OLIGOMERIC HALOGENATED CHAIN EXTENDERS FOR PREPARING EPOXY RESINS
An oligomeric halogenated chain extender composition comprising the reaction product of: (a) an excess of a halogenated phenolic compound; and (b) a halogenated epoxy resin; in the presence of (c) a solvent; and a halogenated epoxy resin composition comprising the reaction product of the oligomeric halogenated chain extender composition with an epoxy resin.
1 . A process comprising forming a reaction mixture containing at least one epoxide-reactive compound and at least one halogenated epoxy resin in the presence of a solvent, and subjecting the reaction mixture to conditions sufficient to form a solution of an oligomer composition in the solvent, wherein the oligomer composition contains terminal epoxide-reactive groups.
2 . The process of claim 1 wherein the epoxide-reactive compound includes a brominated epoxide-reactive compound.
3 . The process of claim 2 wherein the halogenated epoxy resin contains at least one bromine atom.
4 . The process of claim 3 wherein the brominated epoxide-reactive compound is a phenolic compound having at least 2 epoxide-reactive groups and at least one bromine atom bonded to a carbon atom on an aromatic ring.
5 . The process of claim 4 wherein the halogenated epoxy resin contains at least one bromine atom bonded to a carbon atom of an aromatic ring.
6 . The process of claim 4 wherein the oligomer composition also contains residual epoxide groups.
7 . The process of claim 6 wherein the ratio of equivalents of epoxide-reactive groups to equivalents of residual epoxide groups in the oligomer composition is from 2:1 to 30:1.
8 . The process of claim 7 wherein the ratio of equivalents of epoxide-reactive groups to equivalents of residual epoxide groups in the oligomer composition is 2:1 to 8:1.
9 . The process of claim 1 wherein the reaction mixture further contains at least one non-halogenated epoxy resin.
10 . The process of claim 9 wherein at least 95 percent by weight of the epoxy resins in the reaction mixture contain 2 epoxy groups/molecule.
11 . The process of claim 2 wherein the reaction mixture further contains at least one non-halogenated epoxy-reactive compound.
12 . The process of claim 2 wherein the oligomeric composition contains from 10 to 60 percent by weight halogen atoms.
13 . The process of claim 12 wherein the brominated epoxide-reactive compound is a brominated bisphenol, and the halogenated epoxy resin is a diglycidyl ether of a halogenated bisphenol.
14 . The process of claim 1 wherein the solvent constitutes from 10 to 75 percent of the combined weight of the solvent, epoxide-reactive compound(s) and epoxy resin(s).
15 . The process of claim 1 , further comprising mixing the oligomer solution with at least one additional epoxy resin and subjecting the mixture to conditions sufficient to form an advanced, halogenated epoxy resin.
16 . The process of claim 15 , wherein the additional epoxy resin is not halogenated.
17 . The process of claim 16 , wherein the additional epoxy resin has an average functionality of at least 2.0 epoxide groups per molecule.
18 . The process of claim 17 , wherein the additional epoxy resin is a glycidyl ether of a polyhydric phenol compound, a diglycidyl ether of an aliphatic glycol, a diglycidyl ether of a polyether glycol, a cresol-formaldehyde novolac epoxy resin, a phenol-formaldehyde novolac epoxy resin, a bisphenol A novolac epoxy resin, a cyclopentadiene phenol novolac resin, tris(glycidyloxyphenyl)methane, tetrakis(glycidyloxyphenyl)ethane, or a mixture of any two or more thereof.
19 . The process of claim 17 , wherein the additional epoxy resin is a glycidyl ether of resorcinol, catechol, hydroquinone, bisphenol, bisphenol A, bisphenol AP, bisphenol F or bisphenol K.
20 . The process of claim 15 further comprising curing the advanced, halogenated epoxy resin by reacting it with at least one epoxy curing agent.
21 . The process of claim 18 further comprising curing the advanced, halogenated epoxy resin by reacting it with at least one epoxy curing agent.
22 . A process comprising forming a mixture of (1) a solution of a halogenated oligomer composition having terminal epoxide-reactive groups and (2) an epoxy resin, and subjecting the mixture to conditions sufficient to form and advanced, halogenated epoxy resin.
23 . The process of claim 21 , wherein the epoxy resin is not halogenated.
24 . The process of claim 23 , wherein the epoxy resin has an average functionality of at least 2.0 epoxide groups per molecule.
25 . The process of claim 24 , wherein the additional epoxy resin is a glycidyl ether of a polyhydric phenol compound, a diglycidyl ether of an aliphatic glycol, a diglycidyl ether of a polyether glycol, a cresol-formaldehyde novolac epoxy resin, a phenol-formaldehyde novolac epoxy resin, a bisphenol A novolac epoxy resin, a cyclopentadiene phenol novolac resin, tris(glycidyloxyphenyl)methane, tetrakis(glycidyloxyphenyl)ethane, or a mixture of any two or more thereof.
26 . The process of claim 25 wherein the oligomer composition also contains residual epoxide groups.
27 . The process of claim 26 wherein the ratio of equivalents of epoxide-reactive groups to equivalents of residual epoxide groups in the oligomer composition is from 2:1 to 30:1.
