Dual cure reaction products of self-photoinitiating multifunctional acrylates with thiols and synthetic methods
View Patent ↗Self-photoinitiating liquid oligomeric compositions are disclosed. The oligomeric compositions are formed from multifunctional mercaptans and Michael addition polyacrylate resins, synthesized from multifunctional acrylates and β-dicarbonyl Michael donors, specifically β-keto esters, β-diketones, β-ketoamides or β-ketoanilides or combinations thereof The oligomeric compositions are provided along with uses thereof and methods of fabricating.
1. A liquid oligomeric composition comprising:
a multifunctional mercaptan;
an acidifying agent; and
an organic soluble, ungelled, uncrosslinked, Michael addition product said Michael addition product formed from:
a multifunctional acrylate Michael acceptor and a β-dicarbonyl Michael donor.
2. The liquid oligomeric composition, according to claim 1 , wherein said β-dicarbonyl Michael donor is selected from the group consisting of β-keto esters, β-diketones, β-ketoamides, β-ketoanilides, and mixtures thereof.
3. The liquid oligomeric composition, according to claim 2 , wherein said β-dicarbonyl has equivalent functionality (N) wherein N=2,4,6, or 8.
4. The liquid oligomeric composition, according to claim 3 , comprising a β-dicarbonyl donor compound having functionality=2 selected from the group consisting of: ethyl acetoacetate, methyl acetoacetate, 2-ethylhexyl acetoacetate, lauryl acetoacetate, t-butyl acetoacetate, acetoacetanilide, N-alkyl acetoacetanilide acetoacetamide, 2-acetoacetoxylethyl methacrylate, arlyl acetoacetate, benzyl acetoacetate, 2,4-pentanedione, 2,4-hexanedione, 3,5-heptanedione isobutyl acetoacetate, 2-methoxyethyl acetoacetate, and mixtures thereof.
5. The liquid oligomeric composition, according to claim 3 , comprising a β-dicarbonyl donor compound having functionality=4 selected from the group consisting of: 1,4-butanediol diacetoacetate, 1,6-bexanediol diacetoacetate, neopentyl glycol diacetoacetate, cyclohexane dimethanol diacetoacetate, alkoxylated bisphenol A diacetoacetate, and mixtures thereof.
6. The liquid oligomeric composition, according to claim 3 , comprising a β-dicarbonyl donor compound having functionality=6 selected from the group consisting of: trimethylol propane triacetoacetate, glycerin triacetoacetate, and polycaprolactone triacetoacetates, alkoxylated derivates thereof, and mixtures thereof.
7. The liquid oligomeric composition, according to claim 3 , comprising a β-dicarbonyl donor compound having functionality=8 selected from the group consisting of pentaerythritol tetraacetoacetate and alkoxylated derivates thereof.
8. The liquid oligomeric composition, according to claim 1 , wherein said multifunctional acrylate Michael acceptor is selected from the group consisting of diacrylates, triacrylates, and tetaacrylates.
9. The liquid oligomeric composition, according to claim 8 , wherein a ratio of acceptor to donor functional groups is selected from the group consisting of ≧1:1 where said β-dicarbonyl functionality=2, ≧4.5:1 where said β-dicarbonyl functionality=6, and ≧3.5:1 where said β-dicarbonyl functionality=8.
10. The liquid oligomeric composition, according to claim 8 , wherein a ratio of acceptor to donor functional groups is selected from the group consisting of ≧2.1 where said β-dicarbonyl functionality=2, ≧6.4:1 where said β-dicarbonyl functionality=4, ≧7.8:1 where said β-dicarbonyl functionality=6, and ≧7.4:1 where said β-dicarbonyl functionality=8.
11. The liquid oligomeric composition, according to claim 8 , wherein a ratio of acceptor to donor functional groups is selected from the group consisting of ≧3.3 where said acetoacetate functionality=2, ≧12.3:1 where said β-dicarbonyl functionality=4, ≧13.2:1 where said β-dicarbonyl functionality=6, and ≧12.7:1 where said β-dicarbonyl functionality=8.
12. The liquid oligomeric composition, according to claim 8 , comprising a diacrylate Michael acceptor selected from the group consisting of:
ethylene glycol diacrylate, propylene glycol diacrylate, diethylene glycol diacrylate, dipropylene glycol diacrylate, triethylene glycol diacrylate, tripropylene glycol diacrylate, tertraethylene glycol diacrylate, tetrapropylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, ethoxylated bisphenol A diacrylate,
bisphenol A diglycidyl ether diacrylate, resorcinol diglycidyl ether diacrylate, 1,3-propanediol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, cyclohexane dimethanol diacrylate,
ethoxylated neopentyl glycol diacrylate, propoxylated neopentyl glycol diacrylate, ethoxylated cyclohexanedimethanol diacrylate, propoxylated cyclohexanedimethanol diacrylate, acrylated epoxy diacrylates, aryl urethane diacrylates, aliphatic urethane diacrylates, polyester diacrylates, and mixtures thereof.
