US 3,948,855 AGrant
Process for Reacting a Phenol With a Vicinal Epoxy Compound in the Presence of Phosphorus or Carbon Containing Acid, Ester or Acid Ester
Issue Date:1976-04-06
•20 Claims
Abstract
A process for the preparation of phenolic hydroxy ethers whereby an aromatic hydroxyl-containing compound is reacted with a vicinal epoxy-containing compound in the presence of a phosphonium salt of an acid, ester or acid ester of an element selected from carbon or phosphorus, and to precatalyzed epoxy resin compositions comprising an epoxy resin and a catalyst as defined above.
Metadata
Assignee
- The Dow Chemical Company
Inventor
- William O. Perry
Application Information
Application Number:US 372364&
Filing Date:1973-06-21
Priority Date:1970-05-28
Art Unit:143
Classifications
IPC:
C08G 3004
Field of Search:
26025247 EP;2 EP;149;613 B;57;606.5 F;541431 P;437;2 P;45.7 P;18 PF;78.4 EP
Patent Drawings
This patent does not have any drawings.
Description
EXAMPLE 1
To a reaction vessel equipped with a means for stirring, temperature indication and control and nitrogen purge was charged 326.1 grams of the diglycidyl ether of 4,4'-isopropylidine diphenol (bisphenol A) having an epoxide equivalent weight (EEW) of 187, 169.0 grams of 4,4'-isopropylidinediphenol (bisphenol A), 4.9 grams of the hydrolyzed product of the diglycidyl ether of 4,4'-isopropylidine diphenol, and 0.606 grams of ethyltriphenyl phosphonium diethylphosphate (ETPP.sup.. DEP) dissolved in methanol. The reaction mass was heated at a rate of 5.degree. C per minute. At a temperature of about 130.degree. C, an exotherm began and when the temperature reached 150.degree. C, the heating device was turned off. The exotherm peaked at about 246.degree. C. After the exotherm had subsided, the temperature was maintained at 180.degree. C for 5 hours.
The resultant product was a frangible solid which had properties as listed in Table I.
EXAMPLE 2
The reaction of Example 1 was repeated, except that 0.703 grams of methyltrioctylphosphonium dimethylphosphate (MTOP.sup.. DMP) was employed as the catalyst.
The exotherm peak occurred at 240.degree. C.
The product was a frangible solid which had properties as listed in Table I.
EXAMPLE 3
The reaction of Example 1 was repeated except that 0.475 grams of ethyltriphenylphosphonium acetate, acetic acid complex (ETPP.sup.. AC.sup.. HAC) dissolved in methanol was employed as the catalyst.
The peak exotherm occurred at about 240.degree. C.
The product was a frangible solid which had properties as listed in Table I.
EXAMPLE 4
The procedure of Example 1 was followed employing the following charge to the reaction vessel.
377.4 grams of the diglycidyl ether of bisphenol A having an EEW of 187,
5.7 grams of the hydrolysis product of the diglycidyl ether of bisphenol A,
116.9 grams of bisphenol A
0.694 gram ethyl triphenyl phosphonium diethylphosphate dissolved in methanol.
The exotherm peak occurred at about 230.degree. C, after which the resin was heated at 160.degree. C for about 4 hours.
The product was a frangible solid which had properties as listed in Table I.
EXAMPLE 5
Same procedure as in Example 4 except that the catalyst employed was 0.703 gram of ethyltriphenylphosphonium acetate, acetic acid complex (ETPP.sup.. Ac.sup.. HAc) dissolved in methanol.
The peak exotherm was about 230.degree. C.
The product was a frangible solid which had the properties listed in Table I.
EXAMPLE 6
Same procedure as in Example 4 except that 0.703 gram methyltrioctylphosphonium dimethyl phosphate, (MTOP.sup.. DMP) dissolved in methanol, was employed as catalyst. The exotherm peak was about 230.degree. C.
The product was a frangible solid which had the properties listed in Table I.
EXAMPLE 7
The procedure of Example 1 was followed employing the following charge to the reaction vessel.
346 grams of the diglycidyl ether of bisphenol A having an EEW of 187
148.4 grams bisphenol A
5.3 grams of the hydrolysis product of the diglycidyl ether of bisphenol A
0.352 gram of ethyltriphenylphosphonium diethylphosphate (ETPP.sup.. DEP) dissolved in methanol.
The exotherm peak was about 245.degree. C and the resin was heated at 170.degree. C for about 4 hours.
The product was a frangible solid which had the properties listed in Table I.
EXAMPLE 8
The procedure of Example 1 was followed employing the following charge to the reaction vessel.
