Adhesives and related methods
View Patent ↗Cure in place pressure sensitive adhesive compositions are described that comprise one or more of a bodying component, a structural diluent, a radical diluent as well as additives such as crosslinkers, external catalysts, photoinitiators and stabilizers/process aids. The bodying component can be acrylic or non-acrylic.
1. A cure in place composition comprising:
a pressure sensitive adhesive including 20-80 wt % of a pre-polymerized acrylic backbone base polymer having a molecular weight (Mw) of 100,000 to 1,000,000;
0-30 wt % of tackifier;
5-40 wt % of at least one reactive oligomer;
0-30 wt % of at least one of an acrylic-epoxy functional component;
0-30 wt % epoxy functional olefin; and
0-2 wt % of at least one of a metal chelate crosslinker-catalyst and external catalyst,
wherein the composition forms a structural adhesive upon exposure to a stimulus.
2. The cure in place composition of claim 1 further includes at least one structural diluent.
3. The cure in place composition of claim 1 wherein the acrylic backbone base polymer has a Mw of 250,000 to 750,000.
4. The cure in place composition of claim 1 wherein the acrylic backbone base polymer includes an acrylic block polymer.
5. The cure in place composition of claim 4 wherein the acrylic block polymer includes two reactive functional end segments and one non-reactive middle segment.
6. The cure in place composition of claim 5 wherein the non-reactive segment is non-reactive with the reactive functional group of the reactive segments.
7. The cure in place composition of claim 5 wherein the reactive segments include one or more monomers of the non-reactive segment.
8. The cure in place composition of claim 4 wherein the acrylic block polymer includes one reactive functional end segment and one non-reactive middle segment.
9. The cure in place composition of claim 8 wherein the non-reactive segment is non-reactive with the reactive functional group of the reactive segment.
10. The cure in place composition of claim 8 wherein the reactive segment includes one or more monomers of the non-reactive segment.
11. The cure in place composition of claim 2 wherein the structural diluent is selected from the group consisting of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (S-21), Bis[(3,4-epoxycyclohexyl)methyl]adipate (S-28), difunctional bisphenol A/epichlorohydrin derived liquid epoxy resin (Epon 828), Bisphenol A epoxy resin having a weight per epoxide of 235-263 g/eq as measured by ASTM D1652 (Epon 834), beta-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (A-186), gamma-glycidoxypropyltrimethoxysilane (A-187), glycidyl ester of neodecanoic acid (EP-10), isocyanate-functional urethane acrylate (Desmolux D100), isocyanate-bearing urethane acrylate (Desmolux D200), aliphatic polyisocyanate (low-viscosity hexamethylene diisocyanate (HDI) biuret) (Desmodur N3200), aliphatic polyisocyanate (hexamethylene diisocyanate (HDI) biuret) (Desmodur N100), aliphatic polyisocyanate (hexamethylene diisocyanate (HDI) trimer) (Desmodur N3300), poly(propylene oxide) (PPO) oligomer having a molecular weight (Mw) of less than 5,000 daltons, trimethylolpropane oxetane (TMPO), poly(ethylene oxide) (PEO) oligomer having a molecular weight (Mw) of less than 5,000 daltons, ethyl hexyl oxetane (2EH oxetane), difunctional oxetane, trimethylolpropane triacrylate (TMPTA) of the following formula (5), tripropyleneglycol diacrylate (TPGDA) of the following formula (6), ethoxylated bisphenol A diacrylate of the following formula (7) in which n+m=3, ethoxylated trimethylolpropane triacrylate of the following formula (8), bisphenol A diglycidyl ether diacrylate of the following formula (9), 1,2-cyclic ethers, 1,3-cyclic ethers, 1,4-cyclic ethers, anhydrides, lactones, lactams, cyclic ethers, siloxanes, oxazolines, oxalidines, and bismaleimides;
12. The cure in place composition of claim 2 wherein the structural diluent is selected from the group consisting of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (S-21), Bis[(3,4-epoxycyclohexyl)methyl]adipate (S-28), difunctional bisphenol A/epichlorohydrin derived liquid epoxy resin (Epon 828), Bisphenol A epoxy resin having a weight per epoxide of 235-263 g/eq as measured by ASTM D1652 (Epon 834), beta-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (A-186), gamma-glycidoxypropyltrimethoxysilane (A-187), glycidyl ester of neodecanoic acid (EP-10), isocyanate-functional urethane acrylate (Desmolux D100), isocyanate-bearing urethane acrylate (Desmolux D200), aliphatic polyisocyanate (low-viscosity hexamethylene diisocyanate (HDI) biuret) (Desmodur N3200), aliphatic polyisocyanate (hexamethylene diisocyanate (HDI) biuret) (Desmodur N100), aliphatic polyisocyanate (hexamethylene diisocyanate (HDI) trimer) (Desmodur N3300), poly(propylene oxide) (PPO) oligomer having a molecular weight (Mw) of less than 5,000 daltons, trimethylolpropane oxetane (TMPO), poly(ethylene oxide) (PEO) oligomer having a molecular weight (Mw) of less than 5,000 daltons, ethyl hexyl oxetane (2EH oxetane), difunctional oxetane, ethoxylated bisphenol A diacrylate of the following formula (7) in which n+m=3, ethoxylated trimethylolpropane triacrylate of the following formula (8), bisphenol A diglycidyl ether diacrylate of the following formula (9), 1,2-cyclic ethers, 1,3-cyclic ethers, 1,4-cyclic ethers, anhydrides, lactones, lactams, cyclic ethers, siloxanes, oxazolines, oxalidines, and bismaleimides;
