Multifunctional polymerizible alkoxy siloxane oligomers

• US 6,069,259 A
• Filed: 02/06/1998
• Issued: 05/30/2000
• Est. Priority Date: 02/06/1998
• Status: Expired due to Term

• Current Assignee: Rensselaer Polytechnic Institute
• Original Assignee: Rensselaer Polytechnic Institute
• Inventors: Crivello, James Vincent
• Primary Examiner(s): NAZARIO GONZALEZ, PORFIRIO
• Application Number:
  US09/019,632
• Time in Patent Office: 844 Days
• Field of Search: 556/458, 556/460, 556/467, 528/27, 528/32, 528/33, 528/41, 549/214, 549/215
• US Class Current: 549/214
• CPC Class Codes: C07F 7/0838 Compounds with one or more Si-O-Si sequences compounds with a ring containing only alternating Si and O atoms, i.e. cyclosilanes C07F7/21
• CPC Class Codes: C08G 77/045 containing less than 25 silicon atoms
• CPC Class Codes: C08G 77/14 containing silicon bound to oxygen-containing groups C08G77/045 takes precedence

Abstract

A composition relating to an oligomeric alkoxy siloxane substituted with polymerizible epoxy or 1-alkenyl groups, and a process for the production of that composition, are disclosed. The process entails a hydrolysis-condensation oligomerization of an epoxy- or 1-alkenyl ether-functional trialkoxy silane, catalyzed by an ion exchange resin, and separation of the resin from the resulting oligomer.

Claims

1. A polymerizable siloxane oligomer comprising the structure of Formula I:

##STR8## wherein R is an alkyl group of 1-10 carbons;

FG is a functional group and each FG in said oligomer is independently chosen from

linear, branched and cyclic alkyl residues of 1 to 20 carbons terminating in a 1-alkenyl ether;

linear, branched and cyclic alkyl ether residues of 1 to 20 carbons and 1 to 9 oxygens terminating in a 1-alkenyl ether;

linear, branched and cyclic alkyl residues of 1 to 20 carbons terminating in an acrylate, an alpha-chloroacrylate, an alpha-cyanoacrylate or a methacrylate;

linear, branched and cyclic alkyl ether residues of 1 to 20 carbons and 1 to 9 oxygens terminating in an acrylate, an alpha-chloroacrylate, an alpha-cyanoacrylate or a methacrylate;

linear, branched and cyclic alkyl residues of 1 to 20 carbons substituted with an epoxide;

linear, branched and cyclic alkyl ether residues of 1 to 20 carbons and 1 to 9 oxygens substituted with an epoxide;

arylalkyl residues of 1 to 20 carbons substituted with an epoxide;

arylalkyl ether residues of 1 to 20 carbons and 1 to 9 oxygens substituted with an epoxide; and

epoxy-functional organosiloxane residues of 1 to 20 silicons and 1 to 20 carbons;

R¹ is R or ##STR9## R² is R or ##STR10## and m and n are independently 2 to 50.

2. The composition of claim 1, wherein each FG has a structure independently chosen from the group consisting of the structures of Formulae A-P. ##STR11##

3. The composition of claim 1, wherein each FG is independently 2-(3,4-epoxycyclohexylethyl), 3-glycidoxypropyl, or 1-propenoxy-2-ethoxy ethyl.

4. The composition of claim 1, wherein each FG is independently 2-(3,4-epoxycyclohexylethyl) or 3-glycidoxypropyl.

5. The composition of claim 1, wherein m and n are independently 2 to 20.

6. A process for preparing a polymerizible alkoxy siloxane oligomer comprising reacting one or more silane monomers of formula (RO)₃ Si FG, wherein R is methyl or ethyl, and FG is independently chosen for each monomer from the group consisting of

linear, branched and cyclic alkyl residues of 1 to 20 carbons terminating in a 1-alkenyl ether;

linear, branched and cyclic alkyl ether residues of 1 to 20 carbons and 1 to 9 oxygens terminating in a 1-alkenyl ether;

