Alkene functionalized activators and their use in electrical applications

Patent metadata

Field	Value
Publication number	US-2023183401-A1
Application number	US-202017607638-A
Country	US
Kind code	A1
Filing date	Apr 30, 2020
Priority date	Apr 30, 2019
Publication date	Jun 15, 2023
Grant date	—

Abstract

Processes of polymerizing polyolefins and synthesis of activators. The polymerization processes include polymerizing one or more (C2-C12)α-olefin monomers in the presence of at least one catalyst and at least one co-catalyst to produce a polyolefin. The co-catalyst includes a cation and an anion, in which the anion has a structure having a vinyl terminated alkene, one boron atom or more than one boron atoms, and at least four halogen atoms. The anion of the co-catalysts is incorporated into a polymer chain of the polyolefin.

First claim

1 . A polymerization process comprising:
polymerizing one or more (C 2 -C 12 )α-olefin monomers in the presence of at least one catalyst and at least one co-catalyst to produce a polyolefin;
wherein the co-catalyst comprises a cation and an anion, wherein the anion has a structure having a vinyl terminated alkene, one boron atom or more than one boron atoms, and at least four halogen atoms; and
inserting the anion of the co-catalyst into a polymer chain of the polyolefin;
wherein the polyolefin comprises:
(1) greater than 0 and less than 1 mole % of the anion of the co-catalyst based on the molar composition of the polyolefin, and
(2) a density in the range from 0.853 to 0.920 g/cm 3 .

2 . A polymerization process comprising:
polymerizing one or more (C 2 -C 12 )α-olefin monomers in the presence of at least one catalyst and at least one co-catalyst to produce a polyolefin; wherein the co-catalyst comprises a cation and an anion, the anion has a structure according to formula (I):

where R 1 is an unsaturated (C 2 -C 20 )hydrocarbyl having a vinyl terminated alkene;
and each X is independently a halogen atom; and

inserting the anion of the co-catalyst into a polymer chain of the polyolefin.

3 . The process of claim 2 , wherein the polyolefin has a dissipation factor less than that of a corresponding polyolefin composition produced under identical polymeric conditions except the molar amount of the anion of formula (I) is replaced by a comparative anion having the formula (Ia):

4 . A polymerization process comprising:
copolymerizing ethylene monomer and one or more (C 3 -C 12 )α-olefin monomers in the presence of at least one catalyst and at least one co-catalyst to produce a polyolefin
wherein the co-catalyst comprises a cation and an anion, the anion according to formula (II):
− BR 2 R 3 R 4 R 5   (II)

where R 2 , R 3 , R 4 and R 5 is chosen from (C 1 -C 40 )hydrocarbyl, wherein each (C 1 -C 40 )hydrocarbyl is substituted with at least one halogen, and wherein at least one (C 1 -C 40 )hydrocarbyl is substituted with a vinyl terminated alkene; and

inserting the anion of the co-catalyst into a polymer chain of the polyolefin, wherein the polyolefin comprises less than 1 mole percent of the anion of the co-catalyst.

5 . The polymerization process of claim 1 , wherein the vinyl terminated alkene has a structure according to formula (III):

where n is an integer from 1 to 10.

6 . The polymerization process of any one of claim 1 , wherein the vinyl terminated alkene has a structure according to formula (V):

where y is an integer from 1 to 10, and x is 0, 1, 2, and 3.

7 . The polymerization process of claim 5 , wherein the vinyl terminated alkene according to formula (V) has a structure according to formula (IV):

where y and x are as defined in claim 5 .

8 . The polymerization process of claim 1 , wherein the ethylene-based polymer has a dissipation factor of less than 0.10 at a frequency of 100 Hz and a temperature of 130° C. or the ethylene-based polymer has a dissipation factor of less than 1.00 at a frequency of 10 Hz and a temperature of 130° C.

9 . (canceled)

10 . The polymerization process of claim 1 , wherein the ethylene-based polymer has a dissipation factor of less than 10 at a frequency of 1.0 Hz and a temperature of 130° C. or the ethylene-based polymer has a dissipation factor of less than 100 at a frequency of 0.10 Hz and a temperature of 130° C.

11 . (canceled)

12 . The polymerization process of claim 1 , wherein the cation of the co-catalyst is + N(H)R N 3 , where each R N is chosen from (C 1 -C 20 )alkyl or (C 6 -C 20 )aryl.

13 . The polymerization process of claim 1 , wherein the cation of the co-catalyst is + N(H)R N 3 , where at least two R N are chosen from (C 10 -C 20 )alkyl.

14 . The polymerization process of claim 1 , wherein the cation of the co-catalyst is + C(C 6 H 5 ) 3 .

15 . The polymerization process of claim 1 , wherein the cation of the co-catalyst is + C(C 6 H 4 R C ) 3 , where R C is (C 1 -C 20 )alkyl.

16 . The polymerization process of claim 1 , wherein the polyolefin is a polyethylene, polyoctene, or an ethylene-based copolymer.

17 .- 20 . (canceled)

21 . The polymerization process of claim 1 , wherein each X is a chlorine atom.

22 .- 25 . (canceled)

Assignees

• Dow Global Technologies Llc
• Texas A & M Univ Sys

Inventors

• Keaton Richard J
• Ozerov Oleg V
• Lai Qingheng
• Klosin Jerzy
• Lesniak Michael J
• Pearson David M
• Senecal Todd D
• Woodward William H H
• Mukhopadhyay Sukrit
• Stutzman John R
• Gunther Susan O

Classifications

• C08F4/65908

  in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+ · CPC title

• C08F4/6592

  containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring · CPC title

• C08F2500/18

  Bulk density · CPC title

• C08F210/16 Primary

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

• C08F210/14 Primary

  Monomers containing five or more carbon atoms · CPC title