13. The cure in place composition of claim 2 wherein the structural diluent is selected from the group consisting of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (S-21), Bis[(3,4-epoxycyclohexyl)methyl]adipate (S-28), difunctional bisphenol A/epichlorohydrin derived liquid epoxy resin (Epon 828), Bisphenol A epoxy resin having a weight per epoxide of 235-263 g/eq as measured by ASTM D1652 (Epon 834), beta-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (A-186), gamma-glycidoxypropyltrimethoxysilane (A-187), glycidyl ester of neodecanoic acid (EP-10), isocyanate-functional urethane acrylate (Desmolux D100), isocyanate-bearing urethane acrylate (Desmolux D200), aliphatic polyisocyanate (low-viscosity hexamethylene diisocyanate (HDI) biuret) (Desmodur N3200), aliphatic polyisocyanate (hexamethylene diisocyanate (HDI) biuret) (Desmodur N100), aliphatic polyisocyanate (hexamethylene diisocyanate (HDI) trimer) (Desmodur N3300), poly(propylene oxide) (PPO) oligomer having a molecular weight (Mw) of less than 5,000 daltons, trimethylolpropane oxetane (TMPO), poly(ethylene oxide) (PEO) oligomer having a molecular weight (Mw) of less than 5,000 daltons, ethyl hexyl oxetane (2EH oxetane), difunctional oxetane, ethoxylated bisphenol A diacrylate of the following formula (7) in which n+m=3, ethoxylated trimethylolpropane triacrylate of the following formula (8), bisphenol A diglycidyl ether diacrylate of the following formula (9), 1,2-cyclic ethers, 1,3-cyclic ethers, 1,4-cyclic ethers, butyrolactone, valerolactone, caprolactone, methy-butyrolactone, butyrolactam, valerolactam, caprolactam, cyclic ethers, siloxanes, oxazolines, oxalidines, bismaleimides,
and
lactones of the following formulas (10)-(12)
wherein n is 4 or 5, h, i, k, and m are independently 1 or 2 and each R is independently chosen from H or hydrocarbyl containing up to 12 carbon atoms.
14. The cure in place composition of claim 1 wherein the at least one reactive oligomer is a silane-terminated polyether (STPE).
15. A cure in place composition comprising:
a pressure sensitive adhesive including 20-80 wt % of a pre-polymerized acrylic backbone base polymer having a molecular weight (Mw) of 100,000 to 1,000,000;
0-30 wt % of tackifier;
5-40 wt % of at least one reactive oligomer, the at least one reactive oligomer is a silane-terminated polyether (STPE);
0-30 wt % of at least one of an acrylic-epoxy functional component;
0-30 wt % epoxy functional olefin; and
0-2 wt % of at least one of a metal chelate crosslinker-catalyst and external catalyst,
wherein the composition forms a structural adhesive upon exposure to a stimulus.
16. The cure in place composition of claim 15 further includes at least one structural diluent.
17. The cure in place composition of claim 15 wherein the acrylic backbone base polymer includes an acrylic block polymer.
18. The cure in place composition of claim 17 wherein the acrylic block polymer includes two reactive functional end segments and one non-reactive middle segment.
19. The cure in place composition of claim 18 wherein the non-reactive segment is non-reactive with the reactive functional group of the reactive segments.
20. The cure in place composition of claim 18 wherein the reactive segments include one or more monomers of the non-reactive segment.
21. The cure in place composition of claim 17 wherein the acrylic block polymer includes one reactive functional end segment and one non-reactive middle segment.
22. The cure in place composition of claim 21 wherein the non-reactive segment is non-reactive with the reactive functional group of the reactive segment.
23. The cure in place composition of claim 21 wherein the reactive segment includes one or more monomers of the non-reactive segment.
24. A construction comprising:
a substrate; and
the cure in place composition of claim 1 disposed on the substrate.
25. The construction of claim 24 wherein the pressure sensitive adhesive and the reactive oligomer are configured to crosslink to a structural adhesive upon exposure to a stimulus.
26. The construction of claim 25 wherein the stimulus is selected from the group consisting of radiation, heat, moisture, pressure, ultrasound, chemical exposure, and combinations thereof.
27. The construction of claim 24 wherein the pressure sensitive adhesive exhibits a subsequent crosslinked state including a structural adhesive formed from the pressure sensitive adhesive and the reactive oligomer.
28. The construction of claim 24 wherein the pressure sensitive adhesive and the reactive oligomer are selected to crosslink in the presence of a stimulus.
29. The construction of claim 28 wherein the stimulus is selected from the group consisting of radiation, heat, moisture, pressure, ultrasound, chemical exposure, and combinations thereof.
30. The cure in place composition of claim 1 wherein the stimulus is selected from the group consisting of radiation, heat, moisture, pressure, ultrasound, chemical exposure, and combinations thereof.