Vinyl-containing compounds with high heat distortion
A process for forming a thermosetting resin in a nitrogen atmosphere is provided. The process includes the steps of a) reacting a polycarboxylic acid and/or anhydride and a polyhydric alcohol to provide a hydroxyl-containing intermediate; b) reacting the hydroxyl-containing intermediate with a vinyl-containing organic acid or vinyl containing alkyl ester in the presence of an esterification catalyst, a polymerization inhibitor and an azeotropic agent; and c) reacting any residual vinyl-containing organic acid and residual esterification catalyst with an epoxide.
1. A process for forming a thermosetting resin having a heat distortion temperature (HDT) of greater than 150° C., wherein the process is conducted in a nitrogen atmosphere and comprises the steps of:
a) reacting a polycarboxylic acid and/or anhydride with a polyhydric alcohol to provide a hydroxyl containing intermediate, wherein the polycarboxylic acid and/or anhydride comprises fumaric acid;
b) reacting the hydroxyl-containing intermediate with a vinyl-containing organic acid or vinyl-containing alkyl ester in the presence of an esterification catalyst and a polymerization inhibitor;
c) reacting any residual vinyl-containing organic acid and esterification catalyst with an epoxide to provide a thermosetting resin having an HDT of greater than 150° C.
2. The process of claim 1 , wherein the HDT is greater than or equal to 180° C.
3. The process of claim 1 , wherein the polycarboxylic acid and/or anhydride further comprises one or more anhydrides selected from the group consisting of propionic anhydride, maleic anhydride, phthalic anhydride, tetrabromophthalic anhydride, succinic anhydride, tetrahydrophthalic anhydride, citraconic anhydride, itaconic anhydride, aryl-, alkyl-, and halogen-substituted derivatives thereof and mixtures of any thereof.
4. The process of claim 1 , wherein the polycarboxylic acid and/or anhydride further comprises a polycarboxylic acid and/or anhydride monomer containing no carbon-carbon unsaturated functionality, said monomer selected from the group consisting of isophthalic acid, terephthalic acid, adipic acid, cyclohexane dicarboxylic acid, succinic anhydride, adipic acid, sebacic acid, azealic acid, malonic acid and alkenyl succinic acids and anhydrides thereof.
5. The process of claim 1 , wherein the polycarboxylic acid i& and/or anhydride further comprises a polycarboxylic acid and/or anhydride selected from the group consisting of 1,2,4-benzenetricarboxylic acid, 1,3,5-benzene tricarboxylic acid, 1,2,4-cyclohexane tricarboxylic acid, 2,5,7-naphthalene tricarboxylic acid, 1,2,4-naphthalene tricarboxylic acid, 1,3,4-butane tricarboxylic acid, 1,2,5-hexane tricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-carboxymethylpropane, tetra(carboxymethyl)methane, 1,2,7,8-octane tetracarboxylic acid, anhydrides thereof and mixtures of any thereof.
6. The process of claim 1 , wherein the polyhydric alcohol is selected from the group consisting of ethylene glycol, diethylene glycol, neopentyl glycol, dibromoneopentyldiol, 2-methyl-1,3-propanediol, 2,2 4-trimethyl-1,3-pentadiol, 2-butyl-2-ethyl 1,3-propanediol, polyethoxylated bisphenol A, polypropoxylated bisphenol A, 1,4-cyclohexane dimethanol, trimethylol propane diallylether, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 1,3 hexanediol, 1,3-butylene glycol, 1,6-hexanediol, hydrogeneated bisphenol A, 1,4-cyclohexanol, ethylene oxide adducts of bisphenols, propylene oxide adducts of bisphenols, sorbitol, 1,2,3,6-hexatetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, sucrose, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methyl-propanetriol, 2-methyl-1,2,4-butanetriol, trimethylol ethane, trimethylol propane 1,3,5-trihydroxyethyl benzene, halogen and phosphorus containing derivatives thereof and mixtures of any thereof.
7. The process of claim 1 , wherein the weight equivalent ratio of polycarboxylic acid or anhydride to polyhydric alcohol is in a range from about 1:1 to about 1:10.
