PHOTOCROSSLINKABLE BLOCK COPOLYMERS FOR HOT-MELT ADHESIVES

• US 20160168298A1
• Filed: 12/15/2014
• Published: 06/16/2016
• Est. Priority Date: 12/15/2014
• Status: Active Grant

• Current Assignee: Henkel AG & Co KGaA
• Original Assignee: Henkel Corporation (Henkel AG & Co KGaA)
• Inventors: Chauveau, Guillaume, Woods, John G., Palasz, Peter D., Slark, Andrew
• Granted Patent: US 9,587,062 B2
• Time in Patent Office: Days
• US Class Current: 1/1
• CPC Class Codes: C08F 120/14 Methyl esters , e.g. methyl (meth)acrylate
• CPC Class Codes: C08F 2438/00 Living radical polymerisation
• CPC Class Codes: C08F 2438/01 Atom Transfer Radical Polymerization [ATRP] or reverse ATRP
• CPC Class Codes: C08F 265/06 Polymerisation of acrylate or methacrylate esters on to polymers thereof
• CPC Class Codes: C08F 293/005 using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent

Abstract

Disclosed is a method for formation of block copolymers using a Single Electron Transfer Living Radical Polymerization (SET-LRP) process. The process can be used to form di and tri-block copolymers from vinyl monomers. In one embodiment the SET-LRP process comprises initially forming a macroinitiator using SET-LRP to form a first block of a di or tri-block copolymer and then using SET-LRP to form additional blocks of the copolymer. The produced block copolymers have very narrow polydispersity indexes and controlled molecular weights. The process permits incorporation of photoinitiators in any of the block formation reactions. The method also includes purification processes that result in a block copolymer having very low color making it useful in a variety of applications. In one application block copolymers prepared according to the present process can be used in hot-melt adhesives.

Claims

1. A method of forming a macroinitiator polymer by a single electron transfer living radical polymerization comprising the steps of:

a) providing a reaction mixture comprising a plurality of vinyl monomers, a halogen terminated initiator, and a ligand in a solvent;

b) purging the reaction mixture with nitrogen; and

c) adding to the reaction mixture a solid copper hydrazine-activated catalyst and polymerizing the reaction mixture in the presence of the catalyst under a positive pressure of nitrogen to produce a macroinitiator polymer having a molecular weight of from 55,000 to 75,000 grams/mole, a polydispersity index of 1.2 to 1.8, and a glass transition temperature of less than 20°

C.

2. The method of claim 1, wherein step a) comprises providing vinyl monomers selected from the group consisting of 2-ethylhexyl acrylate, methacrylate, n-butyl acrylate, tert-butyl acrylate, and mixtures thereof.

3. The method of claim 1, wherein step a) comprises providing a bromine terminated initiator.

4. The method of claim 1, wherein step a) comprises providing as the initiator one of dimethyl 2,6-dibromoheptanedioate and methyl-2-bromopropionate.

5. The method of claim 1, wherein step a) comprises providing as the ligand hexamethylated tris (2-aminoethyl) amine.

6. The method of claim 1, wherein step a) comprises providing as the solvent a blend of dimethyl sulfoxide and ethyl acetate.

7. The method of claim 1, further comprising in step a) providing at least one polymerizable photoinitiator in said reaction mixture, said photoinitiator polymerizing into said macroinitiator polymer in step c) and providing UV curable crosslinking functionality to said polymer.

8. The method of claim 7 wherein said polymerizable photoinitiator is selected from the group consisting of 4-benzoylphenyl methacrylate, a benzophenone-functionalized monomer, a (methyl)acrylate ester substituted xanthone, a thioxanthone, a benzyl, a phenanthrenequinone, an anthraquinone, a substituted benzophenone, and mixtures thereof.

9. The method of claim 7 wherein said polymerizable photoinitiator is present in an amount of up to 1 mole % based on the total number of moles of monomer in the reaction mixture in step a).

10. A method of forming a block copolymer by a single electron transfer living radical polymerization comprising the steps of:

a) combining the macroinitiator polymer from claim 1 with at least one additional vinyl monomer, additional solvent, and 1 equivalent of a source of Cl per terminal halogen equivalent in the macroinitiator polymer to form a halogen exchange reaction mixture;

b) incubating the halogen exchange reaction mixture at 35°

C. for at least 3 hours with stirring;

c) after step b) adding to the halogen exchange reaction mixture a solid copper hydrazine-activate catalyst and polymerizing the at least one additional vinyl monomer for a period of time sufficient to increase the molecular weight of the macroinitiator polymer by 4,000 to 15,000 gram/mole while maintaining the polydispersity index at 1.2 to 1.8.

11. The method of claim 10, wherein step a) comprises using as said at least one additional vinyl monomer methyl methacrylate.

12. The method of claim 10, further comprising after step c) a purification process comprising:

d) adding to the product of step c) 3000 ppm of etidronic acid and incubating the mixture at 40°

C. for 2 hours;

e) adding additional solvent to the mixture of step d) and filtering the mixture through a filter having pores of 0.5 microns;

f) washing the filtrate of step e) with a brine solution of 20% sodium chloride a plurality of times and retaining the organic phase from each washing; and

g) drying the organic phase and then removing the solvent by evaporation to produce a powdered form of the block copolymer.

13. The method of claim 10, further comprising in step a) of claim 10 providing at least one polymerizable photoinitiator in said halogen exchange reaction mixture, said photoinitiator polymerizing into said polymer in step c) of claim 10 and providing UV curable crosslinking functionality to said block copolymer.

