Crosslinkable Polymer Systems

• US 20070270542A1
• Filed: 08/02/2007
• Published: 11/22/2007
• Est. Priority Date: 10/08/2004
• Status: Abandoned Application

• Current Assignee: Reichhold Incorporated
• Original Assignee: Reichhold Incorporated
• Inventors: Nava, Hildeberto, Small, Aaron
• Application Number:
  US11/832,938
• Publication Number:
  US 20070270542A1
• Time in Patent Office: Days
• US Class Current: 524/548
• CPC Class Codes: C08F 299/00 Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
• CPC Class Codes: C08K 5/098 Metal salts of carboxylic acids
• CPC Class Codes: C08L 25/08 Copolymers of styrene C08L29/08, C08L35/06, C08L55/02 take precedence
• CPC Class Codes: C08L 25/14 with unsaturated esters
• CPC Class Codes: C08L 2666/06 Homopolymers or copolymers of unsaturated hydrocarbons; Derivatives thereof
• CPC Class Codes: C08L 2666/14 Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
• CPC Class Codes: C08L 67/06 Unsaturated polyesters

Abstract

The present invention provides a crosslinkable polymer system that can be crosslinked to form a wide variety of polymeric, copolymeric and oligomeric compounds. The crosslinkable system comprises (a) product Q formed from an aromatic ethylenically unsaturated moiety and a first reactive ethylenically unsaturated moiety, and (b) a second reactive ethylenically unsaturated moiety at least partially reacted with the first reactive ethylenically unsaturated moiety.

Claims

1. A crosslinkable polymer system comprising

(a) a product Q formed from an aromatic ethylenically unsaturated moiety and a reactive ethylenically unsaturated moiety, said product Q providing carbon-carbon linkages in the backbone of said crosslinkable system, and

(b) a thermosettable moiety, a thermoplastic moiety or a monomer wherein said product Q and said thermosettable moiety, thermoplastic moiety or monomer is crosslinkable with said reactive ethylenically unsaturated moiety of product Q.

2. The crosslinkable polymer system according to claim 1 wherein the aromatic ethylenically unsaturated monomer is selected from the group consisting of styrene and derivatives thereof, 2-vinyl pyridine, 6-vinyl pyridine, 2-vinyl pyrrole, 2-vinyl pyrrole, 5-vinyl pyrrole, 2-vinyl oxazole, 5-vinyl oxazole, 2-vinyl thiazole, 5-vinyl thiazole, 2-vinyl imidazole, 5-vinyl imidazole, 3-vinyl pyrazole, 5-vinyl pyrazole, 3-vinyl pyridazine, 6-vinyl pyridazine, 3-vinyl isoxozole, 3-vinyl isothiazole, 2-vinyl pyrimidine, 4-vinyl pyrimidine, 6-vinyl pyrimidine, and vinyl pyrazines.

3. The crosslinkable polymer system according to claim 1, wherein the first reactive ethylenically unsaturated monomer has the formula

wherein R₁, R₂, R₃ and R₄ are independently selected from the group consisting of H, halogen, CN, straight or branched alkyl having 1 to 20 carbon atoms, halogen-substituted straight or branched alkyl having 1 to 20 carbon atoms, β

-unsubstituted straight or branched alkenyl having 2 to 10 carbon atoms, halogen-substituted, -straight or branched alkenyl having 2 to 10 carbon atoms, unsubstituted straight or branched alkynyl having 2 to 10 carbon atoms, halogen-substituted straight or branched aklynyl having 2 to 10 carbon atoms, C₃ to C₈ cycloalkyl, amines, substituted phosphorus, sylyl, siloxy, epoxy, isocyanate, and hydroxyl.

4. The crosslinkable polymer system according to claim 1, wherein the second reactive ethylenically unsaturated moiety is selected from the group consisting of (meth)acrylates, polyfunctional acrylates, vinyl aromatics, heterocyclyls vinyl halides, vinyl esters of carboxylic acids, and methyl(allylic) monomers.

5. The crosslinkable polymer system of claim 1, further comprising a polymerization initiator having one or more atoms or atomic groups that are radically transferable.

