Method for producing an article containing a radiation cross-linked polymer and the article produced thereby

• US 4,908,229 A
• Filed: 09/09/1988
• Issued: 03/13/1990
• Est. Priority Date: 03/11/1986
• Status: Expired due to Term

• Current Assignee: Rohm and Haas Company (Dow, Inc.)
• Original Assignee: Union Oil Company of California (Chevron Corp.)
• Inventors: Kissel, Charles L.
• Primary Examiner(s): SILVERMAN, STANLEY S
• Application Number:
  US07/243,056
• Time in Patent Office: 550 Days
• Field of Search: 523/222, 428/224, 428/198, 428/288, 428/262, 428/290, 428/394, 427/54.1
• US Class Current: 427/513
• CPC Class Codes: C08F 220/283 and containing one or more carboxylic moiety in the chain, e.g. acetoacetoxyethyl(meth)acrylate
• CPC Class Codes: D06M 15/263 of unsaturated carboxylic acids; Salts or esters thereof
• CPC Class Codes: D06M 15/285 of unsaturated carboxylic acid amides or imides
• CPC Class Codes: D21H 17/38 containing crosslinkable groups
• CPC Class Codes: D21H 19/16 comprising curable or polymerisable compounds D21H19/24 takes precedence
• CPC Class Codes: D21H 25/06 of impregnated or coated paper D21H25/08 takes precedence

Abstract

A polymer comprising pendant functional groups having the formula ##STR1## wherein R₁ is a divalent radical and X is selected from the group consisting of organoacyl and cyano, is cross-linked by exposure to radiation having a wavelength in the range of about 10^-3 to about 400 nm.

Claims

1. A method of producing an article comprising the steps of:

(a) contacting a substrate with a polymer to form a substrate/polymer combination, the polymer comprising (i) at least about 10 weight percent olefinically unsaturated, carboxylic acid ester monomers, (ii) a backbone and (iii) a plurality of pendant functional groups, the pendant functional groups having the formula selected from the group consisting of ##STR14## wherein R₁ is a divalent radical; and

R₂ is selected from the group consisting of hydrogen and alkyl, arylalkyl, alkyloxy aryloxy, arylalkyloxy, alkenyl, alkenyloxy, alkynyl, alkynyloxy, and arylalkenyl radicals; and

(b) curing the polymer by exposing the substrate/polymer combination to radiation having a wavelength within the range of about 10^-3 to about 400 nm.

2. The method of claim 1 wherein the radiation is ultraviolet light.

3. The method of claim 2 wherein the ultraviolet light has a wavelength in the range of about 10 to about 300 nm.

4. The method of claim 2 wherein the ultraviolet light has a wavelength in the range of about 10 to about 250 nm.

5. The method of claim 2 wherein the ultraviolet light has a wavelength of about 10 to about 225 nm.

6. The method of claim 2 wherein the ultraviolet light has a wavelength of about 225 to about 265 nm.

7. The method of claim 1 wherein the substrate/polymer combination is exposed to the radiation for a period of time of up to about 15 minutes.

8. The method of claim 1 wherein the polymer is a constituent of a solution.

9. The method of claim 1 wherein the polymer is a constituent of a colloid.

10. The method of claim 9 wherein the colloid has a pH of about 2 to about 8.

11. The method of claim 1 wherein R₂ is hydrogen or an alkyl group containing up to about 10 atoms in addition to any hydrogen atoms present in the alkyl group.

12. The method of claim 1 wherein pendant functional groups have the formula ##STR15## wherein Y is selected from the group consisting of O, S, and NR₄ ;

Z is selected from the group consisting of O, S, and NR₄ ;

R₃ is a divalent organic radical at least 2 atoms in length; and

R₄ is selected from the group consisting of H and hydrocarbyl radicals having up to 6 carbon atoms.

13. The method of claim 12 wherein Y is O.

14. The method of claim 12 wherein Z is O.

15. The method of claim 12 wherein R₃ comprises up to about 40 atoms.

16. The method of claim 12 wherein R₃ comprises up to about 20 atoms.

17. The method of claim 12 wherein R₃ is selected from the group consisting of substituted and unsubstituted alkylenes, polyoxyalkylenes, polythiolalkylenes, and polyaminoalkylenes.

18. The method of claim 12 wherein R₃ is selected from the group consisting of ##STR16## wherein m is 0 or 1;

n is 0 or 1;

R₆ is a divalent organic radical at least one atom in length; and

R₇ is a divalent organic radical at least one atom in length.

19. The method of claim 1 wherein R₂ contains up to about 6 carbon atoms.

20. The method of claim 19 wherein R₂ is methyl.

21. The method of claim 1 wherein the substrate is a textile.

22. The method of claim 1 further comprising the step of forming the backbone by combining one or more olefinically unsaturated monomers.

