Adjustble Block Copolymer Having Acid Functional Groups and Adhesive and Thermoplastic Compositon Containing It

• US 20080214712A1
• Filed: 04/10/2006
• Published: 09/04/2008
• Est. Priority Date: 04/08/2005
• Status: Abandoned Application

• Current Assignee: Arkema France (Arkema)
• Original Assignee: Arkema France (Arkema)
• Inventors: Gerard, Pierre, Magnet, Stephanie, Guerret, Olivier, Passade Boupat, Nicolas
• Application Number:
  US11/910,799
• Publication Number:
  US 20080214712A1
• Time in Patent Office: Days
• US Class Current: 524/272
• CPC Class Codes: C08F 293/00 Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule on to polymers modified by introduction of unsaturated end groups C08F290/02
• CPC Class Codes: C08F 8/44 Preparation of metal salts or ammonium salts

Abstract

The invention relates to a linear ethylenic block copolymer comprising:

• • at least a first block A having a glass transition temperature above 20° C.;
  • at least a second block B having a glass transition temperature below 15° C.; and
  • at least a third block C having a glass transition temperature above 20° C.;
    said first block A and third block C being identical or different and at least one of them comprising at least one monomer unit comprising at least one —CO₂H and/or carboxylate —COO⁻ functional group.

Use of this copolymer in adhesive compositions and thermoplastic compositions.

Claims

1. Linear ethylenic block copolymer comprising:

at least a first block A having a glass transition temperature above 20°

C.;

at least a second block B having a glass transition temperature below 15°

C.; and

at least a third block C having a glass transition temperature above 20°

C.;

said first block A and third block C being identical or different and at least one of them comprising at least one monomer unit comprising at least one —

CO₂H and/or carboxylate —

COO⁻

functional group.

2. Copolymer according to claim 1, in which the monomer unit comprising at least one —

CO₂H and/or —

COO⁻

functional group is present in an amount ranging from 0.5 to 99 mol %.

3. Copolymer according to claim 2, in which the monomer unit comprising at least one —

CO₂H functional group is present in an amount ranging from 3 to 30 mol %.

4. Copolymer according to claim 1, in which the first block A and/or the third block C have a glass transition temperature above 60°

C.

5. Copolymer according to claim 1, in which the second block B has a glass transition temperature below −

30°

C.

6. Copolymer according to claim 1, in which the monomer unit comprising at least one —

CO₂H functional group is derived from a monomer corresponding to the formula (I) below;

7. Copolymer according to claim 6, in which, in the formula (I), R₁ is a hydrogen atom or a methyl group, x is equal to 0 and m is equal to 0.

8. Copolymer according to claim 6, in which R₂ is:

an alkylene group;

an (ortho, meta or para)-C₆H₄—

phenylene group, optionally substituted by a C₁-C₁₂ alkyl group optionally comprising from 1 to 8 heteroatoms chosen from O, N, S and P;

or else a —

C₆H₄—

CH₂—

benzylene group optionally substituted by a C₁-C₁₂ alkyl group optionally comprising from 1 to 8 heteroatoms chosen from O, N, S and P; and

a group of formula —

CH₂—

CHOH—

, —

CH₂—

CH₂—

CHOH—

, —

CH₂—

CH₂—

CH(NH₂)—

, —

CH₂—

CH(NH₂)—

, —

CH₂—

CH₂—

CH(NHR′

)—

, —

CH₂—

CH(NHR′

)—

, —

CH₂—

CH₂—

CH(NR′

R″

)—

, —

CH₂—

CH(NR′

R″

)—

, —

CH₂—

CH═

CH—

with R′ and

R″

representing a C₁-C₁₈ linear or branched alkyl group.

9. Copolymer according to claim 1, in which the unit comprising at least one —

CO₂H functional group is derived from a monomer chosen from acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, diacrylic acid, dimethylfumaric acid, citraconic acid, vinylbenzoic acid, acrylamidoglycolic acid of formula CH₂═

CH—

CONHCH(OH)COOH, diallyl maleate of formula C₃H₅—

CO₂—

CH═

CH—

CO₂—

C₃H₅, butyl (meth)acrylate, carboxylic anhydrides bearing a vinyl bond, and also salts thereof; and

mixtures thereof.

10. Copolymer according to claim 1, in which the monomer unit comprising at least one carboxylate —

COO⁻

functional group is derived from an amphoteric monomer of formula (II) below;

11. Copolymer according to claim 10, in which R₃ is:

an alkylene group;

an (ortho, meta or para)-C₆H₄—

phenylene group optionally substituted by a C₁-C₁₂ alkyl group optionally comprising from 1 to 5 heteroatoms chosen from O, N, S, F, Si and P;

or else a —

C₆H₄—

CH₂—

benzylene group optionally substituted by a C₁-C₁₂ alkyl group optionally comprising from 1 to 5 heteroatoms chosen from O, N, S and P.