13. The liquid oligomeric composition, according to claim 8 , comprising a tricrylate Michael acceptor selected from the group consisting of: trimethylol propane triacrylate, glycerol triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, tris(2-hydroxyethyl) isocyanurate triacrylate, ethoxylated glycerol triacrylate, propoxylated glycerol triacrylate, pentaerythritol triacrylate, aryrl urethane triacrylates, aliphatic urethane triacrylates, melamine triacrylates, aliphatic epoxy triacrylates, epoxy novolac triacrylates, polyester triacrylates and mixtures thereof.
14. The liquid oligomeric composition, according to claim 8 , comprising a tetraacrylate Michael acceptor selected from the group consisting of: pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, propoxylated pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, ethoxylated dipentaerythritol tetraacrylate, propoxylated dipentaerythritol tetraacrylate, aryl urethane tetraacrylates, aliphatic urethane tetraacrylates, melamine tetraacrylates, epoxy novolac tetraacrylates, and mixtures thereof.
15. The liquid oligomeric composition, according to claim 1 , wherein said β-dicarbonyl Michael donor is a β-diketone or a β-ketoester.
16. The liquid oligomeric composition, according to claim 1 , wherein said mercaptan is a dimercaptan.
17. The liquid oligomeric composition, according to claim 16 , wherein said dimercaptan is selected from the group consisting of
ethylene glycol dimercaptopropionate,
diethylene glycol dimercaptopropionate,
4-t-butyl-1,2-benzenedithiol,
bis-(2-mercaptoethyl)sulfide,
4,4′-thiodibenzenethiol,
benzenedithiol,
glycol dimercaptoacetate,
glycol dimercaptopropionate ethylene bis(3-mercaptopropionate),
polyethylene glycol dimercaptoacetates,
polyethylene glycol di(3-mercaptopropionates),
2,2-bis(mercaptomethyl)-1,3-propanedithiol,
2,5-dimercaptomethyl-1,4-dithiane,
bisphenofluorene bis(ethoxy-3-mercaptopropionate),
4,8-bis (mercaptomethyl)-3,6,9-trithia-1,11-undecanedithiol,
2-mercaptomethyl-2-methyl-1,3-propanedithiol,
1,8-dimercapto-3,6-dioxaoctane, and
thioglycerol bismercapto-acetate.
18. The liquid oligomeric composition, according to claim 16 , wherein said di-functional mercaptan is ethylene glycol dimercaptopropionate.
19. The liquid oligomeric composition, according to claim 1 , wherein said mercaptan is a trimercaptan.
20. The liquid oligomeric composition, according to claim 19 , wherein said trimercaptan is selected from the group consisting of
trimethylol propane(tris-mercaptopropionate) (TMPTMP),
trimethyloipropane tris(3-mercaptopropionate),
trimethylolpropane tris(3-mercaptoacetate),
Tris-(3-mercaptopropyl) isocyanurate,1,2,3-trimercaptopropane,
dipentaerythrithiol,
1,2,4-trimercaptomethyl benzene, and
tris(3-mercaptopropionate)triethyl-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione.
21. The liquid oligomeric composition, according to claim 19 , wherein said tri-functional mercaptan is trimethylol propane (tris-mercaptopropionate) (TMPTMP).
22. The liquid oligomeric composition, according to claim 1 , wherein said mercaptan is a polyfunctional mercaptan.
23. The liquid oligomeric composition, according to claim 22 , wherein said polyfunctional mercaptan is selected from the group consisting of
Poly(mercaptopropyl methyl) siloxane (PMPMS),
4-mercaptomethyl-3,6-dithia-1,8-octanedithiolpentaerythritol tetrakis (3-mercaptoacetate), and
pentaerythritol tetrakis(3-mercapto-propionate).
24. The liquid oligomeric composition, according to claim 22 , wherein said polyfunctional mercaptan is poly(mercaptopropyl methyl)siloxane (PMPMS).
25. The liquid oligomeric composition, according to claim 1 , wherein said Michael addition reaction is carried out in the presence of a strong base.
26. The liquid oligomeric composition, according to claim 25 , wherein said base is chosen from the group consisting of cyclic amidines, guanidines, group I alkoxides, quaternary hydroxides, quaternary alkoxides, and alkoxide bases generated in situ by reaction between a halide anion and an epoxy moiety.
27. The liquid oligomeric composition, according to claim 26 , wherein said alkoxide is generated in-situ by reaction between a quaternary halide and an epoxide moiety.
28. The liquid oligomeric composition, according to claim 25 , wherein said base is chosen from the group consisting of diazabicycloundecene (DBU), diazabicyclo-nonene (DBN), and 1,1,3,3-tetramethyl guanidine.
