Peroxy-derivative functionalization of polypropylene via solid-state shear pulverization

Patent metadata

Field	Value
Publication number	US-9695255-B2
Application number	US-201615206978-A
Country	US
Kind code	B2
Filing date	Jul 11, 2016
Priority date	Sep 21, 2012
Publication date	Jul 4, 2017
Grant date	Jul 4, 2017

Abstract

Functionalization of polymers, including polyolefins, via decomposition of organic peroxides through the use of solid-state shear pulverization.

First claim

We claim:

1. A method of preparing a functionalized polymer, said method comprising:
providing a mixture comprising a polymer component and organic peroxide; and
applying a mechanical energy to said mixture through solid-state shear pulverization in the presence of cooling at least partially sufficient to maintain said polymer in a solid state during said pulverization, said pulverization at least partially sufficient to graft a peroxy derivative onto said polymer component, said pulverization providing a functionalized polymer.

2. The method of claim 1 wherein said polymer component is selected from polyolefins, copolymers of said polyolefins and combinations thereof.

3. The method of claim 2 wherein said polymer component is selected from polyethylene, polypropylene and copolymers thereof.

4. The method of claim 1 wherein said organic peroxide is selected from disubstituted peroxides of a formula RO—OR′, where R and R′ are independently selected from alkyl, cycloalkyl, alkenyl, alkenoyl, acryloyl, aryl, aroyl and acyl groups; and said peroxy derivative is selected from alkoxy, cycloalkoxy, alkenyloxy, alkenoyloxy, acryloyloxy, aroyl, aroyloxy and acyloxy moieties.

5. The method of claim 4 wherein said organic peroxide is benzoyl peroxide, and said peroxy derivative is a benzoyloxy moiety.

6. The method of claim 5 wherein said organic peroxide comprises about 0.01 wt. % to about 10 wt. % of said mixture.

7. The method of claim 1 wherein said mixture comprises a filler component selected from cellulose, rice husk ash, talc, silica, modified clay, unmodified clay, modified graphite, unmodified graphite, graphene, single-walled carbon nanotubes, multi-walled carbon nanotubes and combinations thereof.

8. The method of claim 7 wherein said filler component comprises about 0.1 wt. % to about 50 wt. % of said mixture.

9. The method of claim 1 wherein said grafting percentage is about 0.01% to about 100%.

10. A method of preparing a functionalized polymer, said method comprising:
providing a mixture comprising a polymer comprising a polypropylene component and an organic peroxide; and
applying a mechanical energy to said mixture through solid-state shear pulverization in the presence of cooling at least partially sufficient to maintain said polymer in a solid state during said pulverization, said pulverization at least partially sufficient to graft a peroxy derivative onto said polypropylene component, said pulverization providing a functionalized polymer.

11. The method of claim 10 wherein said polymer is a polypropylene.

12. The method of claim 10 wherein said organic peroxide is selected from disubstituted peroxides of a formula RO—OR′, where R and R′ are independently selected from alkyl, cycloalkyl, alkenyl, aryl, aroyl, alkenoyl, acryloyl and acyl groups; and said peroxy decomposition moiety is selected from alkoxy, cycloalkoxy, alkenyloxy, aroxy, acryloyloxy, aroyloxy and acyloxy moieties.

13. The method of claim 10 wherein said polymer is a polypropylene, and said organic peroxide is benzoyl peroxide.

14. The method of claim 10 wherein said functionalized polymer is blended with a polymer more polar than said polypropylene component of said polymer.

15. A method of functionalizing polypropylene with a benzoyloxy moiety, said method comprising:
providing a mixture comprising a polymer comprising a polypropylene component and benzoyl peroxide; and
applying a mechanical energy to said mixture through solid-state shear pulverization in the presence of cooling at least partially sufficient to maintain said polymer in a solid state during said pulverization, said pulverization at least partially sufficient to graft a benzoyloxy moiety onto said polypropylene component, said pulverization providing a benzoyloxy-functionalized polymer.

16. The method of claim 15 wherein said polymer is a polypropylene.

17. The method of claim 15 wherein said benzoyloxy-functionalized polymer is blended with a polymer more polar than said polypropylene.

18. The method of claim 17 wherein said functionalized polymer is blended with a nylon.

19. The method of claim 15 wherein said benzoyloxy moiety is up to about 0.50 wt. % of said polypropylene component.

20. A method of using solid-state shear pulverization to prepare a functionalized polymer, said method comprising:
providing a mixture comprising a polymer comprising a polypropylene component and a disubstituted organic peroxide of a formula RO—OR′, wherein R and R′ are independently selected from alkyl, cycloalkyl, alkenyl, alkenoyl, acryloyl, aroyl, aryl and acyl groups;
introducing said mixture to a solid-state shear pulverization apparatus, said apparatus comprising a cooling component; and
applying a mechanical energy to said mixture through solid-state shear pulverization in the presence of cooling at least partially sufficient to maintain said polymer in a solid state during said pulverization, said pulverization at least partially sufficient to graft a peroxy derivative into said polypropylene component, said derivative selected from alkoxy, cycloalkoxy, alkenoxy, alkenoyloxy, acryloyloxy, aroxy, aroyloxy and acyloxy moieties, said pulverization providing a functionalized polymer.

21. The method of claim 20 wherein said polymer is a polypropylene.

22. The method of claim 21 wherein said organic peroxide is benzoyl peroxide.

23. The method of claim 20 wherein said polymer is a polypropylene, and said organic peroxide is benzoyl peroxide.

24. A method of using solid-state shear pulverization to control molecular weight reduction during functionalization of polypropylene, said method comprising:
providing a mixture comprising a polypropylene component and benzoyl peroxide;
introducing said mixture into a solid-state shear pulverization apparatus, said apparatus comprising a cooling component; and
applying a mechanical energy to said mixture through solid-state shear pulverization in the presence of cooling at least partially sufficient to maintain polypropylene in a solid state during said pulverization, said pulverization at least partially sufficient to graft a benzoyloxy moiety onto polypropylene, said pulverization providing a benzoyloxy-functionalized polypropylene; and
annealing said functionalized polypropylene under vacuum conditions sufficient to remove said unreacted benzoyl peroxide from said functionalized polypropylene and suppress reduction of the molecular weight of said polypropylene component.

25. The method of claim 24 wherein said annealing is at a temperature sufficient to inhibit decomposition of said unreacted benzoyl peroxide.

26. The method of claim 24 wherein said molecular weight reduction of said polypropylene component is less than about 30%.

Assignees

• Univ Northwestern

Inventors

• Torkelson John M
• Diop Jeanette M

Classifications

• C08F10/06

  Propene · CPC title

• C08F110/06

  Propene · CPC title

• C08F8/14 Primary

  Esterification · CPC title

• C08F8/00

  Chemical modification by after-treatment (graft polymers, block polymers, crosslinking with unsaturated monomers or with polymers C08F251/00 - C08F299/00; of conjugated diene rubbers C08C) · CPC title

• C08F8/06

  Oxidation · CPC title