Bridged Bis(Indenyl) Transitional Metal Complexes, Production, and Use Thereof

Patent metadata

Field	Value
Publication number	US-2018201630-A1
Application number	US-201715852410-A
Country	US
Kind code	A1
Filing date	Dec 22, 2017
Priority date	Jan 13, 2017
Publication date	Jul 19, 2018
Grant date	—

Abstract

The present disclosure relates to bridged metallocene catalysts that include at least one indenyl ligand substituted at the 2-position with a C 3 -C 10 branched alkyl, such as isopropyl. Catalyst systems including the catalysts, polymerization processes using the catalysts, and polymers made using the catalysts are also described.

First claim

What is claimed is:

1 . A catalyst compound represented by Formula (I):

wherein M 1 is selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten;
R 1 and R 2 are independently hydrogen, halogen, hydroxyl, hydrocarbyl, or substituted hydrocarbyl;
R 3 is linear alkyl;
R 9 is C 3 -C 10 branched alkyl;
each of R 3 , R 4 , R 6 , R 7 , R 8 , R 10 , R 11 , R 12 , and R 13 is independently hydrogen, halogen, C 1 -C 40 hydrocarbyl or C 1 -C 40 substituted hydrocarbyl, —NR′ 2 , —SR′, —OR, —OSiR′ 3 , —PR′ 2 , where each R′ is hydrogen, halogen, C 1 -C 10 alkyl, or C 6 -C 10 aryl;
R 5 is hydrogen, halogen, C 1 -C 40 hydrocarbyl or C 1 -C 40 substituted hydrocarbyl, —NR′ 2 , —R′, —OR, —OSiR′ 3 , —PR′ 2 , where each R′ is hydrogen, halogen, C 1 -C 10 alkyl, or C 6 -C 10 aryl, or two or more adjacent radicals R 5 to R 8 together form one or more saturated or unsaturated rings;
R 19 is —B(R 20 )—, —Al(R 20 )—, —Ge—, —Sn—, —O—, —S—, —SO—, —SO 2 —, —N(R 20 )—, —CO—, —P(R 20 )—, or —P(O)(R 20 )—, an amidoborane radical or one of the following:

wherein each of R 20 , R 21 , R 22 is independently hydrogen, halogen, C 1 -C 20 alkyl, C 1 -C 20 fluoroalkyl or silaalkyl, C 6 -C 30 aryl, C 6 -C 30 fluoroaryl, C 1 -C 20 alkoxy, C 2 -C 20 alkenyl, C 7 -C 40 arylalkyl, C 8 -C 40 arylalkenyl, C 7 -C 40 alkylaryl, or one R 20 and one R 21 , together with the atoms in R 19 connecting them, form one or more rings; M 2 is one or more carbons, silicon, germanium or tin;
R 14 is substituted or unsubstituted C 6 -C 10 aryl;
R 18 is hydrogen, halogen, substituted or unsubstituted C 3 -C 20 alkyl, substituted or unsubstituted C 6 -C 40 aryl, C 2 -C 10 alkenyl, —NR′ 2 , —SR′, —OR, —OSiR′ 3 or —PR′ 2 , wherein each R′ is hydrogen, halogen, C 1 -C 10 alkyl, or C 6 -C 10 aryl;
R 15 and R 17 are independently hydrogen, C 2 -C 20 alkyl which may be substituted, C 6 -C 40 aryl which may be substituted, or C 2 -C 10 alkenyl; and
R 16 is selected from hydrogen, halogen, C 1 -C 10 alkyl which may be substituted, C 6 -C 20 aryl which may be substituted, C 2 -C 10 alkenyl which may be substituted, or two or more adjacent radicals R 15 to R 18 together form one or more rings, and —XR′n, wherein X is a Group 14-17 heteroatom having an atomic weight of 13 to 79 and R′ is one of hydrogen, halogen, C 1 -C 10 alkyl, or C 6 -C 10 aryl and n is 0, 1, 2, or 3.

2 . The catalyst compound of claim 1 , wherein R 9 is isopropyl.

3 . The catalyst compound of claim 1 , wherein R 14 is phenyl.

4 . The catalyst compound of claim 1 , wherein R 5 is

5 . The catalyst compound of claim 1 , wherein R 6 and R 7 or R 7 and R 8 combine to form a cyclobutyl ring, a cyclopentyl ring or cyclohexyl ring.

6 . The catalyst compound of claim 1 , wherein R 3 is methyl.

7 . The catalyst compound of claim 1 , wherein R 15 and R 17 are hydrogen.

8 . The catalyst compound of claim 1 , wherein R 6 and R 7 or R 7 and R 8 combine to form a cyclobutyl ring, a cyclopentyl ring or cyclohexyl ring.

9 . The catalyst compound of claim 8 , wherein R 6 and R 7 combine to form a cyclopentyl ring.

10 . The catalyst compound of claim 1 , wherein R 16 is —NR′ 2 , —SR′, —OR′, —OSiR′ 3 , —SiR′ 3 , or —PR′ 2 , wherein R′ is one of a hydrogen atom, halogen, C 1 -C 10 alkyl, or C 6 -C 10 aryl.

11 . The catalyst compound of claim 1 , wherein R 15 is n-butyl-, iso-butyl-, or tert-butyl and R 16 is —OR′ wherein R′ is C 1 -C 10 alkyl.

