Universal alpha-olefin polymerization catalyst, and application thereof

Patent metadata

Field	Value
Publication number	US-11220560-B2
Application number	US-201716335929-A
Country	US
Kind code	B2
Filing date	Oct 25, 2017
Priority date	Sep 29, 2017
Publication date	Jan 11, 2022
Grant date	Jan 11, 2022

Abstract

Disclosed are a universal alpha-olefin polymerization industrial catalyst, and an application thereof, specifically an industrial production catalyst which consists of (A) a solid catalyst component, (B) a cocatalyst organoaluminium compound and (C) an external electron donor compound, and is used for various alpha-olefin polymerization or copolymerization processes. The solid catalyst component (A) is prepared from a dibutyl phthalate or diisobutyl phthalate and 9,9-bis(methoxymethyl)fluorene composite internal electron donor. A hydrocarbyl alkoxy silicon, an organic acid ester or a hydrocarbyl alkoxy silicon and organic acid ester composite acts as the external electron donor component (C). The solid catalyst component (A), the cocatalyst organoaluminium compound (B) and the external electron donor compound (C) are used together in industrial devices for various alpha-olefin polymerization or copolymerization processes to produce new grades of poly-alpha-olefins.

First claim

We claim:

1. A catalyst for large-scale industrial preparation of poly-α-olefins in various polymerization processes, comprising a catalyst component A, a cocatalyst alkyl aluminum B, and an external electron donor C;
wherein:
(1) the catalyst component A consists of titanium ions and a composite internal electron donor aromatic diaciddialkyl ester and 1,3-diether supported on magnesium chloride;
(2) the cocatalyst alkyl aluminum B is triethyl aluminum, triisobutyl aluminum or a mixture thereof; and
(3) the external electron donor C comprises an organic acid ester or a hydrocarbylalkoxy silicon and organic acid ester composite, and
wherein the cocatalyst alkylaluminum B and titanium ions (Ti) have a molar ratio in the range of 60-75.

2. The catalyst according to claim 1 , wherein in the catalyst component A, the aromatic diaciddialkyl ester is diisobutyl phthalate.

3. The catalyst according to claim 2 , wherein in the catalyst component A, the 1,3-diether is 9,9-bis(methoxymethyl)fluorene.

4. The catalyst according to claim 3 , wherein in the catalyst component A, the mass fraction of titanium is 2.0-3.8%, the mass fraction of magnesium is 15.0-20.0%, the mass fraction of diisobutyl phthalate is 1.0-7.0%, and the mass fraction of 9,9-bis(methoxymethyl)fluorene is 1.0-9.0%.

5. The catalyst according to claim 3 , wherein a molar ratio of diisobutyl phthalate and 9,9-bis(methoxymethyl) fluorene is 1-9.9:10.

6. The catalyst according to claim 1 , wherein the preparation method of the catalyst component A comprises one of a)-c):
a) co-precipitation of a magnesium chloride alcoholate, a composite internal electron donor and titanium tetrachloride;
b) supporting titanium tetrachloride and a composite internal electron donor on a spherical magnesium chloride alcoholate support; or
c) supporting a composite internal electron donor on magnesium chloride generated by reaction of diethoxymagnesium and titanium tetrachloride.

7. The catalyst according to claim 1 ,
wherein:
the organic acid ester is a C 10-20 linear natural fatty acid C 3-5 branched alkyl ester; and
the hydrocarbylalkoxy silicon and organic acid ester composite is selected from the group consisting of propyltrimethoxysilicon and isopropyl myristate, dicyclopentyldimethoxysilicon and isopropyl myristate, and diphenyldimethoxysilicon and isopropyl myristate composites.

8. The catalyst according to claim 1 , wherein a molar ratio of the hydrocarbylalkoxy silicon and the organic acid ester is 1-9.9:10.

9. The catalyst according to claim 1 , wherein the alpha-olefin polymerization is propylene polymerization, 1-butene polymerization, ethylene and propylene copolymerization, ethylene and 1-butene copolymerization, or propylene and 1-butene copolymerization.

10. A method of using the catalyst according to claim 1 in large-scale industrial production of poly-α-olefins in a polymerization process, the method comprising:
providing the catalyst according to claim 1 , contacting the catalyst with an α-olefin to effect polymerization of the α-olefin;
wherein the process comprises:
(1) a gas phase reaction which is: α-olefin polymerization in a gas-phase fluidized bed reactor process, α-olefin polymerization in a vertical stirred-tank gas-phase reactor process, α-olefin polymerization in a horizontal stirred-tank gas-phase reactor process, or α-olefin polymerization in the a horizontal stirred-tank gas-phase reactor process;
(2) a batch bulk reaction which is an α-olefin polymerization process in a tank reactor; or
(3) a continuous bulk reaction which is an α-olefin polymerization process in a loop reactor process or α-olefin polymerization process having one horizontal bulk reactor and one horizontal gas-phase reactor tank arranged in series.

11. The method of claim 10 , wherein the catalyst is according to claim 4 .

12. The method of claim 10 , wherein the catalyst is according to claim 5 .

13. The method of claim 10 , wherein the catalyst is according to claim 8 .

14. The catalyst according to claim 1 , wherein in the catalyst component A, the aromatic diaciddialkyl ester is di-n-butyl phthalate.

15. The catalyst according to claim 14 , wherein in the catalyst component A, the 1,3-diether is 9,9-bis(methoxymethyl)fluorene.

16. The catalyst according to claim 15 , wherein a molar ratio of di-n-butyl phthalate and 9,9-bis(methoxymethyl) fluorene is 1-9.9:10.

17. The catalyst according to claim 15 , wherein in the catalyst component A, the mass fraction of titanium is 2.0-3.8%, the mass fraction of magnesium is 15.0-20.0%, the mass fraction of di-n-butyl phthalate is 1.0-7.0%, and the mass fraction of 9,9-bis(methoxymethyl)fluorene is 1.0-9.0%.

18. A catalyst for large-scale industrial preparation of poly-α-olefins in various polymerization processes, comprising a catalyst component A, a cocatalyst alkyl aluminum B, and an external electron donor C;
wherein:
(1) the catalyst component A consists of titanium ions and a composite internal electron donor aromatic diaciddialkyl ester and 1,3-diether supported on magnesium chloride;
(2) the cocatalyst alkyl aluminum B is triethyl aluminum, triisobutyl aluminum or a mixture thereof; and
(3) the external electron donor C is a hydrocarbylalkoxy silicon, an organic acid ester or a hydrocarbylalkoxy silicon and organic acid ester composite, and
wherein the cocatalyst alkylaluminum B and titanium ions (Ti) have a molar ratio in the range of 60-75.

Assignees

• Yingkou Xiangyang Catalyst Co Ltd
• Univ Dalian Tech

Inventors

• Wang Licai
• Gao Zhanxian
• Yu Limei
• Wang Huan
• Li Wei
• Zheng Guotong
• Dong Qingxin

Classifications

• C08F4/649

  organic · CPC title

• C08F4/646

  Catalysts comprising at least two different metals, in metallic form or as compounds thereof, in addition to the component covered by group C08F4/64 {(C08F4/64003 - C08F4/64196 take precedence)} · CPC title

• C08F110/06

  Propene · CPC title

• C08F10/00

  Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond · CPC title

• C08F210/06

  Propene · CPC title