Olefin polymerization catalyst comprising cyclotriveratrylene and derivatives thereof

Patent metadata

Field	Value
Publication number	US-11401356-B2
Application number	US-201816631482-A
Country	US
Kind code	B2
Filing date	Jul 19, 2018
Priority date	Jul 19, 2017
Publication date	Aug 2, 2022
Grant date	Aug 2, 2022

Abstract

The present invention discloses a Ziegler-Natta catalyst system for olefin polymerization, comprising at least one compound represented by formula (I) as (i) an internal electron donor, (ii) an external electron donor, or (iii) the both, wherein M1, M2, M3, M4, M5, M6, M1′, M2′, M3′, M4′, M5′ and M6′ are each independently selected from the group consisting of hydrogen, hydroxy, amino, aldehyde group, carboxy, acyl, halogen atoms, —R1 and —OR2, wherein R1 and R2 are each independently a C1-C10 hydrocarbyl, which is unsubstituted or substituted by a substituent selected from the group consisting of hydroxy, amino, aldehyde group, carboxy, acyl, halogen atoms, C1-C10 alkoxy and heteroatoms; and wherein, when among M1-M6 and M1′-M6′, any two adjacent groups on the same phenyl ring are each independently selected from the group consisting of R1 and —OR2, the two adjacent groups may optionally be linked to form a ring, with a proviso that M1, M2, M3, M4, M5, M6, M1′, M2′, M3′, M4′, M5′ and M6′ are not simultaneously hydrogen.

First claim

What is claimed is:

1. A Ziegler-Natta catalyst system for olefin polymerization, comprising at least one compound represented by formula (I) as (i) an internal electron donor, (ii) an external electron donor, or (iii) the both,

wherein M 1 , M 2 , M 3 , M 4 , M 5 , M 6 , M 1 ′, M 2 ′, M 3 ′, M 4 ′, M 5 ′ and M 6 ′ are each independently selected from the group consisting of hydrogen, hydroxy, amino, aldehyde group, carboxy, acyl, halogen atoms, —R 1 and —OR 2 , where R 1 and R 2 are each independently a C 1 -C 10 hydrocarbyl, which is unsubstituted or substituted by a substituent selected from the group consisting of hydroxy, amino, aldehyde group, carboxy, acyl, halogen atoms, C 1 -C 10 alkoxy and heteroatoms; and wherein, when among M 1 -M 6 and M 1 ′-M 6 ′, any two adjacent groups on the same phenyl ring are each independently selected from the group consisting of R 1 and —OR 2 , the two adjacent groups may optionally be linked to form a ring,
with a proviso that M 1 , M 2 , M 3 , M 4 , M 5 , M 6 , M 1 ′, M 2 ′, M 3 ′, M 4 ′, M 5 ′ and M 6 ′ are not simultaneously hydrogen.

2. The catalyst system according to claim 1 , wherein the compound represented by formula (I) is selected from those represented by formula (I′):

wherein M 1 , M 2 , M 3 , M 4 , M 5 and M 6 are each independently selected from the group consisting of hydrogen, hydroxy, amino, aldehyde group, carboxy, acyl, halogen atoms, —R 1 and —OR 2 , where R 1 and R 2 are each independently a C 1 -C 10 hydrocarbyl, which is unsubstituted or substituted by a substituent selected from the group consisting of hydroxy, amino, aldehyde group, carboxy, acyl, halogen atoms, C 1 -C 10 alkoxy and heteroatoms, with a proviso that when two adjacent groups on the same phenyl ring, i.e., M 1 and M 2 , or M 3 and M 4 , or M 5 and M 6 , are each independently selected from the group consisting of —R 1 and —OR 2 , the two adjacent groups may optionally be linked to form a ring, and further with a proviso that M 1 , M 2 , M 3 , M 4 , M 5 and M 6 are not simultaneously hydrogen.

3. The catalyst system according to claim 2 , wherein in the formula (I′), M 1 , M 2 , M 3 , M 4 , M 5 and M 6 are each independently selected from the group consisting of hydroxy, amino, aldehyde group, halogen atoms, —R 1 and —OR 2 , where R 1 and R 2 are each independently selected from the group consisting of unsubstituted or halogen-substituted C 1 -C 10 hydrocarbyl groups.