320.2 grams of the diglycidyl ether of bisphenol A having an EEW of 187.
175.0 grams bisphenol A.
4.8 grams of the hydrolysis product of the diglycidyl ether of bisphenol A.
0.650 gram methyltrioctylphosphonium dimethylphosphate (MTOP.sup.. DMP).
The product was a frangible solid which had the properties listed in Table I.
EXAMPLE 9
The reaction of Example 1 was repeated, except that the following charge was employed.
324.0 grams of the diglycidyl ether of bisphenol A having an EEW of 188
171.0 grams of bisphenol A
4.9 grams of the hydrolysis product of the diglycidyl ether of bisphenol A
0.48 gram ethyltriphenylphosphonium diphenyl phosphinate dissolved in methanol.
The peak exotherm was 225.degree. C, after which the resin was heated at 180.degree. C for 5 hours. The product was a frangible solid having an EEW of 231.0.
EXAMPLE 10
The reaction of Example 1 was repeated, except that the following charge was employed.
324.0 grams of the diglycidyl ether of bisphenol A having an EEW of 188
171.0 grams of bisphenol A
4.9 grams of the hydrolysis product of the diglycidyl ether of bisphenol A
0.375 gram of methyltriphenylphosphonium dimethylphosphonate dissolved in methanol
The exotherm peak was 211.degree. C, after which the resin was heated at 180.degree. C. for 5 hours. The product was a frangible solid having an EEW of 2415.
EXAMPLE 11
A. To a reaction vessel equipped with a means for stirring, temperature control and indication, and nitrogen purge was charged 375.3 grams of the diglycidyl ether of 4,4'isopropylidine diphenol (bisphenol A) having an epoxide equivalent weight (EEW) of 183, 124.7 grams of bisphenol A, and 0.456 grams of ethyltriphenylphosphonium diethylphosphate (ETPP.sup.. DEP) dissolved in methanol. The reaction mass was heated at the rate of 5.degree.C/minute. At a temperature of 130.degree. C, an exotherm began and when the temperature reached 150.degree. C, the heat was turned off. The exotherm peak was 228.degree. C. After the exotherm subsided, the temperature was maintained at 160.degree. C for 4 hours. The resultant product was a frangible solid having an EEW of 548.
B. The method of the above example was repeated except that the following charge was employed.
371.8 grams of the diglycidyl ether of bisphenol A (EEW = 183)
5.6 grams hydrolysis product of the diglycidyl ether of bisphenol A
122.6 grams of bisphenol A
0.456 grams ethyltriphenylphosphonium diethylphosphate dissolved in methanol.
After an exotherm peak of 226.degree. C, the resin was heated at 160.degree. C for 4 hours. The product was a frangible solid having an EEW of 547.
EXAMPLE 12
Stability Experiment
A precatalyzed mixture was prepared by blending the following:
100 parts by weight of a diglycidyl ether of bisphenol A
1.5 parts by weight of hydrolyzed diglycidyl ether of bisphenol A
0.1 parts by weight of the acetic acid complex of ethyltriphenyl phosphonium acetate.
The above precatalyzed mixture had a % epoxide of 21.76. This mixture was placed in a container and the container with contents were stored at 50.degree. C for 4 weeks. After the 4 weeks storage, the percent epoxide was 21.55. The percent loss in percent epoxide was calculated as follows: ##EQU9##
The above experiment clearly indicates that the precatalyzed mixtures are stable at ordinary storage and transportation temperatures, i.e., 50.degree. C or 122.degree. F.
EXAMPLE 13
The procedure of Example 11 above was followed employing the following charge to the reaction vessel.
256 grams of diglycidyl ether of 4,4'-isopropylidine diphenol (EEW = 183)
64 grams of glycidyl ether of a novolac resin, (EEW - 178), i.e., and a functionality of 3.5, phenol-formaldehyde condensate
180.0 grams 2,6,2',6'-tetrabromo-4,4'-isopropylidine diphenol
0.64 gram of a 25 percent methanol solution of ethyltriphenylphosphonium diethylphosphate (0.16 gram of actual catalyst).
After 2 hours at 150.degree. C, the mixture was cooled to 100.degree. C and 125 grams acetone was added slowly through the condenser with thorough agitation until homogeneity was achieved. The resultant product was a viscous liquid having an EEW of 463 and a viscosity of 1160 centipoise at 25.degree. C.
EXAMPLE 14
The process of the present invention is particularly useful in the preparation of higher molecular weight solid epoxy resins from lower molecular weight liquid epoxy resins by the pre-catalyzed method. In this method, the liquid epoxide resin is blended with the catalyst and oftentimes it is stored in warehouses where high temperatures are encountered for prolonged periods of time before being reacted with the diphenolic compound. The following two experiments demonstrate that a less colored product is obtained when the catalysts of the present invention are employed as compared to the phosphonium catalysts of the prior art.