8. The process of claim 1 , wherein the polymerization inhibitor is one or more selected from the group consisting of phenothiazine, phenol, 2,6-di-tert-butyl-4-methyl phenol, hydroquinone (HQ), tolu-hydroquinone (THQ), bisphenol A (BPA), triphenyl antimony, naphthoquinone (NQ), p-benzoquinone (p-BQ), butylated hydroxy toluene (BHT), hydroquinone monomethyl ether (HQMME), 4-ethoxyphenol, 4-propoxyphenol, monotertiary butyl hydroquinone (MTBHQ), ditertiary butyl hydroquinone (DTBHQ), tertiary butyl catechol (TBC), 1,2-dihydroxybenzene, 2,5-dichlorohydroquinone, 2-acetylhydroquinone, 1,4-dimercaptobenzene, 2,3,5-trimethylhydroquinone, 2-aminophenol, 2-N,N,-dimethylaminophenol, catechol, 2,3-dihydroacetophenone, pyrogallol, 2-methylthiophenol and mixtures of any thereof.
9. The process of claim 1 , wherein the polymerization inhibitor is a stable hindered nitroxyl compound.
10. The process of claim 9 , wherein the stable hindered nitroxyl compound is selected from the group consisting of N,N-di-tert-butylnitroxide; N,N-di-tert-amylnitroxide; N-tert-butyl-2-methyl-1-phenyl-propylnitroxide; N-tertbutyl-1-diethyl phosphono-2,2-dimethyl propyl nitroxide; 2,2,6,6-tetramethyl-piperidinyloxy; 4-amino-2,2,6,6-tetramethyl-piperidinyloxy; 4-hydroxy-2,2,6,6-tetramethyl-piperidinyloxy; 4-oxo-2,2,6,6-tetramethyl-piperidinyloxy; 4-dimethylamino-2,2,6,6-tetramethyl-piperidinyloxy; 4-ethanoyloxy-2,2,6,6-tetramethyl-piperidinyloxy; 2,2,5,5-tetramethylpyrrolidinyloxy; 3-amino-2,2,5,5-tetramethylpyrrolidinyloxy; 2,2,4,4-tetramethyl-1-oxa-3-azacyclopentyl-3-oxy; 2,2,4,4-tetramethyl-1-oxa-3-pyrrolinyl-1-oxy-3-carboxylic acid; 2,2,3,3,5,5,6,6-octamethyl-1,4-diazacyclohexyl-1,4-dioxy; 4-bromo-2,2,6,6-tetramethyl-piperidinyloxy; 4-chloro-2,2,6,6-tetramethyl-piperidinyloxy; 4-iodo-2,2,6,6-tetramethyl-piperidinyloxy; 4-fluoro-2,2,6,6-tetramethyl-piperidinyloxy; 4-cyano-2,2,6,6-tetramethyl-piperidinyloxy; 4-carboxy-2,2,6,6-tetramethyl-piperidinyloxy; 4-cyano-4-hydroxy-2,2,6,6-tetramethyl-piperidinyloxy; 4-methyl-2,2,6,6-tetramethyl-1-piperidinyloxy; 4-carbethoxy-2,2,6,6-tetramethyl-piperidinyloxy; 4-carboxy-4-hydroxy-2,2,6,6-tetramethyl-piperidinyloxy; 4-hydroxy-4-(1-hydroxypropyl)-2,2,6,6-tetramethy 1-piperidinyloxy; and 4-methyl-2,2,6,6-tetraethyl-1,2,5,6-tetrahydropyridinyloxy.
11. The process of claim 1 , wherein the esterification catalyst is an acid esterification catalyst.
12. The process of claim 11 , wherein the acid esterification catalyst is one or more selected from the group consisting of sulfuric acid, hydrochloric acid, alkyl sulfonic acids, 2-methyl-1-phenol-4-sulfonic acid, alkylbenzene sulfonic acids and mixtures of any thereof.
13. The process of claim 11 , wherein the acid esterification catalyst is selected from the group consisting of toluenesulfonic acid, benzenesulfonic acid, xylenesulfonic acid, methanesulfonic acid and mixtures of any thereof.
