CN1004356B - Process method for reducing total halide content in epoxy resin - Google Patents
Process method for reducing total halide content in epoxy resin Download PDFInfo
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- CN1004356B CN1004356B CN85108970.4A CN85108970A CN1004356B CN 1004356 B CN1004356 B CN 1004356B CN 85108970 A CN85108970 A CN 85108970A CN 1004356 B CN1004356 B CN 1004356B
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- epoxy resin
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- alkali metal
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Epoxy Resins (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Epoxy Compounds (AREA)
Abstract
将含有卤化物的环氧树脂溶解在由至少一种酮、至少一种芳香烃和可选择性的至少一种化合物（该化合物至少含有一个脂肪族羟基）组成的溶剂混合物中，在碱金属氢氧化物存在下将该溶液加热一段时间，使总卤化物含量充分降低，以此方法使环氧树脂中的总卤化物含量降低。dissolving a halide-containing epoxy resin in a solvent mixture consisting of at least one ketone, at least one aromatic hydrocarbon, and optionally at least one compound containing at least one aliphatic hydroxyl group, in the presence of alkali metal hydrogen The total halide content of the epoxy resin is reduced by heating the solution in the presence of the oxide for a period of time such that the total halide content is sufficiently reduced.
Description
The present invention relates to a process for reducing the hydrolyzable and/or bound (sum) halide content in epoxy resins.
The electronics industry often uses epoxy resins as sealants, potting compounds, electrical insulation layers, and the like. This sector has found that the halide content in the epoxy resin has an adverse effect on the electrical properties of the final product formed. The higher the halide content, the greater the damage, and the present invention provides a process for reducing the total halide content (hydrolyzable and/or bound) in an epoxy resin.
The present invention relates to a process for reducing the total halide content of an epoxy resin containing hydrolyzable and/or bound halide, the process comprising:
(A) Dissolving the epoxy resin in a solvent system, wherein the solvent comprises:
(1) At least one ketone in an amount of 25 to 75% by weight, preferably 50 to 75% by weight;
(2) At least one aromatic hydrocarbon is present in an amount of 75 to 25% by weight, preferably 50 to 25% by weight.
(B) At least one compound containing at least one aliphatic group per molecule is added as a cosolvent in an amount of 0.1 to 5% by weight, preferably 0.2 to 1% by weight, based on the weight of the epoxy resin.
(C) The resultant solution is heated to a temperature of 50 to 200 ℃.
(D) 0.25 to 10 molar alkali metal hydroxide, preferably 1 to 5 molar and most preferably 1 to 3 molar, based on the total halide equivalent.
(E) The heating is continued for a period of time sufficient to reduce the total halide content of the epoxy resin.
(F) Washing the product of step (E) with a dilute aqueous solution of water, a weak mineral acid, a salt of an acid or a mixture thereof.
(G) Recovering the epoxy resin having a reduced total halogen content from the product of step (F).
Suitable epoxy resins include any epoxy resin containing an undesirable total amount of hydrolyzable and/or tethered halide groups containing an average of more than one ortho epoxy group per molecule. And is combined with
The most suitable epoxy resins include polyglycidyl ethers having an average of more than one hydroxyl group per molecule, the resins having a total halide content of at least 10PPM, such as glycidyl ethers of bisphenol, glycidyl ether novolac epoxy resins, epoxy novolac resins, and mixtures thereof.
Suitable ketones include, for example, acetone, butanone, methyl isobutyl ketone, cyclohexanone, and mixtures thereof.
Suitable aromatic hydrocarbons include, for example, benzene, toluene, xylene, and mixtures thereof.
Suitable compounds containing at least one aliphatic hydroxyl group per molecule include, for example, aliphatic alcohols, diols, triols and polyoxyalkylene compounds containing 1-3 hydroxyl groups per molecule and mixtures thereof, these compounds having an average molecular weight of 100-600, preferably 200-400.
Most suitable are polyoxyethylene glycols, sometimes referred to as polyethylene glycols, and mixtures thereof.
Suitable alkali metal hydroxides include, for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, and mixtures thereof. The alkali metal hydroxide may be used in solid form or in aqueous solution, and the aqueous solution is preferably 10 to 70% by weight, more preferably 40 to 60% by weight, of the alkali metal hydroxide.
