IP Library Granted Patent US 8,241,753
Granted Patent B2
US 8,241,753 · App. 11/810,030 · Granted Aug 14, 2012

Composite thermoplastic elastomer structures with high adhesion performance and uses for the same

Assignee: ExxonMobil Chemical Patents Inc.
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Quick Facts
Patent No.
US 8,241,753
App. No.
11/810,030
Granted
Aug 14, 2012
Kind
B2
Abstract

Provided is a composition thermoplastic elastomer structure comprising (1) a first component comprising a first elastomeric component comprising an at least partially vulcanized rubber and a thermoplastic resin, (2) an adhesive later comprising a grafted random propylene copolymer and (3) a third component comprising a polyamide or polyester. The third component is at least partially adhered to the adhesive component, which is in turn, partially adhered to the first component. The structure has superior adhesive properties between structures. Also provided are articles made from the structures, particularly automotive weather seals, glass run channels, a noise attenuating device, automotive interior part, automotive belt, automotive hose, industrial belt, industrial hose, packaging material, construction material, decorative building material, and other consumer goods.

Claims (91)

1. A composite structure comprising:

a. a first component;

b. a second component comprising a grafted propylene-based elastomer comprising

i. propylene-derived monomer units; and

ii. from 0.1 to 10 wt %, based on the weight of the grafted propylene-based elastomer, graft comonomer units;

wherein, the grafted propylene-based elastomer has a heat of fusion of less than 75 J/g and a T m of less than 105° C.; and

c. a third component comprising a polar material,

wherein the third component is at least partially adhered to the second component and the second component is at least partially adhered to the first component.

2. The composite structure of claim 1 , wherein the propylene-based elastomer is a copolymer comprising from 0.1 to 30 wt %, based on the weight of the grafted propylene-based elastomer, primary comonomer units.

3. The composite structure of claim 1 , wherein the first component comprises a rubber and a thermoplastic resin.

4. The composite structure of claim 3 , wherein the rubber is selected from the group consisting of ethylene-propylene rubber (EPR), ethylene-propylene-diene rubber (EPDM), butyl rubber, homopolymers of a conjugated diene, copolymers of at least one conjugated diene with an aromatic monomer, copolymers of at least one conjugated diene with a polar monomer, unsaturated non-polar elastomers, natural rubber, polyisoprene, polybutadiene elastomer, styrene-butadiene elastomer and mixtures thereof; and

the thermoplastic resin is selected from the group consisting of crystallizable polyolefins, polyimides, polyamides, polyesters, poly(phenylene ether), polycarbonates, styrene-acrylonitrile copolymers, polyethylene terephthalate, polybutylene terephthalate, polystyrene, polystyrene derivatives, polyphenylene oxide, polyoxymethylene, fluorine-containing thermoplastics, polyurethanes and mixtures thereof.

5. The composite structure of claim 4 , wherein the thermoplastic resin is polypropylene.

6. The composite structure of claim 1 , wherein the primary comonomer units derived from any of C 2 or C 4 -C 20 alpha olefins.

7. The composite structure of claim 5 , wherein the primary comonomer units are derived from ethylene and the grafted propylene-based elastomer has a heat of fusion of less than 50 J/g.

8. The composite structure of claim 1 , wherein the graft comonomer units are derived from the group consisting of carboxylic acids, carboxylate anhydrides, carboxylate esters, carboxylate amides, carboxylate imides, metal carboxylate salts, epoxides, C 1 -C 8 alkyl esters, C 1 -C 8 glycidyl esters and mixtures thereof.

9. The composite structure of claim 1 , wherein the graft comonomer units are derived from the group consisting of acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, acrylic anhydride, methacrylic anhydride, maleic anhydride, fumaric anhydride, itaconic anhydride, glycidyl methacrylate, glycidyl acrylate, allyl-glycidal ether, methallyl-glycidal ether, glycidyl-2-ethyl acrylate, glycidyl-2-propyl acrylate, isopropenylphenyl-glycidyl ethers and mixtures thereof.

10. The composite structure of claim 1 , wherein the third component is a fiber, the fiber having a length of from 0.1 mm to 5.0 mm and a fineness of from 0.1 decitex to 5.0 decitex.

11. The composite structure of claim 10 , wherein third component is selected from polyamides, polyesters, acrylics, rayon and mixtures thereof.