A. A mixture containing 326.0 grams of the diglycidyl ether of bisphenol A having an EEW of 188, 4.8 grams of the hydrolysis product of the diglycidyl ether of bisphenol A, and 0.398 grams ethyl triphenyl phosphonium diethylphosphate was heat aged in an oven at 80.degree. C for 7 days, after which time the resin was reacted with 169.0 grams of bisphenol A employing the procedure of Example 1. The peak exotherm was 242.degree. C. The resultant product had an EEW of 2070 and a Gardner color of 1.
B. Comparative Experiment
A mixture containing 319.0 grams of the diglycidyl ether of bisphenol A having an EEW of 191, 4.8 grams of the hydrolysis product of the diglycidyl ether of bisphenol A and 0.972 grams of ethyltriphenylphosphonium iodide was heat aged in an oven at 80.degree. C for 6 days, after which time the resin was reacted with 163.9 grams of bisphenol A employing the procedure of Example 1. The peak exotherm was about 235.degree. C. The resultant product had an EEW of 2100 and a Gardner color of 4.
The above example clearly demonstrates the improved color of polyepoxides prepared from precatalyzed epoxy resin systems containing the catalysts of the present invention over those of the prior art.
EXAMPLE 15
The following example demonstrates the undesirable color formation when employing amine catalysts.
A. Comparative Example
Employing the procedure of Example 1, 374.9 grams of the diglycidyl ether of bisphenol A having an EEW of 189 was reacted with 119.5 grams of bisphenol A in the presence of 0.684 gram of benzyltrimethylammonium chloride as a 10 percent solution in methanol. After the exotherm, the reaction was maintained at 160.degree. C for 4 hours. The product was a frangible solid which had a softening point of about 77.degree. C, a Gardner color of 4 and a percent epoxide of 7.85.
B. Comparative Example
The reactants and procedures of A above was conducted in the presence of 0.375 grams of N-methylmorpholine as catalyst. The product was a frangible solid which had a melting point of about 78.5.degree. C, a Gardner color of 3 and a percent epoxide of 7.78 percent.
EXAMPLE 16
The following experiments demonstrate that higher molecular weight resins can be prepared when a catalyst of the present invention is employed as compared to a phosphonium halide catalyst.
A. A high molecular weight thermoplastic polymer was prepared according to the process of this invention by charging 239.7 grams of diglycidyl ether of bisphenol A having an epoxide equivalent weight of 170.6 and 160.3 grams of recrystallized bisphenol A to a reaction vessel equipped as in Example 1. To this mixture, 71.0 grams of the monoethylether of ethyleneglycol was added as a diluent in order to facilitate stirring. After adding 0.959 grams of the acetic acid complex of ethyltriphenylphosphonium acetate dissolved in methanol, the reaction mixture was heated to 150.degree. C at a rate of 5.degree. C per minute. The reaction mass exothermed to a peak of 184.degree. C. After the exotherm had subsided, the temperature was maintained at 140.degree. - 150.degree. C for about 2 hours. The heating means was removed and methylethyl ketone was added to the reaction mass until the non-volatiles content was 40 percent to facilitate handling. The resultant resin had a percent epoxide of 0.15 percent and a weight average molecular weight of 28,000 as determined by gel permeation chromatography.
B. Comparative Example
The procedure and charge of Example A above was employed except that the catalyst employed was 1.148 grams of ethyltriphenylphosphonium iodide. The exotherm peak was 173.degree. C and the resin was heated for 4 hours before diluting to 40 percent non-volatiles with methylethyl ketone. The resultant resinous product had an epoxide content of 0.35 percent and a weight average molecular weight of 13,000 as determined by gel permeation chromatography.
EXAMPLE 17
The following examples demonstrate the ability of the phosphonium catalysts of the present invention to produce epoxy resins of improved molecular weight when compared to the corresponding phosphonium halide catalyst taught in U.S. Pat. No. 3,479,990.