14. The method of claim 13 wherein said polymerizable photoinitiator is selected from the group consisting of 4-benzoylphenyl methacrylate, a benzophenone-functionalized monomer, a (methyl)acrylate ester substituted xanthone, a thioxanthone, a benzyl, a phenanthrenequinone, an anthraquinone, a substituted benzophenone, and mixtures thereof.

15. The method of claim 13 wherein said polymerizable photoinitiator is present in an amount of up to 1 mole % based on total number of moles of monomer added into the halogen exchange reaction mixture in step a) of claim 10.

16. A method of forming a macroinitiator polymer a single electron transfer living radical polymerization comprising the steps of:

a) providing a reaction mixture comprising at least one vinyl monomer, a halogen terminated initiator, and a ligand in a solvent;

b) purging the reaction mixture with nitrogen; and

c) adding to the reaction mixture a solid copper hydrazine-activated catalyst and polymerizing the reaction mixture in the presence of the catalyst under a positive pressure of nitrogen to produce a macroinitiator polymer having a molecular weight of from 4,000 to 15,000 grams/mole, a polydispersity index of 1.2 to 1.8, and a glass transition temperature of greater than 80°

C.

17. The method of claim 16, wherein step a) comprises providing as the at least one vinyl monomer methyl methacrylate.

18. The method of claim 16, wherein step a) comprises providing a bromine terminated initiator.

19. The method of claim 16, wherein step a) comprises providing as the initiator one of dimethyl 2,6-dibromoheptanedioate and methyl-2-bromopropionate.

20. The method of claim 16, wherein step a) comprises providing as the ligand hexamethylated tris (2-aminoethyl) amine.

21. The method of claim 16, wherein step a) comprises providing as the solvent dimethyl sulfoxide.

22. The method of claim 16, further comprising in step a) providing at least one polymerizable photoinitiator in said reaction mixture, said photoinitiator polymerizing into said macroinitiator polymer in step c) and providing UV curable crosslinking functionality to said macroinitiator polymer.

23. The method of claim 22 wherein said polymerizable photoinitiator is selected from the group consisting of 4-benzoylphenyl methacrylate, a benzophenone-functionalized monomer, a (methyl)acrylate ester substituted xanthone, a thioxanthone, a benzyl, a phenanthrenequinone, an anthraquinone, a substituted benzophenone, and mixtures thereof.

24. The method of claim 22 wherein said polymerizable photoinitiator is present in an amount of up to 1 mole % based on total number of moles of monomer in the reaction mixture.

25. The method of claim 16 comprising the further steps after step c) of:

d) adding to the product of step c) 3000 ppm of etidronic acid and incubating the mixture at 40°

C. for 2 hours;

e) adding additional solvent to the mixture of step d) and filtering the mixture through a filter having pores of 0.5 microns;

f) washing the filtrate of step e) with a brine solution of 20% sodium chloride a plurality of times and retaining the organic phase from each washing; and

g) drying the organic phase and then removing the solvent by evaporation to produce a powdered form of the macroinitiator polymer.

26. A method of forming a block copolymer by a single electron transfer living radical polymerization comprising the steps of:

a) combining the macroinitiator polymer from claim 25 step g) with at least one additional vinyl monomer, solvent, and ligand to form a reaction mixture;

b) incubating the reaction mixture from step a) with stirring for a period of time sufficient to form a clear reaction mixture;

c) after step b) adding to the clear reaction mixture a solid copper hydrazine-activate catalyst and polymerizing the at least one additional vinyl monomer for a period of time sufficient to increase the molecular weight of the macroinitiator polymer by 55,000 to 75,000 grams/mole while maintaining the polydispersity index at 1.2 to 1.8.

27. The method of claim 26, wherein step a) comprises using as said additional vinyl monomers vinyl monomers selected from the group consisting of 2-ethylhexyl acrylate, methacrylate, n-butyl acrylate, tert-butyl acrylate, and mixtures thereof.

28. The method of claim 26, further comprising after step c) a purification process comprising:

d) adding to the product of step c) 3000 ppm of etidronic acid and incubating the mixture at 40°

C. for 2 hours;

e) adding additional solvent to the mixture of step d) and filtering the mixture through a filter having pores of 0.5 microns;

f) washing the filtrate of step e) with a brine solution of 20% sodium chloride a plurality of times and retaining the organic phase from each washing;

g) drying the organic phase and then removing the solvent by evaporation to produce a powdered form of the block copolymer.

29. The method of claim 26, wherein the period of time for step b) comprises at least 4 hours.

30. The method of claim 26, further comprising in step a) of claim 26 providing at least one polymerizable photoinitiator in said reaction mixture, said photoinitiator polymerizing into said block copolymer in step c) of claim 26 and providing UV curable crosslinking functionality to said block copolymer.

31. The method of claim 30 wherein said polymerizable photoinitiator is selected from the group consisting of 4-benzoylphenyl methacrylate, a benzophenone-functionalized monomer, a (methyl)acrylate ester substituted xanthone, a thioxanthone, a benzyl, a phenanthrenequinone, an anthraquinone, a substituted benzophenone, and mixtures thereof.

32. The method of claim 30 wherein said polymerizable photoinitiator is present in an amount of up to 1 mole % based on total number of moles of monomer in the reaction mixture of step a) of claim 26.