Azide-modified polynorbornene as polymeric coupling agent

Patent metadata

Field	Value
Publication number	US-10829570-B2
Application number	US-201815953247-A
Country	US
Kind code	B2
Filing date	Apr 13, 2018
Priority date	Apr 13, 2017
Publication date	Nov 10, 2020
Grant date	Nov 10, 2020

Abstract

This invention relates to a process for forming a long-chain branched polymer and a long-chain branched polymer resulting from the process. The process comprises reacting (a) a polyolefin base polymer with (b) a coupling agent comprising a polymeric coupling agent, optionally blended with a molecular coupling agent, the polymeric coupling agent being a modified polyolefin having a reactive coupling group at one or more terminal ends of the modified polyolefin chain, to couple the polyolefin base polymer (a) with the coupling agent (b) to form a long-chain branched polymer having a long-chain branching and/or higher surface energy relative to the polyolefin base polymer.

First claim

What is claimed is:

1. A polymeric coupling agent comprising:
a polymer prepared from at least one olefin monomer or derivative thereof containing 5 to 20 carbon atoms, and
one or more reactive coupling groups covalently bonded to one or more terminal ends of the polymer chain and/or one or more repeating units of the polymer, optionally via one or more linking moieties,
wherein the olefin monomer or derivative thereof is a norbornene-based bridged, cyclic olefin monomer, and
wherein the reactive coupling group is selected from the group consisting of a sulfonyl azide, aryl azide, phosphoryl azide, acyl azide, formyl azide, and combinations thereof.

2. The polymeric coupling agent of claim 1 , wherein the reactive coupling groups are covalently bonded to one or more repeating units of the polymer as pendent groups.

3. The polymeric coupling agent of claim 1 , wherein the polymer is a copolymer further comprising one or more olefin comonomers containing 2 to 20 carbon atoms.

4. The polymeric coupling agent of claim 1 , wherein the reactive coupling group is sulfonyl azide.

5. The polymeric coupling agent of claim 1 , wherein the linking moiety is present and selected from a group consisting of —O—, aryl, alkyl, acyl, sulfonyl, sulfonate ester, sulfonamide, phosphate ester, carboxylate ester, amine, amide, and combinations thereof.

6. The polymeric coupling agent of claim 1 , wherein the linking moiety is —C 6 H 4 — and the reactive coupling group is a sulfonyl azide.

7. The polymeric coupling agent of claim 1 , wherein the polymer comprises one or more of the following repeating unit of formula (I):

wherein:
R 1 , R 2 , R 3 , and R 4 are each independently selected from the group consisting of hydrogen; halogen; —OR 5 ; —C(O)OR 5 ; —OC(O)R 5 ; —NR 5 R 6 ; —ONR 5 R 6 ; —N(R 5 )OR 6 ; —SR 5 ; —C(S)SR 5 ; —SC(S)R 5 ; —SC(S)NR 5 R 6 ; —SC(O)SR 5 ; —SC(S)SR 5 ; —OSiR 5 R 6 R 7 ; —C═C—R 5 ; epoxide; peroxide; alkyl borane; isocyanate; silanes; a hydrocarbyl or halohydrocarbyl group selected from the group consisting of linear or branched C 1 -C 16 alkyl, perfluoroalkyl, C 3 -C 12 cycloalkyl, C 6 -C 12 bicycloalkyl, C 7 -C 14 tricycloalkyl, aryl, arylalkyl, perfluoroaryl, and perfluoroarylalkyl; —NH—Y 1 —R 8 —Y 2 —N 3 ; and —X-aryl-SO 2 N 3 ;
Y 1 and Y 2 are each independently absent,

X is selected from the group consisting of: alkyl, aryl, ether, —NH—, —NHSO 2 —, —O—, —CO, —C(O)O, —OC(O), —OC(O)O—, —S, —(CR 5 R 6 ) a —, —O(CR 5 R 6 ) a —, —(CR 5 R 6 ) a O—, —(CR 5 R 6 ) a O(SiR 5 R 6 ) a —, —(CR 5 R 6 ) a O(CR 5 R 6 ) a —, —C(O)(CR 5 R 6 ) a —, —(SiR 5 R 6 ) a O(SiR 5 R 6 ) a —, —(CR 5 R 6 ) a C(O)—, —C(O)O(CR 5 R 6 ) a —, —(CR 5 R 6 ) a C(O)O—, —OC(O)(CR 5 R 6 ) a —, —(CR 5 R 6 ) a OC(O)—(CR 5 R 6 ) a OC(O) a —, —(CR 5 R 6 ) a OC(O)O(CR 5 R 6 ) a —, —OC(O)O(CR 5 R 6 ) a —, —S(CR 5 R 6 ) a —, —(CR 5 R 6 ) a S—, —(SiR 5 R 6 ) a —, —O(SiR 5 R 6 ) a —, and —(SiR 5 R 6 ) a O—;
R 5 , R 6 , and R 7 are each independently hydrogen, linear or branched C 1 -C 12 alkyl, or aryl;
R 8 is absent, aryl, alkyl, or diarylether;
a is an integer from 0 to 12; and
n is 0, 1, or 2.

8. The polymeric coupling agent of claim 7 , wherein at least one of R 1 , R 2 , R 3 , and R 4 is —NH—Y 1 —R 7 —Y 2 —N 3 or —X-aryl-SO 2 N 3 .