4. The catalyst system according to claim 1 , wherein the at least one compound represented by formula (I) is selected from the group consisting of:
Compound A: M 1 =M 2 =M 3 =M 4 =M 5 =M 6 =OCH 3 , M 1 ′=M 2 ′=M 3 ′=M 4 ′=M 5 ′=M 6 ′=H;
Compound B: M 1 =M 2 =M 3 =M 4 =M 5 =M 6 =OCH 2 CH 3 , M 1 ′=M 2 ′=M 3 ′=M 4 ′=M 5 ′=M 6 ′=H
Compound C: M 1 =M 2 =M 3 =M 4 =M 5 =M 6 =OCH 2 CH 2 CH 3 , M 1 ′=M 2 ′=M 3 ′=M 4 ′=M 5 ′=M 6 ′=H;
Compound D: M 1 =M 2 =M 3 =M 4 =M 5 =M 6 =OCH(CH 3 ) 2 , M 1 ′=M 2 ′=M 3 ′=M 4 ′=M 5 ′=M 6 ′=H;
Compound E: M 1 =M 2 =M 3 =M 4 =M 5 =M 6 =OCH 2 CH 2 CH 2 CH 3 , M 1 ′=M 2 ′=M 3 ′=M 4 ′=M 5 ′=M 6 ′=H;
Compound F: M 1 =M 3 =M 5 =OCH 3 , M 2 =M 4 =M 6 =OCH 2 CH 3 , M 1 ′=M 2 ′=M 3 ′=M 4 ′=M 5 ′=M 6 ′=H;
Compound G: M 1 =M 3 =M 5 =OCH 3 , M 2 =M 4 =M 6 =OCH 2 CH 2 CH 3 , M 1 ′=M 2 ′=M 3 ′=M 4 ′=M 5 ′=M 6 ′=H;
Compound H: M 1 =M 3 =M 5 =OCH 3 , M 2 =M 4 =M 6 =OCH 2 CH 2 CH 2 CH 3 , M 1 ′=M 2 ′=M 3 ′=M 4 ′=M 5 ′=M 6 ′=H;
Compound I: M 1 =M 2 =M 3 =M 4 =M 5 =M 6 =OH, M 1 ′=M 2 ′=M 3 ′=M 4 ′=M 5 ′=M 6 ′=H;
Compound J: M 1 =M 3 =M 5 =OCH 3 , M 2 =M 4 =M 6 =OH, M 1 ′=M 2 ′=M 3 ′=M 4 ′=M 5 ′=M 6 ′=H;
Compound K: M 1 =M 3 =M 5 =OCH 3 , M 2 =M 4 =M 6 =NH 2 , M 1 ′=M 2 ′=M 3 ′=M 4 ′=M 5 ′=M 6 ′=H;
Compound L: M 1 =M 3 =M 5 =OCH 3 , M 2 =M 4 =M 6 =Cl, M 1 ′=M 2 ′=M 3 ′=M 4 ′=M 5 ′=M 6 ′=H;
Compound M: M 1 =M 3 =M 5 =OCH 3 , M 2 =M 4 =M 6 =Br, M 1 ′=M 2 ′=M 3 ′=M 4 ′=M 5 ′=M 6 ′=H;
Compound N: M 1 =M 3 =M 5 =OCH 3 , M 2 =M 4 =M 6 =I, M 1 ′=M 2 ′=M 3 ′=M 4 ′=M 5 ′=M 6 ′=H;
Compound O: M 1 =M 3 =M 5 =OCH 3 , M 2 =M 4 =M 6 =CHO, M 1 ′=M 2 ′=M 3 ′=M 4 ′=M 5 ′=M 6 ′=H;
Compound P: M 1 =M 3 =M 5 =OCH 3 , M 2 =M 4 =M 6 =OCH 2 CH 2 CH 2 Br, M 1 ′=M 2 ′=M 3 ′=M 4 ′=M 5 ′=M 6 ′=H;
Compound Q: M 1 =M 2 =M 3 =M 4 =M 5 =M 6 =OCH 2 CH 2 Cl, M 1 ′=M 2 ′=M 3 ′=M 4 ′=M 5 ′=M 6 ′=H;
Compound R: M 1 =M 3 =M 5 =OH, M 2 =M 4 =M 6 =OCH 2 CH 3 , M 1 ′=M 2 ′=M 3 ′=M 4 ′=M 5 ′=M 6 ′=H;
Compound S: M 1 =M 2 =M 3 =M 4 =M 5 =M 6 =OCH 3 , M 1 ′=Cl, M 2 ′=M 3 ′=M 4 ′=M 5 ′=M 6 ′=H;
Compound T: M 1 =M 2 =M 3 =M 4 =M 5 =M 6 =OCH 3 , M 1 ′=M 3 ′=Cl, M 2 ′=M 4 ′=M 5 ′=M 6 ′=H;
Compound U: M 1 =M 2 =M 3 =M 4 =M 5 =M 6 =OCH 3 , M 1 ′=M 3 ′=M 5 ′=Cl, M 2 ′=M 4 ′=M 6 =H; and
Compound V: M 1 =M 2 =M 3 =M 4 =M 5 =M 6 =OCH 3 , M 1 ′=M 3 ′=M 6 ′=Cl, M 2 ′=M 4 ′=M 5 =H.

