounds, and diether compounds.

7. The catalyst composition of claim 6 , wherein the diol ester compounds have a general formula as shown in Formula (II):

wherein, R 1 and R 2 , identical with or different from each other, are selected from the group consisting of substituted or non-substituted C 1 to C 20 alkyl groups, C 3 to C 20 cycloalkyl groups, C 6 to C 20 aryl groups, C 7 to C 20 alkaryl groups, and C 7 to C 20 aralkyl groups;
wherein, R 3 and R 4 , identical with or different from each other, are selected from the group consisting of hydrogen, halogens, and substituted or non-substituted C 1 to C 10 straight-chain alkyl groups, C 3 to C 10 branched-chain alkyl groups, C 3 to C 10 cycloalkyl groups, C 6 to C 10 aryl groups, and C 7 to C 10 alkaryl or aralkyl groups; and
wherein, R 5 and R 6 , identical with or different from each other, are selected from the group consisting of halogens, and substituted or non-substituted C 1 to C 10 straight-chain alkyl groups, C 3 to C 10 branched-chain alkyl groups, C 3 to C 10 cycloalkyl groups, C 6 to C 10 aryl groups, and C 7 to C 10 alkaryl or aralkyl groups.

8. The catalyst composition of claim 6 , wherein the diol ester compounds are at least one selected from the group consisting of 2,4-pentanediol dibenzoate, 2,4-pentanediol di-p-methyl-benzoate, 2,4-pentanediol di-m-methyl-benzoate, 2,4-pentanediol di-o-methyl-benzoate, 2,4-pentanediol di-p-ethyl-benzoate, 2,4-pentanediol di-p-n-propyl-benzoate, 2,4-pentanediol di-p-iso-propyl-benzoate, 2,4-pentanediol di-p-iso-butyl-benzoate, 2,4-pentanediol di-p-n-butyl-benzoate, 2,4-pentanediol di-p-tert-butyl-benzoate, 3-methyl-2,4-pentanediol dibenzoate, 3-ethyl-2,4-pentanediol dibenzoate, 3-n-propyl-2,4-pentanediol dibenzoate, 3-ethyl-2,4-pentanediol di-p-methyl-benzoate, 3-ethyl-2,4-pentanediol di-p-ethyl-benzoate, 3-ethyl-2,4-pentanediol di-p-n-propyl-benzoate, 3-ethyl-2,4-pentanediol di-p-iso-propyl-benzoate, 3-ethyl-2,4-pentanediol di-p-iso-butyl-benzoate, 3-ethyl-2,4-pentanediol di-p-n-butyl-benzoate, 3-ethyl-2,4-pentanediol di-p-tert-butyl-benzoate, 3-n-butyl-2,4-pentanediol dibenzoate, 3,3-di-methyl-2,4-pentanediol dibenzoate, 3-chloro-2,4-pentanediol dibenzoate, 3-bromo-2,4-pentanediol dibenzoate, 3,5-heptanediol dibenzoate, 3,5-heptanediol di-p-methyl-benzoate, 3,5-heptanediol di-p-ethyl-benzoate, 3,5-heptanediol di-p-n-propyl-benzoate, 3,5-heptanediol di-p-iso-propyl-benzoate, 3,5-heptanediol di-p-iso-butyl-benzoate, 3,5-heptanediol di-p-n-butyl-benzoate, 3,5-heptanediol di-p-tert-butyl-benzoate, 4-methyl-3,5-heptanediol dibenzoate, 4,4-dimethyl-3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol di-p-methyl-benzoate, 4-ethyl-3,5-heptanediol di-p-ethyl-benzoate, 4-ethyl-3,5-heptanediol di-p-propyl-benzoate, 4-ethyl-3,5-heptanediol di-p-butyl-benzoate, 4-ethyl-3,5-heptanediol di-p-tert-butyl-benzoate, 4-n-propyl-3,5-heptanediol dibenzoate, 4-n-butyl-3,5-heptanediol dibenzoate, 4-chloro-3,5-heptanediol dibenzoate, and 4-bromo-3,5-heptanediol dibenzoate.

9. The catalyst composition of claim 6 , wherein the phthalate compounds have a general formula as shown in Formula (III):

wherein R 21 is selected from the group consisting of C 1 to C 10 straight-chain alkyl groups, C 3 to C 15 branched-chain alkyl groups, C 3 to C 15 cycloalkyl groups, C 6 to C 20 aryl groups, C 7 to C 20 alkaryl groups, and C 7 to C 20 aralkyl groups; and
wherein R 22 to R 25 , identical with or different from one another, are selected from the group consisting of hydrogen, halogens, and substituted or non-substituted C 1 to C 10 straight-chain alkyl groups, C 3 to

Assignees

• China Petroleum & Chem Corp
• Beijing Res Inst Chemical Ind China Petroleum & Chemical Corp

Inventors

• Li Changxiu
• Gao Mingzhi
• Liu Haitao
• Ma Jing
• Chen Jianhua
• Li Xianzhong
• Cai Xiaoxia
• Ma Jixing
• Wang Jun
• Hu Jianjun

Classifications

• C08F110/06 Primary

  Propene · CPC title

• C08F4/654

  with magnesium or compounds thereof · CPC title

• C08F2/34

  Polymerisation in gaseous state · CPC title

• C08F4/649

  organic · CPC title

• C08F4/651 Primary

  Pretreating with non-metals or metal-free compounds · CPC title