The heating may be performed at or above atmospheric pressure. Pressurization is generally required when the solvent used has a relatively low boiling point. The temperature is preferably 50 to 200℃and more preferably 100 to 130 ℃. Preferably, the temperature is not higher than the boiling point of the solvent system. The pressure may be increased for a lower boiling solvent system so that a temperature above the boiling point may be used.
When the epoxy resin is washed to remove the formed salt and some unreacted alkali metal hydroxide, it is preferable to use a plurality of washing steps, and a diluted solution of an inorganic acid or a diluted aqueous solution of an inorganic acid salt is used for the first washing, and the pH of the acid or acid salt is preferably 2 to 10, more preferably 2 to 7.
Suitable acids and acid salts include, for example, phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, carbonic acid, boric acid, and mixtures thereof.
The organic matter obtained after washing is distilled to remove the solvent from the epoxy resin, and finally the epoxy resin is recovered.
The invention is illustrated by the following examples, but is not to be construed as being limited in scope thereto.
Example 1
75 Grams of a novolac epoxy resin having an average Epoxide Equivalent Weight (EEW) of about 220 and an average epoxy functionality of about 6 and containing 3536PPM by weight of hydrolyzable chloride was dissolved in 75 grams of a butanone (MEK) and toluene mixture having a butanone to toluene weight ratio of 75/25. 0.38 g (0.5% based on the weight of the epoxy resin), polyethylene glycol having an average molecular weight of about 400, was added to the above solution, and the solution was heated to 80 ℃ with stirring. 1.05 g of 50% strength aqueous potassium hydroxide solution (in a proportion of 1 equivalent of hydrolyzable halide to 1.25 equivalents of KOH) were added simultaneously and the reaction mixture was kept at 80℃for 2 hours (7200 seconds) with sufficient stirring.
The reaction mixture was diluted with butanone MEK/toluene mixed solvent to a resin concentration of 20%, neutralized with dilute H 3PO4, and then washed 3 to4 times with water to remove Nacl.
The organic washed with water was placed on a rotary evaporator under high vacuum at 170 ℃ and the solvent was removed entirely. Finally, the purified novolac epoxy resin containing 7PPM hydrolyzable chloride is obtained.
Example 2
The procedure of example 1 was followed using the following ingredients and conditions.
100 Grams of a novolac epoxy resin having an average Epoxide Equivalent Weight (EEW) of 220, an average epoxide functionality of 6, and 3700PPM of hydrolyzable chloride.
100 G of a butanone MEK/toluene mixture in a weight ratio of 75/25. And a sufficient amount of various cosolvents, such as 0.5 weight percent based on the weight of the epoxy resin.
1 Gram of 50% strength aqueous NaOH solution (1.2 equivalents each hydrolyzable chloride).
The reaction was allowed to proceed at 80 ℃ for 2 hours (7200 seconds). The results are shown in Table 1 below.
TABLE 1
Cosolvent hydrolyzable chloride PPM
Glycerol 181
Methanol 95
Isopropyl alcohol 84
Monomethyl ether 83 of propylene glycol
Tetraethylene glycol 54
Polyethylene glycol (molecular weight 200) 60
Polyethylene glycol (molecular weight 300) 55
Polyethylene glycol (molecular weight 400) 54
Polypropylene glycol (molecular weight 425) 159
Example 3
The procedure of example 1 was followed using the following components and conditions.
100 Grams of a novolac epoxy resin having an average epoxide equivalent weight EEW of 220, an average epoxide functionality of 6, and containing 3536ppm hydrolyzable chloride.
100 G of a butanone MEK/toluene mixture in a weight ratio of 75/25.
Different amounts of NaOH or KOH were used at 80 ℃ and several reactions were carried out with and without polyethylene glycol having an average molecular weight of 400, each for 2 hours (7200 seconds). The results are shown in Table 2 below.
TABLE 2
Per equivalent of
Caustic-soluble hydrolytic chlorinated polyethylene glycol hydrolyzable chlorine
Corresponding to
Caustic solution equivalent weight percent (wt.%) of liquid type
Content ppm
NaOH 1.08 0 167
NaOH 1.08 0.5 107
KOH 1.08 0 113
KOH 1.08 0.5 48
NaOH 1.16 0.5 81
KOH 1.16 0.5 33
NaOH 1.25 0.5 34
KOH 1.25 0.5 7
＊ Based on the weight of the epoxy resin.