EXPERIMENT A -- Acetic Acid Complex of Ethyl Tripenyl Phosphonium Acetate
A high molecular weight thermoplastic polymer was prepared according to the process of the invention by charging 249.4 g. of the diglycidyl ether of bisphenol A having an expoxide equivalent weight of 189 and 150.6 g. of bisphenol A to a reaction vessel equipped as in Example 1 of the subject application. To this mixture, 44.5 g. of the mono-ethylether of ethylene glycol was added as a diluent to facilitate stirring. After adding 1.496 g. of the acetic acid complex of ethyl triphenyl phosphonium acetate dissolved in methanol, the reaction was heated to 150.degree. C at the rate of 5.degree. C/min. The reaction mass exothermed to 195.degree. C. After the exotherm subsided, the temperature was maintained at 140.degree. - 150.degree. C for 4 hours. The heating means was removed and a mixture of methyl ethyl ketone and the monoethylether of ethylene glycol was added to the reaction mass until the mon-volatiles content was 40 percent and the solvent consisted of 50 percent methyl ethyl ketone and 50 percent mono-ethylether of ethylene glycol. The resultant resin had a percent epoxide of 0.32 percent and a weight average molecular weight of 22,000 as calculated from a gel permeation chromatogram.
EXPERIMENT B -- Ethyl Triphenyl Phosphonium Acetate
The procedure and charge of Experiment A was employed except that the catalyst used was 1.27 g. of ethyl triphenyl phosphonium acetate. This amount of catalyst is equivalent in phosphonium content to that used in Experiment A. The exotherm peak was 196.degree. C. The resulting resin had a percent epoxide of 0.33 percent and a weight average molecular weight of 20,000 as calculated from a gel permeation chromatogram.
EXPERIMENT C -- Tetrabutyl Phosphonium Acetate-Acetic Acid Complex
The procedure and charge of Experiment A was followed except that the catalyst used was 1.380 g. tetrabutyl phosphonium acetate.sup.. acetic acid complex. This amount of catalyst is equivalent to that used in Experiment A. The exotherm peak was 188.degree. C. The resulting resin had an epoxide content of 0.28 percent and a weight average weight of 22,000 as calculated from a gel permeation chromatogram.
COMPARATIVE EXPERIMENT D -- Ethyl Triphenyl Phosphonium Iodide
The procedure and charge of Experiment A was employed except that the catalyst employed was 1.527 g. of ethyltriphenylphospshonium iodide. This amount of catalyst is equivalent in phosphonium content to that of Experiment A. The exotherm peak was 166.degree. C and the resin was heated for 4 hours at 140.degree. - 150.degree. C before diluting to 40 percent non-volatiles with a mixture of methylethyl ketone and the mono-ethylether of ethylene glycol so that the final solvent composition was 50 percent methylethyl ketone and 50 percent of the monoethylether of ethylene glycol. The resultant resin had a percent epoxide of 0.52 percent and a weight average molecular weight of 12,000 as calculated from a gel permeation chromatogram.
COMPARATIVE EXPERIMENT E -- Ethyl Triphenyl Phosphonium Chloride
The procedure and charge of Experiment A was employed except that the catalyst used was 1.20 g. of ethyl triphenyl phosphonium chloride. This amount of catalyst is equivalent in phosphonium content to that used in Experiment A. The exotherm peak was 190.degree. C. The resulting resin had a percent epoxide of 0.41 percent and a weight average molecular wt. of 17,000 as calculated from a gel permeation chromatogram.
The above Experiments A, B, and C are representative of the present invention and demonstrate their superiority in their ability to produce high molecular weight resins over the catalysts of the prior art as represented by Comparative Experiments D and E.
EXAMPLE 18
A solid epoxy resin was prepared from the following reactor charge:
326.7 grams of a diglycidyl ether of bisphenol A having an epoxide equivalent weight of about 191.6
173.3 grams of bisphenol A
0.33 grams of ethyltriphenylphosphonium acetate.sup.. acetic acid complex.
The above ingredients were charged to a 1 liter, 3-necked glass reaction vessel equipped with stirring and temperature control means. The mixture was heated at the rate of about 5.degree. C/minute, with stirring, to 150.degree. C and then the heat was cut off. The reaction mass exothermed to about 245.degree. C and was therafter allowed to cool to 180.degree. C. This temperature was then maintained for about 5 hours. The resultant product had a Durran's softening point of 134.5.degree. C, a Gardner viscosity (40 percent solution in the n-butyl ether of diethylene glycol) of Z.sub.2 -Z.sub.3 and an epoxide equivalent weight of about 2040.
Claims
I claim:
1. In a process for preparing phenolic hydroxy ethers which comprises reacting a polyhydric phenol with a polyepoxide having more than one 1,2-epoxy group, the improvement comprising employing as the catalyst therefor, a phosphonium salt of an acid, ester or acid ester of the element carbon represented by the general formula ##EQU10## wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are independently selected from the group consisting of aliphatic hydrocarbon radicals containing from about 1 to about 20 carbon atoms, aromatic hydrocarbon radicals, alkyl substituted aromatic hydrocarbon radicals and radicals represented by the formula -R.sub.5 Y wherein R.sub.5 is an aliphatic hydrocarbon radical having from about 1 to about 20 carbon atoms and Y is a member selected from the group consisting of Cl, Br, I, and NO.sub.2, and wherein X is the anion portion of an acid, ester or acid ester of the element carbon and wherein m is the valence of the anion X.