6. The crosslinkable polymer system of claim 1, further comprising a transition metal catalyst.

7. The crosslinkable polymer system of claim 6, wherein said transition metal catalyst includes a polymerization ligand.

8. The crosslinkable polymer system of claim 1, further comprising a polymerization inhibitor.

9. The crosslinkable polymer system of claim 1, further comprising a chain transfer agent.

10. The crosslinkable polymer system of claim 1, further comprising one or more additives selected from the group consisting of fiber reinforcement, antioxidants, fillers, thickening agents, flow agents, lubricants, air release agents, wetting agents, UV stabilizers, compatibilizers and shrink-reducing additives.

11. The crosslinkable polymer system of claim 1, wherein the thermosetting moiety is selected from the group consisting of unsaturated polyesters, vinyl esters, polyurethane acrylates, isocyanurate acrylates, polyamide ester acrylates and polyurethanes.

12. The crosslinkable polymer system of claim 1, wherein the thermoplastic moiety is selected from the group consisting of styrene-based polymers, polyethylene, polyvinyl acetate-based polymers, polyvinyl chloride polymers, polyurethanes ABS copolymers, polyethyl methacrylates, polymethyl methacrylates, polycaprolactone, butadiene-styrene copolymer, saturated polyesters, vinyl chloride/vinyl acetate copolymer, vinyl acetate/acrylic acid copolymer, vinyl acetate/methacrylic acid copolymer, styrene/acrylonitrile copolymer, styrene acrylic acid/allylacrylate copolymer, styrene acrylic acid/allyl methacrylate copolymer, methyl methacrylate/alkyl ester of acrylic acid copolymer, methyl methacrylate/styrene copolymer, and methyl methacrylate/acrylamide copolymer, epoxy intermediates, fatty acid intermediates, isocyanate containing intermediates, and polyurethanes.

13. The crosslinkable polymer system of claim 1 further comprising one or more additives selected from the group consisting of fiber reinforcement, antioxidants, fillers, thickening agents, flow agents, lubricants, air release agents, wetting agents, UV stabilizers, compatibilizers and shrink-reducing additives.

14. The crosslinkable polymer system of claim 1, wherein the polymer is crosslinked with an organic peroxide.

15. The crosslinkable polymer system of claim 1, wherein the mixture of (a) and (b) includes a curing accelerator.

16. The crosslinkable polymer system of claim 1, wherein the polymer is crosslinked with a radiation curing initiator.

17. A crosslinkable polymer system comprising

(a) a product Q formed from an aromatic ethylenically unsaturated moiety and a first reactive ethylenically unsaturated moiety wherein product Q provides carbon-carbon linkages in the backbone of said crosslinkable polymer system,

(b) a second reactive ethylenically unsaturated moiety at least partially reacted with said first reactive ethylenically unsaturated moiety of product Q, and

(c) a thermosettable moiety, a thermoplastic moiety or a monomer wherein said thermosettable moiety, thermoplastic moiety or monomer is crosslinkable with said first or second reactive ethylenically unsaturated moiety or both.

18. The crosslinkable polymer system according to claim 17, wherein the aromatic ethylenically unsaturated monomer is selected from the group consisting of styrene and derivatives thereof, 2-vinyl pyridine, 6-vinyl pyridine, 2-vinyl pyrrole, 2-vinyl pyrrole, 5-vinyl pyrrole, 2-vinyl oxazole, 5-vinyl oxazole, 2-vinyl thiazole, 5-vinyl thiazole, 2-vinyl imidazole, 5-vinyl imidazole, 3-vinyl pyrazole, 5-vinyl pyrazole, 3-vinyl pyridazine, 6-vinyl pyridazine, 3-vinyl isoxozole, 3-vinyl isothiazole, 2-vinyl pyrimidine, 4-vinyl pyrimidine, 6-vinyl pyrimidine, and vinyl pyrazines.