12. The composite structure of claim 11 , wherein third component is selected from nylon, poly(C 1 -C 6 alkylene) terephthalates and mixtures thereof.

13. The composite structure of claim 1 , wherein the graft comonomer units are present in the amount of from 0.1 wt % to 5.0 wt % based on the weight of the grafted propylene-based elastomer.

14. The composite structure of claim 1 , wherein the graft comonomer units are present in the amount of from 0.3 wt % to 1.5 wt % based on the weight of the grafted propylene-based elastomer.

15. The composite structure of claim 1 , wherein the graft comonomer units are present in the amount of from 0.5 wt % to 1.5 wt % based on the weight of the grafted propylene-based elastomer.

16. The composite structure of claim 1 , wherein the grafted propylene-based elastomer has a melt index according to ASTM D1238 at 190° C. and 2.16 kg weight of from 0.1 dg/min to 50 dg/min.

17. The composite structure of claim 1 , wherein the grafted propylene-based elastomer has a melt index according to ASTM D1238 at 190° C. and 2.16 kg weight of from 1.0 dg/min to 25 dg/min.

18. The composite structure of claim 1 , wherein the rubber is at least partially vulcanized.

19. The composite structure of claim 1 , wherein the original Renault adhesion rating is of from 2 to 4+.

20. The composite structure of claim 1 , wherein the cataplasm heat aged Renault adhesion rating is of from 3 to 4+.

21. The composite structure of claim 1 , wherein the original Renault adhesion rating is of from 1 to 4+ and the cataplasm heat aged Renault adhesion rating is of from 3 to 4+.

22. A shaped article comprising the composite structure of claim 1 .

23. The shaped article of claim 21 , wherein the shaped article is selected from automotive weather seals, glass run channels, a noise attenuating device, automotive interior part, automotive belt, automotive hose, industrial belt, industrial hose, packaging material, construction material, decorative building material, handbag, backpack, clothing article, hand or power tool, drawer or cabinet liner, picture frame or hunting decoy.

24. A composite structure comprising:

a. a first component comprising an elastomeric component comprising a rubber and a thermoplastic resin;

b. a second component comprising a grafted propylene-based elastomer comprising

i. propylene-derived monomer units;

ii. from 0.1 to 30 wt %, based on the weight of the grafted propylene-based elastomer, primary comonomer units derived from any of C 2 or C 4 -C 20 alpha olefins;

iii. from 0.1 to 10 wt %, based on the weight of the grafted propylene-based elastomer, graft comonomer units;

wherein, the grafted propylene-based elastomer has a heat of fusion of less than 75 J/g and a T m of less than 105° C.; and

c. an adhesive component; and

d. a third component comprising polyamide, polyester, acrylic, rayon or mixtures thereof,

wherein the third component is at least partially adhered to the adhesive component, the adhesive component is at least partially adhered to the second component and the second component is at least partially adhered to the first component.

25. The composite structure of claim 24 , wherein the rubber is selected from the group consisting of ethylene-propylene rubber (EPR), ethylene-propylene-diene rubber (EPDM), butyl rubber, homopolymers of a conjugated diene, copolymers of at least one conjugated diene with an aromatic monomer, copolymers of at least one conjugated diene with a polar monomer, unsaturated non-polar elastomers, natural rubber, polyisoprene, polybutadiene elastomer, styrene-butadiene elastomer and mixtures thereof;

the thermoplastic resin is selected from the group consisting of crystallizable polyolefins, polyimides, polyamides, polyesters, poly(phenylene ether), polycarbonates, styrene-acrylonitrile copolymers, polyethylene terephthalate, polybutylene terephthalate, polystyrene, polystyrene derivatives, polyphenylene oxide, polyoxymethylene, fluorine-containing thermoplastics, polyurethanes and mixtures thereof; and

the graft comonomer units are derived from the group consisting of carboxylic acids, carboxylate anhydrides, carboxylate esters, carboxylate amides, carboxylate imides, metal carboxylate salts, epoxides, C 1 -C 8 alkyl esters, C 1 -C 8 glycidyl esters and mixtures thereof.

