METHODS FOR PREPARING TOUGHENED EPOXY POLYMER COMPOSITE SYSTEMS
The present invention relates to epoxy resin compositions and more particularly to providing methods for toughening such epoxy resin systems. The methods include mixing a liquid epoxy resin with a glycidyl terminated modifying polymer and copolymerizing the epoxy resin and glycidyl terminated modifying polymer such that a liquid or gel phase comprising the modifying polymer separates from a solidified epoxy polymer to form the epoxy polymer composite system.
1 . A method for preparing a toughened epoxy polymer composite system, comprising
reacting epichlorohydrin with a modifying polymer having at least two terminal proton donating functional groups to terminate the modifying polymer with at least two glycidyl ethers,
mixing a liquid epoxy resin with the glycidyl terminated modifying polymer, and
copolymerizing the epoxy resin and the glycidyl terminated modifying polymer such that a liquid or gel phase comprising the modifying polymer separates from a solidified epoxy polymer to form the epoxy polymer composite system, and
wherein the modifying polymer has a molecular weight of about 2000 daltons or greater.
2 . The method of claim 1 , wherein the proton donating functional groups comprise —COOH, —OH, —NH(R), or —C(O)NH(R), wherein R is H or C 1-4 alkyl.
3 . The method of claim 1 wherein the modifying polymer has a molecular weight of about 3000 daltons or greater.
4 . The method of claim 1 wherein the modifying polymer has a molecular weight of between about 2000 to about 10,000 daltons.
5 . The method of claim 1 wherein the glass transition temperature of the composite system is no lower than about 25° C. below the glass transition temperature of the composite system in the absence of the modifying polymer.
6 . The method of claim 1 , wherein the modifying polymer is present in no more than 40 weight percent based on the total weight of epoxy resin and the modifying polymer.
7 . The method of claim 1 , wherein the modifying polymer is present in no more than 20 weight percent based on the total weight of epoxy resin and the modifying polymer.
8 . The method of claim 1 , wherein the glycidyl terminated modifying polymer is substantially dissolved in the liquid epoxy resin prior to co-polymerization.
9 . The method of claim 1 , wherein the liquid epoxy resin comprises a glycidated Bisphenol A or Bisphenol F.
10 . The method of claim 1 , wherein the modifying polymer is of the general formula
wherein R 1 comprises a polyether, polyester, polyacrylic, polyamide, polyolefin, polydiene, or polydiene/acrylonitrile copolymer, X is an ester, ether, amido or amino linkage, and n is 1-6.
11 . The method of claim 10 , wherein R 1 comprises a polyether, polyester, polybutadiene, or polybutadiene/acrylonitrile copolymer.
12 . The method of claim 10 , wherein R 1 is an alkoxylated diol or polyol.
13 . The method of claim 12 , wherein the polyol is a glycerol, trimethylol propane, pentaerythritol, or sorbitol.
14 . The method of claim 12 , wherein the alkoxylate moiety comprises repeating C 2 -C 4 oxide units, or mixtures thereof.
15 . The method of claim 10 , wherein R 1 is a butadiene or butadiene/acrylonitrile copolymer.
16 . The method of claim 10 , wherein R 1 comprises the condensation reaction product of polymerized fatty acids, linear C 1 -C 6 dioic acids, and C 1 -C 6 diols.
17 . The method of claim 16 , wherein the polymerized fatty acids are dimerized or trimerized fatty acid.
18 . The method of claim 1 , wherein the epoxy polymer composite system further comprises one or more solid fillers.
19 . The method of claim 18 , wherein the one or more solid fillers comprise clays, glass beads, fumed silica, glass fibers, carbon powder, carbon fibers, silicones, or mixtures thereof.
20 . The method of claim 1 , wherein the mixture of the epoxy resin and the glycidyl terminated modifying polymer comprises a polymerization catalyst, curing agent, hardening agent, dye, antioxidant, or stabilizer.
21 . The method of claim 20 , wherein the curing agent is dicyandiamide.
22 . An epoxy polymer composite system prepared by the method of claim 1 .