2. The process of claim 1 wherein the catalyst is a phosphonium salt of an acid, ester or acid ester of the element carbon represented by general formula ##EQU11## wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are as defined in claim 1, m is the valence of the anion X.sub.6 and has a value of 1 to 2, and X.sub.6 is selected from the group represented by the formula ##EQU12## wherein R and R' are independently selected from the same group as R.sub.1, R.sub.2, R.sub.3 and R.sub.4 and additionally R can be selected from an alkenyl group having from about 1 to about 20 carbon atoms and R' can be an alkenylene group having from about 1 to about 20 carbon atoms, y has a value of zero or 1 and wherein n and n' have a value of zero or 1.
3. The process of claim 2 wherein each R.sub.1, R.sub.2, R.sub.3 and R.sub.4 is independently an aliphatic or an aromatic hydrocarbon group.
4. The process of claim 3 wherein X.sub.6 is selected from the group represented by the formula ##EQU13## wherein R is an alkyl group containing from about 1 to about 20 carbon atoms.
5. The process of claim 4 wherein R is a methyl group.
6. The process of claim 5 wherein the catalyst is ethyltriphenylphosphonium acetate.sup.. acetic acid complex.
7. The process of claim 5 wherein the catalyst is ethyltriphenylphosphonium acetate.
8. The process of claim 4 wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are aliphatic hydrocarbon groups having from about 1 to about 20 carbon atoms.
9. The process of claim 8 wherein R is a methyl group.
10. The process of claim 9 wherein the catalyst is tetrabutylphosphonium acetate.sup.. acetic acid complex.
11. The process of claim 1 wherein the polyhydric phenol is a bisphenol and the polyepoxide is a diglycidyl ether of a bisphenol.
12. The process of claim 2 wherein the polyhydric phenol is a bisphenol and the polyepoxide is a diglycidyl ether of a bisphenol.
13. The process of claim 3 wherein the polyhydric phenol is a bisphenol and the polyepoxide is a diglycidyl ether of a bisphenol.
14. A precatalyzed epoxy resin composition comprising an epoxide resin containing an average of more than 1 vicinal epoxy group per molecule and a catalytic quantity of a catalyst as defined in claim 1.
15. A precatalyzed epoxy resin composition comprising an epoxide resin containing an average of more than 1 vicinal epoxy group per molecule and a catalytic quantity of a catalyst as defined in claim 2.
16. A precatalyzed epoxy resin composition comprising as epoxide resin containing an average of more than 1 vicinal epoxy group per molecule and a catalytic quantity of a catalyst as defined in claim 4.
17. A precatalyzed epoxy resin composition comprising an expoxide resin containing an average of more than 1 vicinal epoxy group per molecule and a catalytic quantity of a catalyst as defined in claim 10.
18. A precatalyzed epoxy resin composition comprising an epoxide resin containing an average of more than 1 vicinal epoxy group per molecule and a catalytic quantity of a catalyst as defined in claim 5.
19. A process for preparing high molecular weight resins which comprises reacting a polyepoxide having an epoxy equivalency greater than 1.0 with a polyhydric phenol in the presence of from about 0.001 percent to about 10 percent by weight of the reactants of a hydrocarbon phosphonium acetate-acetic acid complex of the general formula ##EQU14## wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are the same or different and represent hydrocarbon radicals.
20. A process for preparing high molecular weight resins which comprises reacting a polyepoxide having an epoxy equivalency greater than 1.0 with a polyhydric phenol in the presence of from about 0.001 percent to about 10 percent by weight of the reactants of a hydrocarbon phosphonium acetate catalyst of the general formula ##EQU15## wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are the same or different and represent hydrocarbon radicals, and n has a value of zero or one.
Patent Citations (6)
| Patent | Date | Inventor | Cited By |
|---|---|---|---|
| US2916473 | 1959-12-01 | Bullock et al. | |
| US3341580 | 1967-09-01 | Hechenbleikner | |
| US3377406 | 1968-04-01 | Newey et al. | |
| US3412046 | 1968-11-01 | Payne | |
| US3477990 | 1969-11-01 | Dante et al. | |
| US3547885 | 1970-12-01 | Dante et al. |
Non-Patent Literature (1)
- Chem. Abst. Vol. 55 1961 (p4945e).