26. The composite structure of claim 25 , wherein the rubber is selected from the group consisting of ethylene-propylene rubber (EPR), ethylene-propylene-diene rubber (EPDM), butyl rubber and mixtures thereof;

the thermoplastic resin is selected from the group consisting of polypropylene, propylene copolymers and mixtures thereof; and

the graft comonomer units are derived from the group consisting of acrylic acid, methacrylic acid, maleic acid, acrylic anhydride, methacrylic anhydride, maleic anhydride, glycidyl methacrylate, glycidyl acrylate, glycidyl acrylate and isopropenylphenyl-glycidyl ethers and mixtures thereof.

27. The composite structure of claim 26 , wherein the graft comonomer units are present in the amount of from 0.1 wt % to 1.5 wt % based on the weight of the grafted propylene-based elastomer.

28. The composite structure of claim 25 , wherein the adhesive component comprises a polyurethane, acrylic, epoxy or mixtures thereof.

29. The composite structure of claim 25 , wherein the adhesive component is substantially solvent free.

30. The composite structure of claim 25 , wherein the third component is selected from nylon, poly(C 1 -C 6 alkylene) terephthalates and mixtures thereof and is a fiber, the fiber having a length of from 0.1 mm to 5.0 mm and a fineness of from 0.1 decitex to 5.0 decitex.

31. The composite structure of claim 25 , wherein the original Renault adhesion rating is of from 2 to 4+.

32. The composite structure of claim 25 , wherein the cataplasm heat aged Renault adhesion rating is of from 3 to 4+.

33. The composite structure of claim 25 , wherein the original Renault adhesion rating is of from 1 to 4+ and the cataplasm heat aged Renault adhesion rating is of from 3 to 4+.

34. The composite structure of claim 25 , wherein the rubber is at least partially vulcanized.

35. A composite structure comprising a flock and a grafted propylene-based elastomer, the grafted propylene-based elastomer comprising:

i. propylene-derived monomer units;

ii. from 0.1 to 30 wt %, based on the weight of the grafted propylene-based elastomer, primary comonomer units derived from any of C 2 or C 4 -C 20 alpha olefins;

iii. from 0.1 to 10 wt %, based on the weight of the grafted propylene-based elastomer, graft comonomer units;

wherein, the grafted propylene-based elastomer has a heat of fusion of less than 75 J/g and a T m of less than 105° C.; and

where the flock comprising polyamide, polyester, acrylic, rayon or mixtures thereof.

36. The composite structure of claim 35 , wherein the flock is at least partially adhered to the grafted propylene-based elastomer.

37. The composition of claim 35 , wherein the primary comonomer units are present in the amount of from 0.5 wt % to 15 wt % based on the weight of the grafted propylene-based elastomer.

38. The composite structure of claim 35 , wherein in the graft comonomer units are derived from the group consisting of carboxylic acids, carboxylate anhydrides, carboxylate esters, carboxylate amides, carboxylate imides, metal carboxylate salts, epoxides, C 1 -C 8 alkyl esters, C 1 -C 8 glycidyl esters and mixtures thereof.

39. The composite structure of claim 35 , wherein the graft comonomer units are derived from the group consisting of acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, acrylic anhydride, methacrylic anhydride, maleic anhydride, fumaric anhydride, itaconic anhydride, glycidyl methacrylate, glycidyl acrylate, allyl-glycidal ether, methallyl-glycidal ether, glycidyl-2-ethyl acrylate, glycidyl-2-propyl acrylate, isopropenylphenyl-glycidyl ethers and mixtures thereof.

40. The composition of claim 35 , wherein the graft comonomer units are present in the amount of from 0.5 wt % to 2.0 wt % based on the weight of the grafted propylene-based elastomer.

41. The composite structure of claim 35 , wherein the third component is a fiber, the fiber having a length of from 0.1 mm to 5.0 mm and a fineness of from 0.1 decitex to 5.0 decitex.

42. The composite structure of claim 35 , wherein the flock is selected from nylon, poly(C 1 -C 6 alkylene) terephthalates and mixtures thereof.

43. The composite structure of claim 35 , wherein the grafted propylene-based elastomer has a melt index according to ASTM D1238 at 190° C. and 2.16 kg weight of from 1.5 dg/min to 10 dg/min.

44. A useful article comprising the composite structure of claim 35 , wherein the useful article is a noise attenuating device, automotive interior part, automotive belt, automotive hose, industrial belt, industrial hose, packaging material, construction material, decorative building material, handbag, backpack, clothing article, hand or power tool, drawer or cabinet liner, picture frame or hunting decoy.