23. The method of claim 22 wherein at least one of the olefinically unsaturated monomers has the formula ##STR17## wherein R₉ and R₁₀ are each independently selected from the group consisting of hydrogen, halo, thio, and monovalent organic radicals.

24. The method of claim 23 wherein at least one of the monomers is selected from the group consisting of (a) monocarboxylic acid esters, (b) polycarboxylic acid esters, (c) salts of (a) and (b), and (d) mixtures thereof.

25. The method of claim 23 wherein at least one of the monomers is selected from the group consisting of acrylic acid, itaconic acid, hydroxyethyl acrylate, acrylonitrile, and acrylamide.

26. The method of claim 1 wherein the polymer comprises at least about 0.5 weight percent of the pendant functional groups.

27. The method of claim 1 wherein the polymer comprises up to about 20 weight percent of the pendant functional groups.

28. A method of producing an article comprising the steps of:

(a) reacting one or more monomers with at least one polymerizable functional monomer to form a polymer, the polymer comprising at least about 10 weight percent olefinically unsaturated, carboxylic acid ester monomers, and the polymerizable functional monomer having the formula;

##STR18## wherein R₁ is a divalent organic radical of at least 3 atoms in length;

R₂ is selected from the group consisting of hydrogen and alkyl, arylalkyl, alkyloxy, aryloxy, arylalkyloxy, alkenyl, alkenyloxy, alkynyl, alkynyloxy, and arylalkenyl radicals;

R₉ is selected from the group consisting of hydrogen, halo, thio, and monovalent organic radicals;

R₁₀ is selected from the group consisting of hydrogen, halo, thio, and monovalent organic radicals;

(b) contacting the polymer with a substrate to form a substrate/polymer combination; and

(c) curing the substrate/polymer combination by exposing the substrate/polymer combination to ultraviolet light.

29. The method of claim 28 wherein the polymerizable functional monomer has the formula ##STR19## wherein Y is selected from the group consisting of O, S, and NR₄ ;

Z is selected from the group consisting of O, S, and NR₄ ;

R₃ is a divalent organic radical having at least two atoms; and

R₄ is selected from the group consisting of hydrogen and hydrocarbyl radicals containing up to about 6 carbon atoms.

30. The method of claim 28 wherein the polymerizable functional monomer has the formula selected from the group consisting of ##STR20##

31. A method of curing a polymer comprising the step of exposing the polymer to radiation having a wavelength within the range of about 10^-3 to about 400 nm, the polymer comprising (i) a backbone, (ii) at least about 10 weight percent olefinically unsaturated, carboxylic acid ester monomers, and (iii) a plurality of pendant functional groups, the pendant functional groups having the formula selected from the group consisting of ##STR21## wherein R₁ is a divalent radical;

and

R₂ is selected from the group consisting of hydrogen and alkyl, arylalkyl, alkyloxy, aryloxy, arylalkyloxy, alkenyl, alkenyloxy, alkynyl, alkynyloxy, and arylalkenyl radicals.

32. The method of claim 31 wherein the radiation is ultraviolet light.

33. The method of claim 31 wherein R₂ is hydrogen or an alkyl group containing up to about 10 atoms in addition to any hydrogen atoms present in the alkyl group.

34. The method of claim 31 wherein pendant functional groups have the formula ##STR22## wherein Y is selected from the group consisting of O, S, and NR₄ ;

Z is selected from the group consisting of O, S, and NR₄ ;

R₃ is a divalent organic radical at least 2 atoms in length; and

R₄ is selected from the group consisting of H and hydrocarbyl radicals having up to 6 carbon atoms.

35. The method of claim 31 further comprising the step of forming the backbone by combining one or more olefinically unsaturated monomers.

36. The method of claim 35 wherein at least one of the olefinically unsaturated monomers has the formula ##STR23## wherein R₉ and R₁₀ are each independently selected from the group consisting of hydrogen, halo, thio, and monovalent organic radicals.

37. A method of curing a polymer comprising the step of exposing the polymer to radiation having a wavelength within the range of about 10^-3 to about 400 nm, the polymer comprising at least about 10 weight percent olefinically unsaturated, carboxylic acid ester monomers, and being formed by reacting one or more monomers with at least one polymerizable functional monomer having the formula:

##STR24## wherein R₁ is a divalent radical;

R₉ and R₁₀ are each independently selected from the group consisting of hydrogen, halo, thio, and monovalent organic radicals; and

R₂ is selected from the group consisting of hydrogen and alkyl, arylalkyl, alkyloxy, aryloxy, arylalkyloxy, alkenyl, alkenyloxy, alkynyl, alkynyloxy, and arylalkenyl radicals.