5. A solid catalyst component for olefin polymerization, comprising magnesium, titanium, halogen and an internal electron donor compound, wherein the internal electron donor compound comprises at least one compound of the formula (I) as defined in claim 1 .

6. The solid catalyst component according to claim 5 , comprising at least one titanium compound and the at least one compound represented by formula (I), supported on a magnesium halide.

7. The solid catalyst component according to claim 5 , wherein a molar ratio of the at least one compound represented by formula (I) to magnesium ranges from 0.0005:1 to 0.1:1, or from 0.001:1 to 0.1:1, or from 0.002:1 to 0.05:1.

8. The solid catalyst component according to claim 6 , wherein the at least one titanium compound is selected from the group consisting of titanium trichloride and those having general formula Ti(OR) n X′ 4-n , where R is a C 1 -C 8 hydrocarbyl, X′ is a halogen atom, and 0≤n≤4; or the at least one titanium compound is selected from the group consisting of titanium trichloride, titanium tetrachloride, titanium tetrabromide, tetraethoxy titanium, triethoxy titanium chloride, diethoxy titanium dichloride, tetrabutoxy titanium and ethoxy titanium trichloride.

9. The solid catalyst component according to claim 5 , comprising a reaction product of:
1) a magnesium halide-alcohol adduct;
2) a titanium compound;
3) an internal electron donor compound; and
4) optionally, an organic aluminum compound,
wherein the internal electron donor compound comprises the at least one compound represented by formula (I).

10. The solid catalyst component according to claim 9 , having at least one feature of the followings:
the organic aluminum compound is of general formula AlR 1 a X 1 b H c , where R 1 is a C 1 -C 14 hydrocarbyl; X 1 is a halogen atom; a, b and c are each a number of from 0 to 3; and a+b+c=3;
the content of the at least one compound represented by formula (I) is at least 0.0005 moles, or at least 0.001 moles, or from 0.001 to 0.1 moles, relative to one mole of magnesium;
the magnesium halide-alcohol adduct is of general formula MgX 2 .m(ROH), where X is Cl, Br or I; R is a C 1 -C 6 alkyl; and m ranges from 0.5 to 4.0, or from 2.5 to 4.0;
the titanium compound is of general formula Ti(OR 2 ) n X 2 4-n , where R 2 is a C 1 -C 8 hydrocarbyl; X 2 is Cl, Br or I; and 0≤n≤4; or the titanium compound is selected from the group consisting of TiCl 4 , Ti(OC 2 H 5 )Cl 3 , Ti(OCH 3 )Cl 3 , Ti(OC 4 H 9 )Cl 3 , Ti(OC 4 H 9 ) 4 and mixtures thereof; and
in a reaction for forming the solid catalyst component, relative to one mole of magnesium, the amount of the titanium compound used ranges from 0.1 to 100 moles, or from 1 to 50 moles, and the amount of the or

Assignees

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

Inventors

• Huang Ting
• Guo Zifang
• Sun Zhufang
• Zhou Junling
• Xie Lunjia
• Yang Hongxu
• Li Bingyi
• Gou Qingqiang
• Huang Tingjie
• Kou Peng
• Zhang Xiaofan
• Fu Meiyan
• Lin Jie
• Ma Yonghua

Classifications

• C07C43/225

  containing halogen · CPC title

• C08F2410/01

  Additive used together with the catalyst, excluding compounds containing Al or B · CPC title

• C07C43/21

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

• C08F10/00 Primary

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

• C08F4/6541

  and metals of C08F4/64 or compounds thereof · CPC title