12 . The catalyst compound of claim 1 , represented by the formula (II):

wherein M 1 , R 1 , R 2 , R 3 , R 4 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 17 , and R 19 are as defined in claim 1 ,
wherein each of R 18 , R 23 , and R 27 is independently hydrogen, halogen, substituted or unsubstituted C 3 -C 20 alkyl, substituted or unsubstituted C 6 -C 40 aryl, C 2 -C 10 alkenyl, —NR′ 2 , —SR′, —OR, —OSiR′ 3 or —PR′ 2 , wherein each R′ is hydrogen, halogen, C 1 -C 10 alkyl, or C 6 -C 10 aryl;
R 24 and R 26 are independently substituted or unsubstituted C 2 -C 20 alkyl, substituted or unsubstituted C 6 -C 40 aryl, C 2 -C 10 alkenyl; and
R 16 and R 25 are independently —(XR′ n ), wherein X is a Group 14-17 heteroatom having an atomic weight of 13 to 79 and R′ is one of hydrogen, halogen, C 1 -C 10 alkyl, or C 6 -C 10 aryl and n is 0, 1 2, or 3.

13 . The catalyst compound of claim 12 , wherein R 16 and R 25 are independently —NR′ 2 , —SR′, —OR′, —OSiR′ 3 , —SiR′ 3 , or —PR′ 2 , wherein R′ is one of hydrogen, halogen, C 1 -C 10 alkyl, or C 6 -C 10 aryl.

14 . The catalyst compound of claim 12 , wherein R 15 , R 16 and R 17 is hydrogen, R 24 and R 26 are selected from the group consisting of n-butyl-, iso-butyl-, and tert-butyl groups and R 25 is —OR′, wherein R′ is a C 1 -C 10 alkyl group.

15 . The catalyst compound of claim 12 , wherein:
R 1 and R 2 are methyl; each of R 4 , R 6 , R 7 , and R 11 is independently hydrogen or C 1 -C 10 alkyl; each of R 15 , R 16 , R 17 , R 18 , R 23 , and R 27 is hydrogen; R 19 is —SiR″ 2 —, wherein each R″ is independently hydrogen or methyl; R 24 and R 26 are tert-butyl; and R 25 is hydrogen or methoxy.

16 . A catalyst compound selected from:
dimethylsiladiyl (2-methyl, 4-[3′,5′-di-tert-butyl-4′-methoxyphenyl], 1,5,6,7-tetrahydro-s-indacenyl)(2-isopropyl, 4-[o-biphenyl] indenyl)Zr(CH 3 ) 2 ; dimethylsiladiyl (2-ethyl, 4-[3′,5′-di-tert-butyl-4′-methoxyphenyl], 1,5,6,7-tetrahydro-s-indacenyl)(2-isopropyl, 4-[o-biphenyl] indenyl)Zr(CH 3 ) 2 ; dimethylsiladiyl (2-propyl, 4-[3′,5′-di-tert-butyl-4′-methoxyphenyl], 1,5,6,7-tetrahydro-s-indacenyl)(2-isopropyl, 4-[o-biphenyl] indenyl)Zr(CH 3 ) 2 ; dimethylsiladiyl (2-butyl, 4-[3′,5′-di-tert-butyl-4′-methoxyphenyl], 1,5,6,7-tetrahydro-s-indacenyl)(2-isopropyl, 4-[o-biphenyl] indenyl)Zr(CH 3 ) 2 ; dimethylsiladiyl (2-methyl, 4-[3′,5′-bistrifluoromethyl-4′-methoxyphenyl], 1,5,6,7-tetrahydro-s-indacenyl)(2-isopropyl, 4-[o-biphenyl] indenyl)Zr(CH 3 ) 2 ; dimethylsiladiyl (2-ethyl, 4-[3′,5′-bistrifluoromethyl-4′-methoxyphenyl], 1,5,6,7-tetrahydro-s-indacenyl)(2-isopropyl, 4-[o-biphenyl] indenyl)Zr(CH 3 ) 2 ; dimethylsiladiyl (2-propyl, 4-[3′,5′-bistrifluoromethyl-4′-methoxyphenyl], 1,5,6,7-tetrahydro-s-indacenyl)(2-isopropyl, 4-[o-biphenyl] indenyl)Zr(CH 3 ) 2 ; dimethylsiladiyl (2-butyl, 4-[3′,5′-bistrifluoromethyl-4′-methoxyphenyl], 1,5,6,7-tetrahydro-s-indacenyl)(2-isopropyl, 4-[o-biphenyl] indenyl)Zr(CH 3 ) 2 ; dimethylsiladiyl (2-methyl, 4-[3′,5′-di-iso-propyl-4′-methoxyphenyl], 1,5,6,7-tetrahydro-s-indacenyl)(2-isopropyl, 4-[o-biphenyl] indenyl)Zr(CH 3 ) 2 ; dimethylsiladiyl (2-ethyl, 4-[3′,5′-di-iso-propyl-4′-methoxyphenyl], 1,5,6,7-tetrahydro-s-indacenyl)(2-isopropyl, 4-[o-biphenyl] indenyl)Zr(CH 3 ) 2 ; dimethylsiladiyl (2-propyl, 4-[3′,5′-di-iso-propyl-4′-methoxyphenyl], 1,5,6,7-tetrahydro-s-indacenyl)(2-isopropyl, 4-[o-biphenyl] indenyl)Zr(CH 3 ) 2 ; dimethylsiladiyl (2-butyl, 4-[3′,5′-di-iso-pr

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Yang Jian
• Lian Xiongdong

Classifications

• B01J2531/48

  Zirconium · CPC title

• C07F7/006 Primary

  Chemistry & Metallurgy · mapped topic

• C08F210/16

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

• C08F4/76

  selected from titanium, zirconium, hafnium, vanadium, niobium or tantalum · CPC title

• B01J31/2295

  Cyclic compounds, e.g. cyclopentadienyls · CPC title