Catalyst system for olefin polymerization and use thereof

Patent metadata

Field	Value
Publication number	US-11840508-B2
Application number	US-202017629300-A
Country	US
Kind code	B2
Filing date	Jul 24, 2020
Priority date	Jul 26, 2019
Publication date	Dec 12, 2023
Grant date	Dec 12, 2023

Abstract

A catalyst system for olefin polymerization contains a main catalyst and a cocatalyst. The cocatalyst contains a twelve-membered ring compound represented by formula (M). The catalyst system is suitable for preparing polypropylene products having high stereoregularity and low ash, and can regulate the melt index of the products within a wide range by adjusting the amount of hydrogenation. It is also suitable for copolymerization systems to improve the copolymerization yield.

First claim

The invention claimed is:

1. A catalyst system for olefin polymerization, comprising a main catalyst and a cocatalyst, wherein the cocatalyst comprises a twelve-membered ring compound represented by formula (M),

wherein in the formula (M), R 1 -R 16 are the same or different, each independently selected from the group consisting of hydrogen, hydroxyl, halogen, cyano, nitro, amino, amine, aldehyde, carboxyl, ketone, alkoxy and hydrocarbyl, and when two adjacent groups on a benzene ring are each selected from the group consisting of alkoxy and hydrocarbyl, the two adjacent groups may optionally form a ring with each other, the ring selected from the group consisting of a saturated or unsaturated monocyclic ring, a saturated or unsaturated polycyclic ring and a combination thereof; and wherein R 17 to R 24 are the same or different, each independently selected from the group consisting of hydrogen and C 1 -C 10 hydrocarbyl, and the amine, aldehyde, carboxyl, ketone, alkoxy and hydrocarbyl may be optionally substituted by one or more substituents.

2. The catalyst system according to claim 1 , characterized in that the main catalyst comprises (i) a solid catalyst component containing magnesium, titanium, halogen and an internal electron donor compound; (ii) an organic aluminum compound; and optionally (iii) an external electron donor compound.

3. The catalyst system according to claim 2 , characterized in that a molar ratio of the external electron donor compound to titanium element in the solid catalyst component is (0-500):1.

4. The catalyst system according to claim 1 , characterized in that,
in the formula (M), R 1 -R 16 are the same or different, each independently selected from the group consisting of hydrogen, hydroxyl, halogen, cyano, nitro, amino, mono-C 1 -C 10 alkyl amine, bis-C 1 -C 10 alkyl amine, C 1 -C 10 aldehyde, C 1 -C 10 carboxyl, R a C(O)—, R a O—, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 6 -C 20 aryl, C 7 -C 20 aralkyl, 4-12-membered heterocycloalkyl and C 5 -C 20 heteroaryl, and when two adjacent groups on a benzene ring are each selected from the group consisting of R a C(O)—, R a O—, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 6 -C 20 aryl, C 7 -C 20 aralkyl, 4-12-membered heterocycloalkyl and C 5 -C 20 heteroaryl, the two adjacent groups may optionally form a ring with each other, the ring selected from the group consisting of a saturated or unsaturated monocyclic ring, a saturated or unsaturated polycyclic ring and a combination thereof,
wherein R a is selected from the group consisting of C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 6 -C 20 aryl, C 7 -C 20 aralkyl, 4-12-membered heterocycloalkyl and C 5 -C 20 heteroaryl; and
R 17 to R 24 are the same or different, each independently selected from the group consisting of hydrogen, C 1 -C 10 alkyl, C 2 -C 10 alkenyl, C 2 -C 10 alkynyl, C 3 -C 8 cycloalkyl, C 6 -C 10 aryl, C 7 -C 20 aralkyl, 4-12-membered heterocycloalkyl and C 5 -C 20 heteroaryl, and
any one of the alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, heterocycloalkyl and heteroaryl may be optionally substituted by one or more substituents.

5. The catalyst system according to claim 1 , characterized in that, in the formula (M), the substituents are selected from the group consisting of alkyl, alkoxyl, hydroxyl, halogen, cyano, nitro, amino, alkyl substituted amino, aldehyde, carboxyl and a heteroatom-containing group.

6. The catalyst system according to claim 1 , characterized in that, in the formula (M), R 1 to R 16 are the same or different, and are each independently selected from the group consisting of hydrogen, hydroxyl, halogen, cyano, nitro, amino, mono-C 1 -C 6 alkyl amine, bis-C 1 -C 6 alkyl amine, C 1 -C 6 aldehyde, C 1 -C 6 carboxyl, R a C(O)—, R a O—, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 6 -C 10 aryl, C 7 -C 10 aralkyl, 4-6-membered heterocycloalkyl and C 5 -C 10 heteroaryl, wherein R a is selected from the group consisting of C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 6 -C 10 aryl, C 7 -C 10 aralkyl, 4-6-membered heterocycloalkyl and C 5 -C 10 heteroaryl.