19. The crosslinkable polymer system according to claim 17, wherein the first reactive ethylenically unsaturated monomer has the formula

wherein R₁, R₂, R₃ and R₄ are independently selected from the group consisting of H, halogen, CN, straight or branched alkyl having 1 to 20 carbon atoms, halogen-substituted straight or branched alkyl having 1 to 20 carbon atoms, β

-unsubstituted straight or branched alkenyl having 2 to 10 carbon atoms, halogen-substituted, -straight or branched alkenyl having 2 to 10 carbon atoms, unsubstituted straight or branched alkynyl having 2 to 10 carbon atoms, halogen-substituted straight or branched aklynyl having 2 to 10 carbon atoms, C₃ to C₈ cycloalkyl, heterocyclyl, meth(acrylates), vinyl aromatics, vinyl halides, vinyl esters of carboxylic acids, polyfunctional acrylates, and (meth)allylic monomers.

20. The crosslinkable polymer system according to claim 19, wherein the second reactive ethylenically unsaturated moiety is selected from the group consisting of (meth)acrylates, polyfunctional acrylates, vinyl aromatics, heterocyclyls, vinyl halides, vinyl esters of carboxylic acids, and methyl(allylic) monomers.

21. The crosslinkable polymer system of claim 19, further comprising a polymerization initiator having one or more atoms or atomic groups that are radically transferable.

22. The crosslinkable polymer system of claim 19, further comprising a transition metal catalyst.

23. The crosslinkable polymer system of claim 22, wherein said transition metal catalyst includes a polymerization ligand.

24. The crosslinkable polymer system of claim 22, further comprising a polymerization inhibitor.

25. The crosslinkable polymer system of claim 22, further comprising a chain transfer agent.

26. The crosslinkable polymer system of claim 19, wherein the thermosetting moiety is selected from the group consisting of unsaturated polyesters, saturated polyesters, vinyl esters, polyurethane acrylates, isocyanurate acrylates, polyamide ester acrylates and polyurethanes,

27. The crosslinkable polymer system of claim 19, wherein the thermoplastic moiety is selected from the group consisting of styrene-based polymers, polyethylene, polyvinyl acetate-based polymers, polyvinyl chloride polymers, polyurethanes, ABS copolymers, polyethyl methacrylates, polymethyl methacrylates, polycaprolactone, butadiene-styrene copolymer saturated polyesters, vinyl chloride/vinyl acetate copolymer, vinyl acetate/acrylic acid copolymer, vinyl acetate/methacrylic acid copolymer, styrene/acrylonitrile copolymer, styrene acrylic acid/allylacrylate copolymer, styrene acrylic acid/allyl methacrylate, methyl methacrylate/alkyl ester of acrylic acid copolymer, methyl methacrylate/styrene copolymer, and methyl methacrylate/acrylamide copolymer.

28. The crosslinkable polymer system of claim 19 further comprising one or more additives selected from the group consisting of fiber reinforcement, antioxidants fillers, thickening agents, flow agents, lubricants, air release agents, wetting agents, UV stabilizers, compatibilizers and shrink-reducing additives.

29. The crosslinkable polymer system of claim 19, wherein the polymer is crosslinked with an organic peroxide.

30. The crosslinkable polymer system of claim 19, wherein the system includes a curing accelerator.

31. The crosslinkable polymer system of claim 19, wherein the polymer is crosslinked with a radiation curing initiator.

32. A method of making a crosslinkable polymer system having carbon-carbon linkages in its backbone:

the method comprising the steps of;

(a) forming a product Q by reacting an aromatic ethylenically unsaturated monomer and a first reactive ethylenically unsaturated monomer with a second reactive ethylenically unsaturated monomer, and

(b) reacting at least partially the product Q of step (a) through the second reactive ethylenically unsaturated monomer to provide with carbon-carbon linkages in the backbone of the crosslinkable polymer system.

33. The method according to claim 32, wherein the step of crosslinking occurs in the range of −

20°

to 200°

C.

34. A method of making a crosslinkable polymer system having carbon-carbon linkages in its backbone, the method comprising the steps of:

(a) forming a product Q by reacting an aromatic ethylenically unsaturated monomer and a reactive ethylenically unsaturated monomer; and

(b) reacting the product Q of step (a) with a thermosettable moiety, a thermoplastic moiety or a monomer crosslinkable with the reactive ethylenically unsaturated monomer.