38. The method of claim 37 wherein the polymerizable functional radical has the formula:

##STR25## wherein R₂ is selected from the group consisting of hydrogen and alkyl groups containing up to about 10 atoms in addition to any hydrogen atoms present in the alkyl group.

39. The method of claim 37 wherein the polymerizable functional monomer has the formula ##STR26## wherein Y is selected from the group consisting of O, S, and NR₄ ;

Z is selected from the group consisting of O, S, and NR₄ ;

R₃ is a divalent organic radical having at least two atoms; and

R₄ is selected from the group consisting of hydrogen and hydrocarbyl radicals containing up to about 6 carbon atoms.

40. The method of claim 37 wherein the polymerizable functional monomer has the formula selected from the group consisting of ##STR27##

41. The method of claim 37 wherein the polymer is exposed to radiation for a period of up to about 15 minutes.

42. A method for producing an article comprising the steps of:

(a) contacting a substrate with a polymer to form a substrate/polymer combination, the polymer comprising a backbone and a plurality of pendant functional groups, the pendant functional groups having the formula selected from the group consisting of ##STR28## wherein R₁ is a divalent radical; and

R₂ is selected from the group consisting of hydrogen and alkyl, arylalkyl, alkyloxy, aryloxy, arylalkyloxy, alkenyl, alkenyloxy, alkynyl, alkynyloxy, and arylalkenyl radicals; and

(b) curing the polymer by exposing the substrate/polymer combination to radiation having a wavelength within the range of about 10^-3 to about 400 nm.

43. The method of claim 42 wherein R₂ is hydrogen or an alkyl group containing up to about 10 atoms in addition to any hydrogen atoms present in the alkyl group.

44. The method of claim 42 wherein R₂ is hydrogen or an alkyl group comprising up to about 6 carbon atoms.

45. The method of claim 42 wherein R₂ is methyl.

46. The method of claim 42 wherein pendant functional groups have the formula ##STR29## wherein Y is selected from the group consisting of O, S, and NR₄ ;

Z is selected from the group consisting of O, S, and NR₄ ;

R₃ is a divalent organic radical at least 2 atoms in length; and

R₄ is selected from the group consisting of H and hydrocarbyl radicals having up to 6 carbon atoms.

47. The method of claim 46 wherein R₂ is selected from the group consisting of hydrogen or an alkyl group containing up to about 10 atoms in addition to any hydrogen atoms present in the alkyl group.

48. The method of claim 46 wherein R₂ is hydrogen or an alkyl group comprising up to about 6 carbon atoms.

49. The method of claim 46 wherein R₂ is methyl.

50. A method of producing an article comprising the steps of:

(a) reacting one or more monomers with at least one polymerizable functional monomer to form a polymer, the polymerizable functional monomer having the formula;

##STR30## wherein R₁ is a divalent organic radical of at least 3 atoms in length;

R₂ is selected from the group consisting of hydrogen and alkyl, arylalkyl, alkyloxy, aryloxy, arylalkyloxy, alkenyl, alkenyloxy, alkynyl, alkynyloxy, and arylalkenyl radicals;

R₉ is selected from the group consisting of hydrogen, halo, thio, and monovalent organic radicals;

R₁₀ is selected from the group consisting of hydrogen, halo, thio, and monovalent organic radicals;

(b) contacting the polymer with a substrate to form a substrate/polymer combination; and

(c) curing the substrate/polymer combination by exposing the substrate/polymer combination to ultraviolet light.

51. A method for curing a polymer comprising the step of exposing the polymer to radiation having a wavelength within the range of about 10^-3 to about 400 nm, the polymer comprising a backbone and a plurality of pendant functional groups, the pendant functional groups having the formula selected from the group consisting of:

##STR31## wherein R₁ is a divalent radical; and

R₂ is selected from the group consisting of hydrogen and alkyl, arylalkyl, alkyloxy, aryloxy, arylalkyloxy, alkenyl, alkenyloxy, alkynyl, alkynyloxy, and arylalkenyl radicals.

52. A method for curing a polymer comprising the step of exposing the polymer to radiation having a wavelength within the range of about 10^-3 to about 400 nm, the polymer being formed by reacting one or more monomers with at least one polymerizable functional monomer having the formula:

##STR32## wherein R₁ is a divalent organic radical;

R₂ is selected from the group consisting of hydrogen and alkyl arylalkyl, alkyloxy, aryloxy, arylalkyloxy, alkenyl, alkenyloxy, alkynyl, alkynyloxy, and arylalkenyl radicals; and

R₉ and R₁₀ are each independently selected from the group consisting of hydrogen, halo, thio, and monovalent organic radicals.