7. The catalyst system according to claim 1 , characterized in that, in the formula (M), R 1 , R 4 , R 5 , R 8 , R 9 , R 12 , R 13 and R 16 are each independently selected from the group consisting of hydrogen and C 1 -C 6 alkyl; R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 are each independently selected from the group consisting of hydroxyl, amino, halogen, C 1 -C 6 aldehyde, C 1 -C 6 alkoxyl and halogen substituted C 1 -C 6 alkoxyl.

8. The catalyst system according to claim 1 , characterized in that, in the formula (M), R 17 to R 24 are each independently selected from the group consisting of hydrogen and C 1 -C 10 alkyl.

9. The catalyst system according to claim 1 , characterized in that, the twelve-membered ring compound represented by the formula (M) is represented by formula (N),

10. The catalyst system according to claim 2 , characterized in that the internal electron donor compound is selected from one or more of a diether compound, an alcohol ester compound, an aromatic carboxylic acid ester compound, a succinate compound and a ketone compound.

11. The catalyst system according to claim 10 , characterized in that, the alcohol ester compound is a glycol ester compound represented by formula B,

wherein, in the formula B, R 1 and R 2 are the same or different, each independently selected from the group consisting of C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 3 -C 20 cycloalkyl, C 6 -C 20 aryl, C 7 -C 20 alkaryl, C 7 -C 20 aralkyl and C 10 -C 20 fused ring aryl, the alkyl, alkenyl, cycloalkyl, aryl, alkaryl, aralkyl and fused ring aryl optionally substituted by one or more substituents selected from the group consisting of C 1 -C 10 alkyl, C 1 -C 10 alkoxyl, hydroxyl, halogen, cyano, nitro, amino, mono-C 1 -C 6 alkyl amine, bis-C 1 -C 6 alkyl amine, aldehyde, carboxyl and a heteroatom; and M is a divalent linking group;
the diether compound is a 1,3-diether compound represented by formula E,

wherein, in the formula E, R I , R II , R III , R IV , R V and R VI are the same or different, and are each independently selected from the group consisting of hydrogen, halogen, C 1 -C 20 alkyl, C 3 -C 20 cycloalkyl, C 6 -C 20 aryl, C 7 -C 20 aralkyl and C 7 -C 20 alkaryl; R VII and R VIII are the same or different, and are each independently selected from the group consisting of C 1 -C 20 alkyl, C 3 -C 20 cycloalkyl, C 6 -C 20 aryl, C 7 -C 20 aralkyl and C 7 -C 20 alkaryl, wherein any one of the alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl and alkaryl may be optionally substituted by one or more substituents which are selected from the group consisting of hydroxyl, halogen, cyano, nitro, amino, mono-C 1 -C 10 alkyl amine, bis-C 1 -C 10 alkyl amine, aldehyde, carboxyl and a heteroatom; or, two or more of R I , R II , R III , R IV , R V and R VI are bonded to each other to form a saturated or unsaturated monocyclic or polycyclic ring;
a structure of the aromatic carboxylic acid ester compound is

Assignees

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

Inventors

• Lin Jie
• Zhang Xiaofan
• Huang Ting
• Zhang Junhui
• Zhou Junling
• Sun Zhufang
• Xia Xianzhi
• Zhao Hui
• Guo Zifang
• Zhao Jin
• Liu Haitao
• Fu Meiyan
• Zhang Jigui
• Qi Lin
• Yan Lian
• Cen Wei
• Wang Yu

Classifications

• C07C47/575 Primary

  containing ether groups, [IMAGE cpc-sch-C07C-0958.gif] groups,[IMAGE cpc-sch-C07C-0959.gif] groups, or[IMAGE cpc-sch-C07C-0960.gif] groups · CPC title

• C07C43/21

  containing rings other than six-membered aromatic rings · CPC title

• C08F110/06

  Propene · CPC title

• C07C2603/92

  with a condensed ring system consisting of at least two mutually uncondensed aromatic ring systems, linked by an annular structure formed by carbon chains on non-adjacent positions of the aromatic system, e.g. cyclophanes · CPC title

• C08F10/06 Primary

  Propene · CPC title