14. The process of claim 1 , wherein the esterification catalyst is a metal containing catalyst.
15. The process of claim 14 , wherein the metal containing catalyst is an organo tin catalyst.
16. The process of claim 14 , wherein the metal containing catalyst is one or more selected from the group consisting of dimethyl tin oxide, dibutyl tin diacetate, dibutyl tin di-2-ethylhexoate, dibutyl tin dilaurate, dibutyl tin oxide, dimethyl tin dichloride, sodium and potassium alkoxides, zinc and titanium alkoxides.
17. The process of claim 1 , wherein the weight ratio of vinyl-containing organic acid to polyhydric alcohol is in a range from about 1:1 to about 10:1 by weight.
18. The process of claim 1 , wherein step b) is in the presence of an azeotropic agent, wherein the azeotropic agent is a solvent and has a boiling point range from about 70° C. to about 120° C.
19. The process of claim 18 , wherein the azeotropic solvent is present in the amount ranging from about 5% to 50% based on the weight of the total reaction mixture.
20. The process of claim 1 , wherein the esterification is carried out in a nitrogen atmosphere at atmospheric pressure.
21. The process of claim 1 , wherein the esterification is carried out in a nitrogen atmosphere at subatmospheric or reduced pressure.
22. The process of claim 1 , wherein the epoxide is a polyepoxide.
23. The process of claim 22 , wherein the polyepoxide is a glycidyl ether of a polyhydric alcohol or a polyhydric phenol.
24. The process of claim 1 , wherein a second catalyst is provided to catalyze the reaction between the liquid epoxy and residual vinyl-containing organic acid and esterification catalyst.
25. The process of claim 24 , wherein the second catalyst is an organophosphonium salt, a tertiary amine, a quarternary ammonium salt, or a combination thereof.
26. The process of claim 24 , wherein the second catalyst is one or more selected from the group consisting of organophosphonium salts, 2,4,6-tri(dimethylaminomethyl)phenol [DMP-30], tetramethylammonium chloride tetramethylammonium hydroxide, tetramethylammonium bromide, tetramethylammonium hydrogensulfate, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium hydrogen sulfate, benzyltributylammonium chloride, benzyltributylammonium bromide, benzyltributylammonium hydrogen sulfate, 1,4-diazabicyclo[2.2.2]octane, diazabicyclo[4.3.0]-nonene-(5), 2-methyl imidazol, piperidine, morpholine, triethyl amine, tributyl amine, and mixtures of any thereof.
27. The process of claim 24 , wherein the second catalyst is a phosphorous containing compound and is one or more selected from the group consisting of triphenyl phosphine, tributyl phosphine, tributylphosphonium acetate, tributylphosphonium bromide, tributylphosphonium chloride, tributylphosphonium fluoride, tributylphosphonium iodide, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium acetate, and mixtures of any thereof.
28. The process of claim 1 , wherein the reaction between any residual vinyl-containing organic acid and esterification catalyst with a epoxide is carried out at a temperature ranging from about 15° C. and about 120° C.
29. The process of claim 1 , wherein the reaction between the hydroxyl-containing intermediate with a vinyl-containing organic acid or vinyl-containing alkyl ester in the presence of an esterification catalyst, and a polymerization inhibitor further comprises a free radical scavenger, an antioxidant or a combination thereof.
30. A thermosetting resin prepared by the process of claim 1 .
31. The thermosetting resin of claim 30 , further comprising an additional additive selected from any one of the group consisting of flame retardant compounds, fibers, fillers, reinforcements, thixotropic agents, paraffin waxes, fatty acids, fatty acid derivatives, lubricants, shrink-reducing additives, thermoplastic polymeric materials, low profile agents (LPA), antioxidants, pigments, dyes, paraffins, lubricants, flow agents, air release agents, wetting agents, UV stabilizers, internal release agents, and mixtures of any thereof.
32. The thermosetting resin of claim 30 , further comprising a flame retardant compound.
33. The process of claim 1 , wherein the polycarboxylic acid and/or anhydride consists of fumaric acid.
34. The process of claim 33 , wherein the polyhydric alcohol comprises ethylene glycol and neopentyl glycol.