Method to prepare ethylene copolymers

Patent metadata

Field	Value
Publication number	US-2021024670-A1
Application number	US-202017067287-A
Country	US
Kind code	A1
Filing date	Oct 9, 2020
Priority date	Feb 11, 2014
Publication date	Jan 28, 2021
Grant date	—

Abstract

In both catalyst systems, the R groups can be independently selected from any number of substituents, including, for example, H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group, among others.

First claim

1 .- 44 . (canceled)

45 . A catalyst composition comprising a first catalyst compound and a second catalyst compound that are co-supported forming a commonly supported catalyst system, wherein the first catalyst compound comprises the following formula:
(C 5 H a R 1 b )(A)(C 5 H c R 2 d )HfX 2 wherein each R 1 is independently H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group; each R 2 is independently H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group; a and c are ≥3; a+b=c+d=5; at least one R 1 and at least one R 2 is a hydrocarbyl or substituted hydrocarbyl group; adjacent groups R 1 and R 2 groups may be coupled to form a ring; and each X is independently a leaving group selected from a labile hydrocarbyl, substituted hydrocarbyl, or heteroatom group, or a divalent radical that links to an R 1 or R 2 group; and A is at least one of a bridging group selected from a divalent hydrocarbon, a divalent hydrocarbon containing at least one Group 13 to 16 atom or a combination thereof, and the second catalyst compound comprises at least one of the following formulas:

wherein each R 3 is independently H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group; R 4 is a hydrocarbyl group, a substituted hydrocarbyl group, or a heteoatom group; each R 5 is independently H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group; wherein R 3 , R 4 , and R 5 may be the same or different; wherein R 3 , R 4 , or R 5 groups may be joined with R 3 , R 4 , or R 5 groups on an opposing cyclopentadienyl structure to form one or more bridges if the number of atoms connecting the two cyclopentadienyl rings is ≥3; and each X is independently a leaving group selected from a labile hydrocarbyl, a substituted hydrocarbyl, a heteroatom group, or a divalent radical that links to a R 3 , R 4 , or R 5 substituent.

46 . The catalyst composition of claim 45 , wherein the least one Group 13 to 16 atom are selected from carbon, oxygen, nitrogen, silicon, aluminum, boron, germanium, tin and combinations thereof.

47 . The catalyst composition of claim 45 , wherein the at least one bridging group is selected from a C 1 to C 6 alkylene, a substituted C 1 to C 6 alkylene, R′ 2 C<, R′ 2 Si<, >Si(R′) 2 Si(R′ 2 )<, R′ 2 Ge<, and R′P<, wherein R′ is independently selected from the group consisting of a hydride, a hydrocarbyl, a substituted hydrocarbyl, a halocarbyl, substituted halocarbyl, a hydrocarbyl-substituted organometalloid, a halocarbyl-substituted organometalloid, disubstituted boron, a disubstituted Group 15 atom, a substituted Group 16 atom and a halogen radical.

48 . The catalyst composition of claim 47 , wherein two or more R′ form a ring.

49 . The catalyst composition of claim 45 , wherein the at least one bridging group is selected from a divalent C 1 to C 20 hydrocarbyls and C 1 to C 20 hydrocarbonyls containing one to three heteroatoms.

50 . The catalyst composition of claim 45 , wherein the at least one bridging group is a cyclic structure having 4 to 10 ring members.

51 . The catalyst composition of claim 45 , wherein the second catalyst compound comprises at least one compound with the following formula:

52 . The catalyst composition of claim 45 , wherein the second catalyst compound comprises at least one compound with the following formula:

53 . The catalyst composition of claim 45 , wherein the second catalyst compound comprises at least one compound with the following formula:

wherein each R 4A is independently a methyl, ethyl, propyl, pentyl, hexyl, octyl, nonyl, dodecyl, phenethyl, or other hydrocarbyl.

54 . The catalyst composition of claim 45 , wherein the second catalyst compound comprises at least one compound with the following formula:

55 . The catalyst composition of claim 45 , wherein the second catalyst compound comprises at least one compound with the following formula:

56 . The catalyst composition of claim 45 , wherein the ratio of the first catalyst compound to the second catalyst compound is between about 10:1 to 1:10.

57 . The catalyst composition of claim 45 , wherein the ratio of the first catalyst compound to the second catalyst compound is between about 3:1 to 1:3.

58 . The catalyst composition of claim 45 , comprising an activator comprising an acid derived from a weakly coordinating anion.

59 . The catalyst composition of claim 58 , wherein the activator comprises an aluminoxane compound, an organoboron, an organoaluminum compound or combinations thereof.

60 . The catalyst composition of claim 58 , wherein the activator comprises methyl aluminoxane or modified methylauminoxane.

61 . The catalyst composition of claim 59 , wherein the organoboron compound comprises BAr a R b , or AlAr a R b , wherein a+b=3, a ≥2, and Ar is an aryl or heteroaryl group comprising a substituent containing fluorine and wherein R is independently H, a hydrocarbyl group, a substituted hydrocarbyl group or a heteroatom group.

62 . The catalyst composition of claim 61 , wherein Ar is C 6 F 5 , C 10 F 7 , or C 6 H 3 (CF 3 ) 2 .

63 . The catalyst composition of claim 45 , comprising a support comprising a mineral, a clay, a metal oxide, a metalloid oxide, a mixed metal oxide, a mixed metalloid oxide, a mixed metal-metalloid oxide, a polymer, or any combinations thereof.

64 . The catalyst composition of claim 63 , wherein the support has been thermally treated and/or chemically treated with an acid, an organosilane, an organoaluminum, or a fluoriding agent, or any combinations thereof.

Assignees

• Univation Tech Llc

Inventors

• Rix Francis C
• Lue Ching-Tai
• Harlan C Jeff
• Mccullough Laughlin G

Classifications

• C08F4/65925 Primary

  two cyclopentadienyl rings being mutually non-bridged · CPC title

• C08F210/16 Primary

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

• C08F4/65927

  two cyclopentadienyl rings being mutually bridged · CPC title

• C08F210/18

  with non-conjugated dienes, e.g. EPT rubbers · CPC title

• C08F4/65912

  in combination with an organoaluminium compound · CPC title