9. The polymeric coupling agent of claim 7 , wherein the polymer comprises two or more different repeating units of formula (I).

10. The polymeric coupling agent of claim 9 , wherein at least one of R 1 , R 2 , R 3 , and R 4 in one of the repeating units of formula (I) is —NH—Y 1 —R 7 —Y 2 —N 3 or —X-aryl-SO 2 N 3 .

11. The polymeric coupling agent of claim 1 , wherein the polymer is a copolymer comprising one or more repeating units of

and one or more of the following repeating units:

wherein:
R′ is H, alkyl, vinyl, aryl, —C(O)R″, —CN;
R″ is H, —OH, or alkoxy, NH 2 ;
R 1 , R 2 , R 3 , and R 4 are each independently selected from the group consisting of hydrogen; halogen; —OR 5 ; —C(O)OR 5 ; —OC(O)R 5 ; —NR 5 R 6 ; —ONR 5 R 6 ; —N(R 5 )OR 6 ; —SR 5 ; —C(S)SR 5 ; —SC(S)R 5 ; —SC(S)NR 5 R 6 ; —SC(O)SR 5 ; —SC(S)SR 5 ; —OSiR 5 R 6 R 7 ; —C═C—R 5 ; epoxide; peroxide; alkyl borane; isocyanate; silanes; a hydrocarbyl or halohydrocarbyl group selected from the group consisting of linear or branched C 1 -C 16 alkyl, perfluoroalkyl, C 3 -C 12 cycloalkyl, C 6 -C 12 bicycloalkyl, C 7 -C 14 tricycloalkyl, aryl, arylalkyl, perfluoroaryl, and perfluoroarylalkyl; —NH—Y 1 —R 8 —Y 2 —N 3 ; and —X-aryl-SO 2 N 3 ;
Y 1 and Y 2 are each independently absent,

X is selected from the group consisting of: alkyl, aryl, ether, —NH—, —NHSO 2 —, —O—, —CO—, —C(O)O—, —OC(O)—, —OC(O)O—, —S—, —O—, —CO—, —C(O)O—, —OC(O)—, —OC(O)O—, —S—, —(CR 5 R 6 ) a —, —O(CR 5 R 6 ) a —, —(CR 5 R 6 ) a O—, (CR 5 R 6 ) a O(SiR 5 R 6 ) a —, —(CR 5 R 6 ),O(CR 5 R 6 ) a —, —C(O)(CR 5 R 6 ) a —, —(SiR 5 R 6 ) a O(SiR 5 R 6 ) a —, —(CR 5 R 6 ) a C(O)—, —C(O)O(CR 5 R 6 ) a —, —(CR 5 R 6 ) a C(O)O—, —OC(O)(CR 5 R 6 ) a —, (CR 5 R 6 ) a OC(0), —(CR 5 R 6 ) a OC(O) a —, —(CR 5 R 6 ) a OC(O)O(CR 5 R 6 ) a —, —OC(O)O(CR 5 R 6 ) a —, —S(CR 5 R 6 ) a —, —(CR 5 R 6 ) a S—, —(SiR 5 R 6 ) a —, —O(SiR 5 R 6 ) a —, and —(SiR 5 R 6 ) a O—;
R 5 , R 6 , and R 7 are each independently hydrogen, linear or branched C 1 -C 12 alkyl, or aryl;
R 8 is absent, aryl, alkyl, or diarylether;
a is an integer from 0 to 12; and
n is 0, 1, or 2.

12. The polymeric coupling agent of claim 11 , having one of the following structures:

wherein x+y ranges from 1 to 1,000;

wherein x+y ranges from 1 to 1,000; or

wherein x+y ranges from 1 to 1,000.

13. The polymeric coupling agent of claim 1 , wherein the polymer has a number average molecular weight of less than 100,000 g/mol.

14. The polymeric coupling agent of claim 1 , wherein the polymer has a molecular weight distribution ranging from about 1.0 to about 10.0.

15. The polymeric coupling agent of claim 3 , wherein the olefin comonomer is isoprene.

16. The polymeric coupling agent of claim 3 , wherein the olefin comonomer is styrene.

17. The polymeric coupling agent of claim 11 , wherein one or more of the repeating units is

and R′ is phenyl.

18. The polymeric coupling agent of claim 3 , wherein the olefin comonomer is selected from the group consisting of ethylene; propylene; 1-butene; 2-butene; 1,3-butadiene; isoprene; 1-pentene; 1,3-pentadiene; 1,4-pentadiene; 3-methyl-1-butene; 3-methyl-1,4-pentadiene; 3,3-dimethyl-1,4-pentadiene; 1-hexene; 1,3-hexadiene; 1,4-hexadi

Assignees

• Braskem America Inc

Inventors

• Few Chip
• Fernandes Jonas Alves
• Larson Jon Scott

Classifications

• C08F32/02 Primary

  having no condensed rings · CPC title

• C08L2205/05

  containing polymer components which can react with one another · CPC title

• C08C19/20

  Incorporating sulfur atoms into the molecule · CPC title

• C08F8/36

  Sulfonation; Sulfation · CPC title

• C08C19/22

  Incorporating nitrogen atoms into the molecule · CPC title