Method of making graft polymers

• US 5,986,015 A
• Filed: 05/16/1997
• Issued: 11/16/1999
• Est. Priority Date: 05/16/1997
• Status: Expired due to Fees

• Current Assignee: The Procter & Gamble Company
• Original Assignee: The Procter & Gamble Company
• Inventors: Nijakowski, Timothy Roy, Midha, Sanjeev
• Primary Examiner(s): Dawson, Robert
• Assistant Examiner(s): AYLWARD, DAVID E
• Application Number:
  US08/858,070
• Time in Patent Office: 914 Days
• Field of Search: 525/370, 525/331.4, 525/331.6
• US Class Current: 525/370
• CPC Class Codes: A61K 8/895 containing silicon bound to unsaturated aliphatic groups, e.g. vinyl dimethicone
• CPC Class Codes: A61K 8/91 Graft copolymers A61K8/89 takes precedence
• CPC Class Codes: A61Q 17/04 Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
• CPC Class Codes: A61Q 19/00 Preparations for care of the skin
• CPC Class Codes: A61Q 19/08 Anti-ageing preparations
• CPC Class Codes: A61Q 3/02 Nail coatings
• CPC Class Codes: A61Q 5/02 Preparations for cleaning the hair
• CPC Class Codes: A61Q 5/06 Preparations for styling the hair, e.g. by temporary shaping or colouring
• CPC Class Codes: A61Q 5/12 Preparations containing hair conditioners
• CPC Class Codes: C08F 2438/01 Atom Transfer Radical Polymerization [ATRP] or reverse ATRP
• CPC Class Codes: C08F 265/04 on to polymers of esters
• CPC Class Codes: C08F 291/00 Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00

Abstract

Disclosed is an improved method of making hydrophobic and hydrophilic graft polymers, which method comprises the steps of (a) reacting copolymerizable monomers to form an organic polymeric backbone having a weight average molecular weight of from about 15,000 grams/mole to about 200,000 grams/mole and a plurality of organic halide moieties covalently bonded to the polymeric backbone and pendant from the polymeric backbone and then, without a separate purification or isolation step; (b) reacting copolymerizable monomers with the organic halide moieties of the polymeric backbone by atom transfer free radical polymerization in the presence of a catalytic amount of a Cu(I) salt or other transition metal species complexed to a ligand suitable for solubilizing the salt in the reaction mixture to form a plurality of polymeric side chains covalently bonded to the polymeric backbone and pendant from the polymeric backbone and having a weight average molecular weight of from about 500 grams/mole to about 200,000 grams/mole, wherein the polymeric back bone and the plurality of polymeric side chains form hydrophilic and hydrophobic graft polymers having a weight average molecular weight of from about 16,000 grams/mole to about 10,000,000 grams/mole.

Claims

1. A method of making graft polymers, which process comprises the steps of:

(a) reacting copolymerizable monomers to form an organic polymeric backbone having a weight average molecular weight of from about 15,000 grams/mole to about 9,800,000 grams/mole and a plurality of organic halide moieties covalently bonded to the polymeric backbone and pendant from the polymeric backbone and then without a separate purification or isolation step;

(b) reacting copolymerizable monomers with the organic halide moieties of the polymeric backbone by atom transfer free radical polymerization in the presence of a catalytic amount of a Cu(I) salt complexed to a ligand suitable for solubilizing the salt in the reaction mixture to form a plurality of polymeric side chains covalently bonded to the polymeric backbone and pendant from the polymeric backbone, the polymeric side chains having an average molecular weight of from about 500 grams/mole to about 200,000 grams/mole;

wherein the polymeric backbone and the plurality of polymeric side chains form graft polymers having a weight average molecular weight of from about 16,000 grams/mole to about 10,000,000 grams/mole.

2. The method of claim 1 wherein the Cu(I) salts are selected from the group consisting of Cu(I)Br, Cu(I)Cl, Cu(I)I, Cu(I) thiocyanate, and combinations thereof.

3. The method of claim 2 wherein the ligand is an aprotic bidendate.

4. The method of claim 3 wherein the aprotic bidendate is selected from the group consisting of 2,2'"'"' dipyridyl, diphosphates, C₁ -C₂₀ alkyl substituted bipyridyl, and combinations thereof.

5. The method of claim 4 wherein the alkyl substituted bipyridyl is 4,4'"'"'-di-5-nonyl-2,2'"'"'-bipyridyl, 4,4'"'"'-di-tert-butylbipyridyl, 4,4'"'"'-diheptyl-2,2'"'"'-bipyridyl, or combinations thereof.

6. The method of claim 2 wherein reaction of step (a) is free radical polymerization of the copolymerizable monomers.

7. The method of claim 6 wherein the copolymerizable monomers of step (a) comprise an organic halide-containing vinyl monomer and a second monomer selected from the group consisting of acrylic acid produced by hydrolysis of trimethylsilyl acrylate, methacrylic acid produced by hydrolysis of trimethylsilyl methacrylate, vinyl pyrrolidone, acrylic acid esters of C₁ -C₁₈ alcohols, methacrylic acid esters of C₁ -C₁₈ alcohols, trimethylsilyl acrylate, trimethylsilyl methacrylate, styrene, alpha-methylstyrene, t-butylstyrene, vinyl acetate, vinyl propionate, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, methyl methacrylate, salts thereof, and mixtures thereof.