linear, branched and cyclic alkyl residues of 1 to 20 carbons terminating in an acrylate, an alpha-chloroacrylate, an alpha-cyanoacrylate or a methacrylate;

linear, branched and cyclic alkyl ether residues of 1 to 20 carbons and 1 to 9 oxygens terminating in an acrylate, an alpha-chloroacrylate, an alpha-cyanoacrylate or a methacrylate;

linear, branched and cyclic alkyl residues of 1 to 20 carbons substituted with an epoxide;

linear, branched and cyclic alkyl ether residues of 1 to 20 carbons and 1 to 9 oxygens substituted with an epoxide;

arylalkyl residues of 1 to 20 carbons substituted with an epoxide;

arylalkyl ether residues of 1 to 20 carbons and 1 to 9 oxygens substituted with an epoxide; and

epoxy-functional organosiloxane residues of 1 to 20 silicons and 1 to 20 carbons;

with 0.5 to 2.5 equivalents of water in the presence of an ion exchange resin and separating the resin from said siloxane oligomer.

7. The process of claim 6, wherein said ion exchange resin is comprised of quaternary ammonium functionality.

8. The process of claim 6, wherein R is methyl or ethyl, and FG is independently chosen for each monomer from the group having structures A-P. ##STR12##

9. The process of claim 8, wherein said ion exchange resin is a quaternary ammonium resin.

10. A polymerizible siloxane oligomer produced by reacting one or more alkoxy silane monomers of formula (RO)₃ Si FG, wherein R is alkyl of 1-10 carbons and FG has a structure independently chosen for each monomer from the group consisting of:

linear, branched and cyclic alkyl residues of 1 to 20 carbons terminating in a 1-alkenyl ether;

linear, branched and cyclic alkyl ether residues of 1 to 20 carbons and 1 to 9 oxygens terminating in a 1-alkenyl ether;

linear, branched and cyclic alkyl residues of 1 to 20 carbons terminating in an acrylate, an alpha-chloroacrylate, an alpha-cyanoacrylate or a methacrylate;

linear, branched and cyclic alkyl ether residues of 1 to 20 carbons and 1 to 9 oxygens terminating in an acrylate, an alpha-chloroacrylate, an alpha-cyanoacrylate or a methacrylate;

linear, branched and cyclic alkyl residues of 1 to 20 carbons substituted with an epoxide;

linear, branched and cyclic alkyl ether residues of 1 to 20 carbons and 1 to 9 oxygens substituted with an epoxide;

arylalkyl residues of 1 to 20 carbons substituted with an epoxide;

arylalkyl ether residues of 1 to 20 carbons and 1 to 9 oxygens substituted with an epoxide; and

epoxy-functional organosiloxane residues of 1 to 20 silicons and 1 to 20 carbons;

with 0.5 to 2.5 equivalents of water, in the presence of an ion exchange resin, optionally in the presence of a solvent, and separating the resin from said siloxane oligomer.

11. A polymerizible oligomer according to claim 10, such that said oligomer has a viscosity of between 100 and 1,000,000 cps.

12. A polymerizible oligomer according to claim 10, such that said oligomer has a viscosity of greater than 1,000,000 cps.

13. A polymerizible siloxane oligomer according to claim 10, wherein FG has a structure independently chosen for each monomer from the group consisting of the structures of Formulae A-P. ##STR13##

14. A polymerizible oligomer according to claim 13, wherein said oligomer has a viscosity of between 100 and 1,000,000 cps.

15. A polymerizible oligomer according to claim 13, wherein said oligomer has a viscosity of greater than 1,000,000 cps.

16. A polymerizible siloxane oligomer according to claim 10, wherein FG for each monomer is independently 2-(3,4-epoxycyclohexylethyl) or 3-glycidoxypropyl.

17. A polymerizible oligomer according to claim 16, wherein said oligomer has a viscosity of between 100 and 1,000,000 cps.

18. A polymerizible oligomer according to claim 16, wherein said oligomer has a viscosity of greater than 1,000,000 cps.