28 . The process of claim 27 wherein the ratio of equivalents of epoxide-reactive groups to equivalents of residual epoxide groups in the oligomer composition is 2:1 to 8:1.
29 . The process of claim 22 further comprising curing the advanced, halogenated epoxy resin by reacting it with at least one epoxy curing agent.
30 . The process of claim 25 further comprising curing the advanced, halogenated epoxy resin by reacting it with at least one epoxy curing agent.
31 . The process of claim 26 further comprising curing the advanced, halogenated epoxy resin by reacting it with at least one epoxy curing agent.
32 . The process of claim 28 further comprising curing the advanced, halogenated epoxy resin by reacting it with at least one epoxy curing agent.
33 . A solution of a halogenated oligomer composition in a solvent, wherein the oligomer composition has terminal epoxide-reactive groups.
34 . The solution of claim 33 wherein the oligomer composition also contains residual epoxide groups.
35 . The process of claim 34 wherein the ratio of equivalents of epoxide-reactive groups to equivalents of residual epoxide groups in the oligomer composition is from 2:1 to 30:1.
36 . The process of claim 35 wherein the ratio of equivalents of epoxide-reactive groups to equivalents of residual epoxide groups in the oligomer composition is 2:1 to 8:1.
37 . A varnish comprising a solution of an oligomer composition produced in accordance with claim 1 , an epoxy resin, and at least one epoxy curing agent.
38 . A varnish comprising a solution of an advanced, halogenated epoxy resin produced in accordance with claim 8 , and at least one epoxy curing agent.
39 . A varnish comprising a solution of an advanced, halogenated epoxy resin produced in accordance with claim 15 , and at least one epoxy curing agent.
40 . The varnish of claim 37 , further comprising at least one other epoxy resin.
41 . The varnish of claim 40 , further comprising boric acid or a boron ester.
42 . The varnish of claim 40 , wherein the additional epoxy resin used to make the halogenated, advanced epoxy resin is a glycidyl ether of a polyhydric phenol compound, a diglycidyl ether of an aliphatic glycol, a diglycidyl ether of a polyether glycol, a cresol-formaldehyde novolac epoxy resin, a phenol-formaldehyde novolac epoxy resin, a bisphenol A novolac epoxy resin, a cyclopentadiene phenol novolac resin, tris(glycidyloxyphenyl)methane, tetrakis(glycidyloxyphenyl)ethane, or a mixture of any two or more thereof.
43 . A varnish comprising a solution of an advanced, halogenated epoxy resin produced in accordance with claim 22 , and at least one epoxy curing agent.
44 . The varnish of claim 43 , further comprising at least one other epoxy resin.
45 . The varnish of claim 43 , further comprising boric acid or a boron ester.
46 . The varnish of claim 45 , wherein the epoxy resin is a glycidyl ether of a polyhydric phenol compound, a diglycidyl ether of an aliphatic glycol, a diglycidyl ether of a polyether glycol, a cresol-formaldehyde novolac epoxy resin, a phenol-formaldehyde novolac epoxy resin, a bisphenol A novolac epoxy resin, a cyclopentadiene phenol novolac resin, tris(glycidyloxyphenyl)methane, tetrakis(glycidyloxyphenyl)ethane, or a mixture of any two or more thereof.
47 . A prepreg comprising a substrate material impregnated with the varnish of claim 37 .
48 . A prepreg comprising a substrate material impregnated with the varnish of claim 38 .
49 . A prepreg comprising a substrate material impregnated with the varnish of claim 41 .
50 . A prepreg comprising a substrate material impregnated with the varnish of claim 43 .
51 . The process of claim 22 , further comprising forming a varnish containing the advanced, halogenated epoxy resin and at least one epoxy curing agent, applying the varnish to a substrate, and curing the advanced, halogenated epoxy resin on the substrate.
52 . The process of claim 51 , wherein the varnish is applied to multiple substrates, the substrates are stacked prior to curing the advanced, halogenated epoxy resin, and a laminate is formed by curing the advanced, halogenated epoxy resin.
53 . The process of claim 52 , wherein a metal conductive layer is applied to at least one side of the laminate.
54 . A composite comprising a substrate impregnated with a cured epoxy resin, wherein the composite is characterized by having a T g of at least 140° C., a T d of at least 315° C. and a T260 of at least 5 minutes.
55 . The composite of claim 54 which has a metal conductive layer applied to at least one side of the composite.
56 . A printed wiring board comprising the composite of claim 54 .
57 . The composite of claim 54 which is characterized by having a T g of at least 170° C., a T d of at least 330° C. and a T 260 of at least 60 minutes.
58 . The composite of claim 57 which has a metal conductive layer applied to at least one side of the composite.
59 . A printed wiring board comprising the composite of claim 57 .
60 . A resin-coated foil comprising a metal foil adhered to the surface of a cured halogenated epoxy resin produced in accordance with claim 29 .
61 . A resin-coated foil comprising a metal foil having cured halogenated epoxy resin produced in accordance with claim 51 coated onto its surface.