Long-chain branched polymers and production processes

Patent metadata

Field	Value
Publication number	US-2017145127-A1
Application number	US-201715426863-A
Country	US
Kind code	A1
Filing date	Feb 7, 2017
Priority date	Jun 15, 2015
Publication date	May 25, 2017
Grant date	—

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 2 to 20 carbon atoms, wherein the polymer has one or more reactive coupling groups covalently bonded to one or more terminal ends of the polymer chain.

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

3 . The polymeric coupling agent of claim 1 , wherein the reactive coupling group is an azide.

4 . The polymeric coupling agent of claim 1 , wherein the one or more reactive coupling groups are covalently bonded to one or more terminal ends of the polymer chain via one or more linking moieties.

5 . The polymeric coupling agent of claim 4 , wherein the linking moiety is present and selected from the group consisting of aryl sulfonyl, oxy aryl sulfonyl, ester, amine, amide, derivatives thereof, and combinations thereof.

6 . The polymeric coupling agent of claim 4 , wherein the linking moiety is —C 6 H 4 —SO 2 —.

7 . The polymeric coupling agent of claim 1 , wherein the at least one olefin monomer or derivatives thereof are selected from the group consisting of ethylene; propylene; 1-butene; 2-butene; 1,3-butadiene; 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-hexadiene; 1,5-hexadiene; 4-methyl-1-pentene; 3-methyl-1-pentene; 3-methyl-1,5-hexadiene; 3,4-dimethyl-1,5-hexadiene; 4,6-dimethyl-1-heptene; 1,3-heptadiene; 1,4-heptadiene; 1,5-heptadiene; 1,6-heptadiene; 1-octene; 1,3-octadiene; 1,4-octadiene; 1,5-octadiene; 1,6-octadiene; 1,7-octadiene; 1-decene; 1-undecene; 1-dodecene; 1-tetradecene; 1-hexadecene; 1-octadecene; 1-eicocene; and combinations thereof.

8 . The polymeric coupling agent of claim 7 , wherein the olefin monomer is 1,3-butadiene.

9 . The polymeric coupling agent of claim 1 , wherein the polymer chain comprises one or more of the following repeating units:

10 . The polymeric coupling agent of claim 1 , having the following structure:

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

11 . The polymeric coupling agent of claim 1 , wherein the polyolefin has a number average molecular weight of less than 20,000 g/mol.

12 . The polymeric coupling agent of claim 1 , wherein the polyolefin has a molecular weight distribution ranging from about 1.0 to about 3.0.

13 . A process for forming a long-chain branched polymer, comprising:
reacting (a) a polyolefin base polymer with (b) a polymeric coupling agent to form a long-chain branched polymer, wherein the polymeric coupling agent comprises: a polymer prepared from at least one olefin monomer or derivative thereof containing 2 to 20 carbon atoms, wherein the polymer has one or more reactive coupling groups covalently bonded to one or more terminal ends of the polymer chain.

14 . The process of claim 13 , wherein the one or more reactive coupling groups are covalently bonded to one or more terminal ends of the polymer chain via one or more linking moieties.

15 . The process of claim 13 , wherein the polyolefin base polymer (a) is a polymer or copolymer of one or more olefins having from 2 to 12 carbons and a number average molecular weight of greater than 50,000 g/mol.

16 . The process of claim 15 , wherein the one or more olefins are selected from the group consisting of ethylene; propylene; 1-butene; 2-butene; 1,3-butadiene; 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-hexadiene; 1,5-hexadiene; 4-methyl-1-pentene; 3-methyl-1-pentene; 3-methyl-1,5-hexadiene; 3,4-dimethyl-1,5-hexadiene; 4,6-dimethyl-1-heptene; 1,3-heptadiene; 1,4-heptadiene; 1,5-heptadiene; 1,6-heptadiene; 1-octene; 1,3-octadiene; 1,4-octadiene; 1,5-octadiene; 1,6-octadiene; 1,7-octadiene; 1-decene; 1-undecene; 1-dodecene; 1-tetradecene; 1-hexadecene; 1-octadecene; 1-eicocene, and combinations thereof.

17 . The process of claim 15 , wherein the polyolefin base polymer (a) is polyethylene, polypropylene, a copolymer thereof, or polymer blends containing polyethylene and/or polypropylene and/or copolymer thereof.

18 . The process of claim 13 , wherein the reacting step includes:
subjecting the polyolefin base polymer (a) and polymeric coupling agent (b) to melt processing to blend the polyolefin base polymer and the polymeric coupling agent.

19 . The process of claim 13 , wherein the reacting step takes place under solventless reaction conditions.

20 . The process of claim 18 , wherein the melt processing is an extrusion process.

21 . The process of claim 13 , wherein the reactive coupling group covalently bonded to one or more terminal ends of the polymer chain is an azide group, forming an azide-modified polymeric coupling agent.

22 . The process of claim 21 , wherein the reacting step involves heating the polyolefin base polymer (a) and an azide-modified polymeric coupling agent (b) to the decomposition temperature of the azide-modified polymeric coupling agent (b) to form nitrenes that react with the polyolefin base polymer.

23 . The process of claim 13 , wherein the polymeric coupling agent self-couples to form a polymeric self-coupled coupling agent capable of reacting with the polyolefin base polymer (a).

24 . The process of claim 13 , further comprising blending the long-chain branched polymer with a second polyolefin that is in a different phase than the long-chain branched polymer.

25 . The process of claim 13 , further comprising:
adding, in the reacting step, an inorganic material containing a polar group, wherein the inorganic material is selected from the group consisting of glass fibers, inorganic fibers, functionalized silica nanoparticles, polyhedral oligomeric silsesquioxane (POSS), functionalized carbon nanotubes, clay, and combinations thereof.

26 . A long-chain branched polymer prepared according to the process of claim 13 .

27 . The long-chain branched polymer of claim 26 , wherein one or more polymeric coupling agents are covalently bonded to one or more polyolefin base polymer chains.

28 . A long-chain branched polymer prepared according to the process of claim 23 .

29 . The long-chain branched polymer of claim 28 , wherein the polymer contains branched chains resulting from both the reaction of the polyolefin base polymer (a) with the polymeric coupling agent (b), and the reaction of the polyolefin base polymer (a) with the self-coupled polymeric coupling agent.

Assignees

• Braskem America Inc

Inventors

• Fernandes Jonas Alves

Classifications

• C08F2500/08

  Low density, i.e. < 0.91 g/cm3 · CPC title

• C08G81/021

  Block or graft polymers containing only sequences of polymers of C08C or C08F · CPC title

• C08F126/02 Primary

  by a single or double bond to nitrogen · CPC title

• C08F10/02

  Ethene · CPC title

• C08F210/16

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