45. An automotive weather seal comprising:

a. a first elastomeric component;

b. a second component comprising a grafted propylene-based elastomer comprising

i. propylene-derived monomer units;

ii. from 0.1 to 30 wt %, based on the weight of the grafted propylene-based elastomer, primary comonomer units derived from any of C 2 or C 4 -C 20 alpha olefins;

iii. from 0.1 to 10 wt %, based on the weight of the grafted propylene-based elastomer, graft comonomer units;

wherein, the grafted propylene-based elastomer has a heat of fusion of less than 75 J/g and a T m of less than 105° C.; and

c. an adhesive component; and

d. a third component comprising polyamide, polyester, acrylic, rayon or mixtures thereof,

wherein the third component is at least partially adhered to the adhesive component, the adhesive component is at least partially adhered to the second component and the second component is at least partially adhered to the first component.

46. The automotive weather seal of claim 45 , wherein the first elastomeric component comprises an at least partially vulcanized rubber and a thermoplastic resin.

47. The automotive weather seal of claim 46 , wherein the rubber is selected from the group consisting of ethylene-propylene rubber (EPR), ethylene-propylene-diene rubber (EPDM), butyl rubber, homopolymers of a conjugated diene, copolymers of at least one conjugated diene with an aromatic monomer, copolymers of at least one conjugated diene with a polar monomer, unsaturated non-polar elastomers, natural rubber, polyisoprene, polybutadiene elastomer, styrene-butadiene elastomer and mixtures thereof

the thermoplastic resin is selected from the group consisting of crystallizable polyolefins, polyimides, polyamides, polyesters, poly(phenylene ether), polycarbonates, styrene-acrylonitrile copolymers, polyethylene terephthalate, polybutylene terephthalate, polystyrene, polystyrene derivatives, polyphenylene oxide, polyoxymethylene, fluorine-containing thermoplastics, polyurethanes and mixtures thereof and

the graft comonomer units are derived from the group consisting of carboxylic acids, carboxylate anhydrides, carboxylate esters, carboxylate amides, carboxylate imides, metal carboxylate salts, epoxides, C 1 -C 8 alkyl esters, C 1 -C 8 glycidyl esters and mixtures thereof.

48. The automotive weather seal of claim 47 , wherein the third component selected from nylon, poly(C 1 -C 6 alkylene) terephthalates and mixtures thereof and is a fiber, the fiber having a length of from 0.1 mm to 5.0 mm and a fineness of from 0.1 decitex to 5.0 decitex.

49. A composite structure comprising:

a. a first elastomeric component comprising an at least partially vulcanized rubber and a thermoplastic resin;

b. a second polar component selected from polyamide, polyester, acrylic, rayon and mixtures thereof;

c. optionally, a third adhesive component; and

d. means for adhering the second polar component to at least one of the first elastomeric component or the third adhesive component.

wherein (i) the adhering means comprises a grafted propylene-based elastomer, and (ii) the second polar component is selected from nylon, poly(C 1 -C 6 alkylene) terephthalates and mixtures thereof and is a fiber, the fiber having a length of from 0.1 mm to 5.0 mm and a fineness of from 0.1 decitex to 5.0 decitex.

Assignments (4)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Feb 25, 2022
From: EXXONMOBIL CHEMICAL PATENTS INC.
To: SANTOPRENE PRODUCTION PENSACOLA LLC
Reel/Frame 059248/0456 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Feb 25, 2022
From: SANTOPRENE PRODUCTION PENSACOLA LLC
To: CELANESE INTERNATIONAL CORPORATION
Reel/Frame 059248/0673 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jun 23, 2009
From: ADVANCED ELASTOMER SYSTEMS, L.P.
To: EXXONMOBIL CHEMICAL PATENTS INC.
Reel/Frame 022865/0483 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jun 4, 2007
From: KENENS, LEANDER MICHIEL; JOURDAIN, ERIC PAUL; SCHAUDER, JEAN-ROCH
To: ADVANCED ELASTOMER SYSTEMS, L.P.
Reel/Frame 019442/0578 →
Continuity (1)
Related Publication 20080299397A1 · Dec 4, 2008