12. Copolymer according to claim 1, in which the first block A and/or the third block C comprise(s), moreover, one or more monomer units derived from additional monomers chosen from non-ionic hydrophilic monomers, hydrophobic monomers and mixtures thereof.

13. Copolymer according to claim 12, in which the additional monomer is chosen from, alone or as a mixture:

(i) ethylenic hydrocarbons having 2 to 10 carbons; and

(ii) (meth)acrylates of formula;

14. Copolymer according to claim 12, in which the additional monomer is chosen from, alone or as a mixture:

hydroxyalkyl (meth)acrylates and (meth)acrylamides of which the alkyl group comprises 2 to 4 carbon atoms;

(C₁-C₄)alkoxy (C₁-C₄)alkyl (meth)acrylates and (meth)acrylamides;

(meth)acrylamide and N,N-dimethylacrylamide;

(meth)acrylates and (meth)acrylamides having an —

(OC₂H₄)_m—

OR″

group, with m=5 to 300 and R″

═

H or C₁ to C₄ alkyl;

vinyl lactams;

vinyl ethers;

vinylacetamide, N-vinylpyrrolidone or N-vinylcaprolactam; and

polysaccharide (meth)acrylates such as saccharose acrylate and ethyl glucoside (meth)acrylate.

15. Copolymer according to claim 12, in which the additional monomer is chosen from, alone or as a mixture:

t-butylbenzyl acrylate, t-butylcyclohexyl acrylate, isobornyl acrylate (94°

C.), furfuryl acrylate, n-hexyl acrylate (45°

C.), t-butyl acrylate (50°

C.), cyclohexyl acrylate (19°

C.), hydroxyethyl acrylate (15°

C.), methyl acrylate (10°

C.), ethyl acrylate (−

24°

C.), isobutyl acrylate (−

24°

C.), methoxyethyl acrylate (−

33°

C.), n-butyl acrylate (−

54°

C.), ethylhexyl acrylate (−

50°

C.), hexyl acrylate, octyl acrylate, lauryl acrylate, isooctyl acrylate, isodecyl acrylate;

t-butylbenzyl methacrylate, t-butylcyclohexyl methacrylate, isobornyl methacrylate (111°

C.), methyl methacrylate (100°

C.), cyclohexyl methacrylate (83°

C.), ethyl methacrylate (65°

C.), benzyl methacrylate (54°

C.), isobutyl methacrylate (53°

C.), butyl methacrylate (20°

C.), n-hexyl methacrylate (−

5°

C.), ethylhexyl methacrylate, octyl methacrylate, lauryl methacrylate, isooctyl methacrylate, isodecyl methacrylate;

styrene (100°

C.), vinylcyclohexane, vinylacetate (23°

C.), vinyl methyl ether (−

34°

C.), vinyl neononanoate, vinyl neododecanoate;

N-butylacrylamide, N-isopropylacrylamide, N,N-dimethylacrylamide, N,N-dibutylacrylamide, N-t-butylacrylamide, N-octylacrylamide.

16. Copolymer according to claim 1, in which the block B comprises monomer units derived from non-ionic hydrophilic and/or hydrophobic monomers as defined above.

17. Copolymer according to claim 1, which is a triblock copolymer of A-B-C type.

18. Copolymer according to claim 17, in which the block B is present in an amount ranging from 5 to 95% by weight of the copolymer.

19. Copolymer according to claim 17, in which the block B is present in an amount greater than 50% by weight of the copolymer.

20. Copolymer according to claim 17, in which the block A and/or C comprises:

monomer units derived from non-ionic monomers chosen from;

vinyl compounds of formula CH₂═

CH—

R₉, R₉;

methacrylate compounds of formula;

21. Copolymer according to claim 20, in which the monomer units derived from non-ionic monomers are present in an amount ranging from 1 to 99.5% relative to the total weight of the block.

22. Copolymer according to claim 20, in which the monomer units bearing at least one —

CO₂H functional group are present in an amount ranging from 0.5 to 99% relative to the total weight of the block.

23. Copolymer according to claim 20, in which the block B comprises monomer units derived from monomers chosen from (meth)acrylates of formula:

24. Copolymer according to claim 23, in which the (meth)acrylate monomers are chosen from n-hexyl methacrylate (T_g=−

5°

C.), ethyl acrylate (T_g=−

24°

C.), isobutyl acrylate (T_g=−

24°

C.), n-butyl acrylate (T_g=−

54°

C.), ethylhexyl acrylate (T_g=−

50°

C.).