29. The liquid oligomeric composition, according to claim 1 , wherein said Michael addition reaction occurs in the presence of at least one non-reactive solvent.
30. The liquid oligomeric composition, according to claim 29 , wherein said non-reactive solvent is selected from the group consisting of styrene, t-butyl styrene, α-methyl styrene, vinyl toluene, vinyl acetate, allyl acetate, allyl methacrylate, diallyl phthalate, C1–C18-methacrylate esters, dimethacrylates, and trimethacrylates.
31. The liquid oligomeric composition, according to claim 1 , wherein said composition is shelf stable for more than one month and has residual pendant unsaturated acrylate groups.
32. The Liquid oligomeric composition, according to claim 1 , further comprising a stabilizing agent.
33. The liquid oligomeric composition, according to claim 32 , wherein a preferred stabilizing agent comprises (N-nitroso-N-phenylhydroxylamine) 3 Al.
34. The liquid oligomeric composition, according to claim 1 , wherein said acidifying agent is chosen from a group consisting of phosphoric acids, carboxylic acids, acid half esters, and inorganic acid esters.
35. The liquid oligomeric composition, according to claim 34 , wherein a preferred acidifying agent is selected from the group consisting of phosphate esters of 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, and 4-hydroxybutyl methacrylate.
36. The liquid oligomeric composition, according to claim 1 , further comprising a monoacrylate.
37. The liquid oligomeric composition, according to claim 36 , wherein said monoacrylate is chosen from the group consisting of C 1 –C 18 acrylate esters, isobornyl acrylate (IBOA), tetrahydrofurfuryl acrylate (THFFA), 2-(2ethoxy ethoxy)ethyl acrylate (EOEOEA), phenoxyethyl acrylate (PEA), hydroxyalkyl acrylate, monoalkyl polyalkylene glycol acrylate, siloxane, silane or silicone acrylate, perfluoroalkyl acrylate, caprolactone acrylate, and mixtures thereof.
38. The liquid oligomeric composition, according to claim 36 , wherein said monoacrylate is present up to about 50 mol %.
39. The liquid oligomeric composition, according to claim 36 , wherein said monoacrylate is present in amounts from greater than 0 to about 25 mol %.
40. The liquid oligonieric composition, according to claim 36 , wherein said monoacrylate is present in amounts from greater than 0 up to about 12.5 mol %.
41. The liquid oligomeric composition, according to claim 1 , further comprising a free-radical generator.
42. The liquid oligomeric composition, according to claim 41 , wherein said free-radical generator comprises a peroxide.
43. The liquid oligomeric composition, according to claim 42 , wherein said peroxide is selected from the group consisting of methyl ethyl ketone peroxide (MEKP), tert-butyl perbenzoate (TBPB), cumyl peroxide, and t-butyl peroxide.
44. A polymerized product obtained by crosslinking:
a liquid oligomeric composition comprising:
a multifunctional mercaptan;
an acidifying agent; and
an organic soluble, ungelled, uncrossliniked, Michael addition product said Michael addition product formed from:
multifunctional acrylate, Michael acceptor and a β-dicarbonyl Michael donor,
wherein said oligomeric composition is crosslinked in the presence of a free-radical generator.
45. The polymerized product, according to claim 44 , wherein said free-radical generator is actinic light.
46. The polymerized product, according to claim 44 , wherein said free-radical generator is a peroxide.
47. A method of making a liquid oligonieric composition, wherein said oligomeric composition has pendant unsaturated acrylate groups, the method comprising:
reacting a multifunctional acrylate Michael acceptor and a β-dicarbonyl Michael donor in the presence of a strong base to form a Michael adduct having pendant unsaturated acrylate groups;
adding an acidifying agent to said adduct in an amount at least stoichiometric with said base; and
admixing a multifunctional mercaptan.
48. A method of using a liquid oligomeric composition comprising:
providing a liquid oligomeric composition comprising:
a multifunctional mercaptan,
an acidifying agent, and
an organic soluble, ungelled, uncrosslinked, Michael addition reaction product said Michael Addition product formed a multifunctional acrylate Michael accepter and a β-dicarbonyl Michael donor;
applying said oligomeric composition to a surface; and
curing said composition in the total absence of exogenous photoinitiator.
49. A method of using a liquid oligomeric composition, according to claim 48 , wherein curing comprises providing a free-radical generator.
50. A method of using a liquid oligomeric composition, according to claim 49 , wherein said free-radical generator is actinic light.
51. A method of using a liquid oligomeric composition, according to claim 49 , wherein curing comprises reacting said composition under base catalyzed conditions.
52. A method of using a liquid oligomeric composition, according to claim 49 , wherein said composition further comprises at least one additive.
53. A method of using a liquid oligomeric composition, according to claim 52 , wherein said additive is selected from the group consisting of pigments, gloss modifiers, flow and leveling agents and other additive as appropriate to formulate coatings, paints, laminates, sealants, adhesives and inks.