Photocurable liquid polyene-polythiol polymer compositions

申请号 US3661744D 申请日 1970-06-08 公开(公告)号 US3661744A 公开(公告)日 1972-05-09
申请人 GRACE W R & CO; 发明人 KEHR CLIFTON L; WSZOLEK WALTER R;
摘要 The invention disclosed is for a new photocurable liquid polymer composition which includes a liquid polyene component having a molecule containing at least two unsaturated carbon-to-carbon bonds disposed at terminal positions on a main chain of the molecule, a polythiol component having a molecule containing a multiplicity of pendant or terminally positioned -SH functional groups per average molecule, and a photocuring rate accelerator. The photocurable liquid polymer composition upon curing in the presence of actinic light forms odorless, solid, elastomeric or resinous products which may serve as sealants, coatings, adhesives and molded articles.
权利要求
  • 2. The composition of claim 1 wherein (A) has the formula: wherein a and b are integers greater than 1; R2 is a member of the group consisting of hydrogen and alkyl; R3 is a member of the group consisting of hydrogen, and saturated alkyl; R4 is a divalent derivative of the group consisting of phenyl, benzyl, alkyl, cycloalkyl, substituted phenyl, substituted benzyl, substituted alkyl and substituted cycloalkyl, said alkyl, cycloalkyl and substituents on members substituted being defined in claim 1.
  • 3. The composition of claim 5 wherein the photocuring rate accelerator is a member selected from the group consisting of aryl aldehyde, diaryl ketone, alkyl aryl ketone, triaryl phosphine, and a blend of carbon tetrahalide with polynuclear aromatic hydrocarbon.
  • 4. The composition of claim 1 wherein the polyene has the formula: wherein n is at least 1; and R7 is a member of the group consisting of CH2=CH CH2n , n, hydrogen, phenyl, cycloalkyl and alkyl; said substituent on member which is substituted, the cycloalkyl, and the alkyl defined as in claim 1.
  • 5. The composition of claim 1 wherein the polyene has the formula:
  • 6. The composition of claim 1 wherein the polyene has the formula:
  • 7. The composition of claim 1 wherein the polyene has the formula:
  • 8. The composition of claim 1 wherein the polyene has the formula:
  • 9. The composition of claim 1 wherein the polyene has the formula:
  • 10. The composition of claim 1 wherein the polyene has the formula:
  • 11. The composition of claim 1 wherein the polyene has the formula:
  • 12. The composition of claim 1 wherein the polyene has the formula:
  • 13. The composition of claim 1 wherein the polyene has the formula: where n is at least 1.
  • 14. The composition of claim 1 wherein the polyene has the formula:
  • 15. The composition of claim 1 wherein the polyene has the formula: wherein the sum of x + y + z is at least 1; n is at least 1; and R7 is a member of the group consisting of CH2=CH CH2n , hydrogen, alkyl, phenyl, and cycloalkyl said alkyl and cycloalkyl defined as in claim 1.
  • 16. The composition of claim 1 wherein the polyene has the formula: wherein the sum of x + y + z in each chain segment is at least 1; n is at least 1; R1 is selected from the group consisting of hydrogen, phenyl, benzyl, alkyl, cycloalkyl, and substituted phenyl; and R7 is a member of the group consisting of CH2=CH CH2n , =, hydrogen, alkyl, phenyl, and cycloalkyl; said member which is substituted, the cycloalkyl and the alkyl defined as in claim 1.
  • 17. The composition of claim 1 wherein the polyene has the formula: wherein the sum of x + y + z in each chain segment is at least 1; n is at least 1; R7 is a member of the group consisting of CH2=CH CH2n , hydrogen, phenyl, cycloalkyl and alkyl; said member which is substituted, the cycloalkyl and the alkyl defined as in claim 1.
  • 18. The composition of claim 1 wherein the polyene has the formula:
  • 19. The composition of claim 1 wherein the polyene has the formula: C3H5-O C3H6-O C3H5 wherein y is at least 1.
  • 20. The composition of claim 1 wherein the mole ratio of ene to thiol is from about 0.2/1 to about 5/1.
  • 21. The composition of claim 1 wherein the mole ratio of ene to thiol is about 0.75/1 to about 1.5/1.
  • 22. A process of forming essentially odorless solid polythioether which comprises I. Admixing: A. a terminally unsaturated polyene component which comprises the formula: (A= X)m wherein m is an integer of at least 2; wherein X is where f is an integer from 1 to 9; R is a radical selected from the group consisting of hydrogen, fluorine, chlorine, furyl, thienyl, pyridyl, phenyl and substituted phenyl, benzyl and substituted benzyl, alkyl and substituted alkyl, alkoxy and substituted alkoxy, cycloalkyl and substituted cycloalkyl; said substituents on said substituted members selected from the group consisting of nitro, chloro, fluoro, acetoxy, acetamide, phenyl, benzyl, alkyl, alkoxy and cycloalkyl; said alkyl and alkoxy having from one to nine carbon atoms and said cycloalkyl having from three to eight carbon atoms; wherein (A) is free of reactive carbon-to-carbon unsaturation; free of highly water-sensitive members; and is a polyvalent chamically compatible member of the group consisting of carbonate, carboxylate, carbonyl, ether, silane, silicate, phosphonate, phosphite, phosphate, alkyl and substituted alkyl, cycloalkyl and substitute cycloalkyl, aryl and substituted aryl, urethane and substituted urethane, urea and substituted urea, amine and substituted amine, amide and substituted amide, hydroxyl, heterocyclic carbon containing radical, and mixtures thereof; said substitutents on said members being defined above, said component having a molecular weight in the range from about 64 to 20,000; and a viscosity in the range from essentially 0 to 20 million centipoises at 70* C.; B. a polythiol component having a molecular weight in the range from about 50 to about 20,000 of the general formula: R8=SH)n wherein R8 is a polyvalent organic moiety free from reactive carbon-to-carbon unsaturation and n is at least 2, the sum of m and n being greater than 4, with the ene/thiol mole ratio being selected so as to provide a cross-linked solid, self-supporting cured product; and C. a photocuring rate accelerator, and thereafter II. exposing the mixture to actinic light.
  • 23. A photocurable composition useful for obtaining an essentially odorless, solid polythioether, said photocurable composition consisting essentially of: A. a terminally unsaturated polyene component having the formula:
  • 24. The solid product prepared by the process of claim 23.
  • 25. The process of claim 23 wherein the actinic light is ultraviolet radiation having a wavelength between about 2,000 A and about 4,000 A.
  • 26. The process of claim 23 wherein the composition contains from 0.0005 to 50 parts by weight of a photocuring rate accelerator.
  • 27. The process of claim 23 wherein the photocuring rate accelerator is selected from the group consisting of aryl aldehyde; diaryl ketone; alkyl aryl ketone; triaryl phosphine; a blend of carbon tetrahalide with polynuclear aromatic hydrocarbon.
  • 28. An article comprising the composition of claim 23 as a coating on a substrate.
  • 29. An article comprising the composition of claim 23 as an adhesive between two substrates.
  • 30. An article comprising the composition of claim 23 as an elastomeric sealant.
  • 31. A shaped, molded article cast from the composition of claim 23.
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