25. Copolymer according to claim 17, in which the triblock copolymer is chosen from poly(styrene-co-methacrylic acid)-b-poly(n-butyl acrylate)-b-poly(styrene-co-methacrylic acid), poly(methyl methacrylate-co-methacrylic acid)-b-poly(n-butyl acrylate)-b-poly(methyl methacrylate-co-methacrylic acid).

26. Copolymer according to claim 25, in which the poly(styrene-co-methacrylic acid)-b-poly(n-butyl acrylate)-b-poly(styrene-co-methacrylic acid) copolymer is that for which:

the poly(n-butyl acrylate) block represents 71% by weight of the total copolymer;

the poly(styrene-co-methacrylic acid) blocks each comprise monomer units derived from methacrylic acid in an amount of 2% by weight of the total copolymer and monomer units derived from styrene in an amount of 12.5% by weight of the total copolymer; and

a weight-average molecular weight of 372 000 g/mol.

27. Copolymer according to claim 25, in which the poly(methyl methacrylate-co-methacrylic acid)-b-poly(n-butyl acrylate)-b-poly(methyl methacrylate-co-methacrylic acid) copolymer is that for which:

the poly(n-butyl acrylate) block represents 35% by weight of the total copolymer;

the poly(methyl methacrylate-co-methacrylic acid) blocks each comprise monomer units derived from methacrylic acid in an amount of 3.25% by weight of the total copolymer and monomer units derived from methyl methacrylate in an amount of 29.25% by weight of the total copolymer; and

a weight-average molecular weight of 150 000 g/mol.

28. Copolymer according to claim 25, in which the poly(methyl methacrylate-co-methacrylic acid)-b-poly(n-butyl acrylate)-b-poly(methyl methacrylate-co-methacrylic acid) copolymer is that for which:

the poly(n-butyl acrylate) block represents 65% by weight of the total copolymer;

the poly(methyl methacrylate-co-methacrylic acid) blocks each comprise monomer units derived from methacrylic acid in an amount of 1.6% by weight of the total copolymer and monomer units derived from methyl methacrylate in an amount of 15.9% by weight of the total copolymer; and

a weight-average molecular weight of 95 000 g/mol.

29. Composition comprising at least 1%—

by weight, relative to the total weight of the composition, of a copolymer as defined according to any one of claim 1.

30. Composition according to claim 29, in which the copolymer is neutralized, completely or partly, by a mineral or organic base.

31. Composition according to claim 30, in which the mineral base is chosen from alkali metal hydroxides, alkaline-earth metal hydroxides, metal hydroxides and metalloid hydroxides.

32. Composition according to claim 31, in which the organic base is an amine.

33. Composition according to claim 31, in which the amine is an amine having a boiling point above 200°

C. at 1 atm.

34. Composition according to claim 30, in which the degree of neutralization is greater than 0.1, preferably greater than 0.5.

35. Composition according to claim 29, which is an adhesive composition.

36. Composition according to claim 35, in which the copolymer is present in an amount of at least 5% by weight relative to the total weight of the composition.

37. Composition according to claim 35, comprising, in addition, an additive chosen from tackifying resins and plasticizers.

38. Composition according to claim 37, in which the plasticizer is chosen from trimellitate type oils and predominantly naphthenic oils.

39. Composition according to claim 37, in which the tackifying resin is chosen from resins based on rosin(s), rosin ester, polyterpene, hydroxylated polyester, terpene-styrene, terpene-pentaerythritol or terpene-phenol.

40. Adhesive strips, labels and tapes comprising a composition as defined according to claim 35.

41. Composition according to claim 29, which is a thermoplastic composition.

42. Composition according to claim 41, comprising, in addition, one or more thermoplastic polymers.

43. Composition according to claim 42, in which the thermoplastic polymer is chosen from polymethyl methacrylate, polystyrene and polyvinyl chloride.

44. Process for preparing a composition as defined in claim 30, comprising a step of bringing the copolymer into contact, in a liquid medium, with a mineral or organic base.

45. Process for preparing a composition as defined in claim 30, comprising a step of bringing the copolymer into contact, via a molten route, with a mineral or organic base.

46. Use of a copolymer as defined according to claim 1, as a hot-melt adhesive.

47. A method comprising providing a hot melt adhesive with a copolymer of claim 1 and applying said hot melt adhesive to a substrate.