Synthetic method for preparing dual curable silicone compositions
A synthetic method for preparing dual curable (e.g., thermal and light curable) silicone compositions is provided. The first step being a chemical modification of silanichydride bonds in cyclic siloxane monomer by the hydrosilylation reaction with acrylate-/methacrylate-containing allylic monomer. The second step being a ring-opening polymerization of the acrylate-/methacrylate-functionalized cyclic siloxane monomer with siloxane monomers using an oligosiloxane as a chain terminator.
1. A synthetic method for preparing a dual curable silicone composition, the method comprising:
a hydrosilylation reaction of hydride functionalized cyclic siloxane monomer with acrylate-/methacrylate-containing allylic monomer, giving an acrylate-/methacrylate-functionalized cyclic siloxane monomer; and
a ring-opening polymerization of the acrylate-/methacrylate-functionalized cyclic siloxane monomer with a linear polysiloxane, an optional C 1-4 alkyl substituted cyclic siloxane monomer, an optional hydride functionalized cyclic siloxane monomer, and an oligosiloxane as a chain terminator, the oligosiloxane having the same or different functional groups at both chain ends.
2. The method of claim 1 , wherein the hydride functionalized cyclic siloxane monomer is selected from the group consisting of tetramethylcyclotetrasiloxane, hexamethylcyclotetrasiloxane, heptamethylcyclotetrasiloxane, pentamethylcyclopentasiloxane, and combinations thereof.
3. The method of claim 1 , wherein the acrylate-/methacrylate-containing allylic monomer is selected from the group consisting of allyl acrylate, allyl methacrylate, di(propylene glycol)allylether methacrylate, and combinations thereof.
4. The method of claim 1 , wherein the C 1-4 alkyl substituted cyclic siloxane monomer is selected from the group consisting of octamethylcyclotetrasiloxane, 2,4,6-triethyl-2,4,6-trimethylcyclotrisiloxane, and combinations thereof.
5. The method of claim 1 , wherein the functional groups of the oligosiloxane are independently selected from the group consisting of vinyl (CH 2 ═CH—), acrylate (—OOCCH═CH 2 ), methacrylate (—OOC(CH 3 )C═CH 2 ), hydroxyl (—OH), hydride (—H), alkyl (—R), and alkoxyl (—OR), wherein said alkyl is optionally substituted with vinyl, acrylate, methacrylate, or hydroxyl.
6. The method of claim 1 , wherein the oligosiloxane is selected from the group consisting of siloxane dimer, siloxane trimer, siloxane tetramer, siloxane pentamer, and siloxane hexamer.
7. The method of claim 6 , wherein the siloxane dimer is selected from the group consisting of 1,3-divinyltetramethyldisiloxane, 1,3-bis(4-methacryloyloxybutyl)-1,1,3,3-tetramethyldisiloxane, 1,3-bis(3-methacryloyloxypropyl)-1,1,3,3-tetramethyldisiloxane, 1,3-dihydroxy-1,1,3,3-tetramethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, hexamethyldisiloxane, pentamethyldisiloxane, and 1,3-diethoxy-1,1,3,3-tetramethyldisiloxane.
8. The method of claim 6 , wherein the siloxane trimer is octamethyltrisiloxane.
9. The method of claim 6 , wherein the siloxane tetramer is 1,1,3,3,5,5,7,7-octamethyltetrasiloxane.
10. The method of claim 1 , wherein the acrylate-/methacrylate-functionalized cyclic siloxane monomer is acrylate-/methacrylate-containing tetramethylcyclotetrasiloxane of Structure 2:
wherein R 2 is a substituted group having acrylate, methacrylate, or di(propylene glycol) methacrylate group.
11. The method of claim 1 , wherein the silicone composition comprises a silicone of Structure 1:
wherein R, at each occurrence, is C 1-4 alkyl group; R 1 , at each occurrence, is a substituted group having an acrylate or methacrylate group; X and Y are independently selected from the group consisting of vinyl, acrylate, methacrylate, hydroxyl, hydride, alkyl, and alkoxyl, wherein said alkyl is optionally substituted with vinyl, acrylate, methacrylate, or hydroxyl; and
m, n, and o are independently an integer from 1-100 inclusive.
12. The method of claim 11 , wherein R, at each occurrence, is methyl or ethyl; R 1 , at each occurrence, is a propyl group comprising an acrylate or methacrylate group; X and Y are independently selected from the group consisting of vinyl, hydroxyl, hydride, and alkyl, wherein said alkyl is optionally substituted with acrylate, methacrylate, or hydroxyl; and m, n, and o are independently an integer from 1-100 inclusive.
13. The method of claim 11 , wherein the combined percentage of n and o with respect to m, n, and o is less than about 50%.
14. The method of claim 11 , wherein the silicone composition is curable by heat and light.