8. The method of claim 7 wherein the organic halide-containing vinyl monomer of step (a) is selected from the group consisting of ##STR6## and combinations thereof, wherein R is methyl or hydrogen;

X is a halogen atom;

R, R¹ and R² are each independently methyl, hydrogen or methoxy; and

R⁴ is an alkyl group having from 1 to 8 carbon atoms.

9. The method of claim 8 wherein the polymeric backbone represents from about 50% to about 99% by weight of the graft polymer, and the plurality of polymeric side chains represent from about 1% to about 50% by weight of the graft polymer.

10. The method of claim 9 wherein the graft polymer is hydrophilic and has a polymeric backbone having a Tg value of less than about 35°

C. and a plurality of polymeric side chains having a Tg value greater than about 50°

C.

11. The method of claim 10 wherein the polymeric backbone has a Tg value of less than about 10°

C. and the plurality of polymeric side chains have a Tg value of greater than 70°

C.

12. The method of claim 9 wherein the graft polymer is hydrophilic and has a polymeric backbone having a Tg value greater than about 30°

C. and a plurality of polymeric side chains having a Tg value less than about 10°

C.

13. The method of claim 12 wherein the polymeric backbone has a Tg value greater than about 50°

C. and the plurality of polymeric side chains have a Tg value less than about -20°

C.

14. The method of claim 9 wherein the graft polymer is hydrophobic.

24. The method of claim 7 wherein the copolymerizable monomers of step (a) further comprise a polysiloxane-containing vinyl macromonomer.

15. A method of making graft polymers, which process comprises the steps of:

(a) reacting by free radical polymerization copolymerizable monomers to form an organic polymeric backbone having a weight average molecular weight of from about 15,000 grams/mole to about 9,800,000 grams/mole and a plurality of organic halide moieties covalently bonded to the polymeric backbone and pendant from the polymeric backbone and then, without a separate purification or isolation step;

(b) reacting copolymerizable monomers with the organic halide moieties of the polymeric backbone by atom transfer free radical polymerization in the presence of a catalytic amount of a Cu(I) halide salt /2,2'"'"' bipyridyl complex to form a plurality of polymeric side chains covalently bonded to the polymeric backbone and pendant from the polymeric backbone, the polymeric side chains having an average molecular weight of from about 500 grams/mole to about 200,000 grams/mole,

wherein the polymeric backbone and the plurality of polymeric side chains form graft polymers having a weight average molecular weight of from about 16,000 grams/mole to about 10,000,000 grams/mole.

16. The method of claim 15 wherein the Cu(I) halide salt is selected from the group consisting of Cu(I)Br, Cu(I)Cl, Cu(I)I, Cu(I) thiocyanate and combinations thereof.

17. The method of claim 16 wherein the copolymerizable monomers of step (a) comprise an organic halide-containing vinyl monomer and a second monomer selected from the group consisting of acrylic acid produced by hydrolysis of trimethylsilyl acrylate, methacrylic acid produced by hydrolysis of trimethylsilyl methacrylate, N,N-dimethyl acrylamide, dimethylaminoethyl methacrylate, quaternized dimethylaminoethyl methacrylate, vinyl pyrrolidone, acrylic acid esters of C₁ -C₁₈ alcohols, methacrylic acid esters of C₁ -C₁₈ alcohols, trimethylsilyl acrylate, trimethylsilyl methacrylate, styrene, alpha-methylstyrene, t-butylstyrene, vinyl acetate, vinyl propionate, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, methyl methacrylate, salts thereof, and mixtures thereof.

18. The method of claim 17 wherein the organic halide-containing vinyl monomer of step (a) is selected from the group consisting of ##STR7## and combinations thereof, wherein R is methyl or hydrogen;

X is a halogen atom;

R, R¹ and R² are each independently methyl, hydrogen or methoxy; and

R⁴ is an alkyl group having from 1 to 8 carbon atoms.

19. The method of claim 18 wherein the polymeric backbone represents from about 50% to about 99% by weight of the graft polymer, and the plurality of polymeric side chains represent from about 1% to about 50% by weight of the graft polymer.

20. The method of claim 19 wherein the graft polymer is hydrophilic and has a polymeric backbone having a Tg value of less than about 35°

C. and a plurality of polymeric side chains having a Tg value greater than about 50°

C.

21. The method of claim 20 wherein the polymeric backbone has a Tg value of less than about 10°

C. and the plurality of polymeric side chains have a Tg value of greater than 70°

C.

22. The method of claim 19 wherein the graft polymer is hydrophilic and has a polymeric backbone having a Tg value greater than about 30°

C. and a plurality of polymeric side chains having a Tg value less than about 10°

C.

23. The method of claim 22 wherein the polymeric backbone has a Tg value greater than about 50°

C. and the plurality of polymeric side chains have a Tg value less than about -20°

C.

25. The method of claim 17 wherein the copolymerizable monomers of step (a) further comprise a polysiloxane-containing vinyl macromonomer.

26. The method of claim 19 wherein the graft polymer is hydrophobic.