Example 4
To a one liter reaction vessel equipped with temperature and pressure control and indication means, means for continuously adding aqueous sodium hydroxide, means for condensing and separating water from co-distilled water, solvent and epichlorohydrin, and means for refluxing solvent and epichlorohydrin, 118.5 g (1 eq) of a novolak resin having an average hydroxyl equivalent of 118.5 and an average functionality of 6, 370 g (4 eq) of epichlorohydrin and 247 g of methyl ether of propylene glycol (1-methoxy-2-yl propane) as solvents were added, and after stirring and thoroughly mixing the components at room temperature and atmospheric pressure, the temperature was raised to 65℃and the pressure was reduced to 180MMHg. Absolute pressure (24 KPa). 75.2 g (0.94 eq) of 50% strength aqueous sodium hydroxide solution are added continuously to the solution at a steady rate over a period of 4 hours (14400 seconds). During the addition of sodium hydroxide, water is distilled with the epichlorohydrin and solvent, whereby the water drops condense the distillate, forming two phases, an aqueous solution phase (upper) and an organic epichlorohydrin solvent phase (lower). The organic phase was refluxed into the reactor. After the sodium hydroxide addition was completed, the reaction mixture was maintained at 65℃and about 180mmHg absolute pressure (24 KPa) for an additional 30 minutes (1800 seconds). The resulting novolac epoxy resin was then distilled under high vacuum at 170 ℃ to completely remove all epichlorohydrin and 1-methoxy-2-hydroxypropane.
The same weight of a mixture of Methyl Ethyl Ketone (MEK) and toluene in a weight ratio of 75/25 was added to the melted novolac epoxy resin. A sample of the suspension was taken and found to contain 1200ppm hydrolyzable chloride. 0.87 g (0.5% by weight based on the epoxy resin) of polyethylene glycol having an average molecular weight of 400 was added to the above mixture, and the mixture was heated to 80℃with stirring. 0.86 g of 50% aqueous potassium hydroxide (1.3 eq KOH relative to 1 g hydrolyzable chloride) was added simultaneously and the reaction mixture was kept under sufficient stirring at 80℃for 2 hours (7200 seconds).
The reaction mixture was diluted to a resin concentration of 20% with a butanone MEK/toluene (75/25) mixed solvent, neutralized with CO 2 and then rinsed 4-5 times with water to remove NaCl.
The organic phase, which was rinsed with water, was placed on a rotary evaporator under high vacuum at 170 ℃ and the solvent was completely removed. A purified novolac epoxy resin containing 7ppm hydrolyzable chloride was obtained.
Example 5
625 G of cresol epoxy novolac containing 553ppm hydrolyzable chloride and 930ppm bound chloride (total chloride content 1483 ppm) are dissolved in 625 g of a butanone MEK/toluene solvent mixture in a weight ratio of 75/25. To this solution was added 1.875 g of polyethylene glycol having an average molecular weight of 400 (0.3% by weight based on the resin) and the solution was heated to 85 ℃ with stirring. 6.7 g of 45% strength aqueous potassium hydroxide (2.1 equivalents of caustic solution to 1 equivalent of chloride) were added simultaneously, and the reaction mixture was kept at 85℃for 6 hours (21600 seconds) with sufficient stirring.
The reaction mixture was diluted to a solids concentration of 20% for a ketone MEK/toluene mixture, neutralized with dilute H 3PO4, and rinsed several times with water to remove Nacl.
The washed organic phase was placed on a rotary evaporator under high vacuum at 170 ℃ and the solvent was completely removed to give a purified cresol epoxy novolac with 7ppm hydrolyzable chloride component and 263ppm bound chloride component (total chloride content 270 ppm).
Example 6
100 G of diglycidyl ether epoxy resin of bisphenol A, which contains 300ppm of hydrolyzable chloride and 900ppm of bound chloride (total chloride content 1200 ppm), were dissolved in 100 g of butanone MEK/toluene solvent mixture. To this solution was added 0.5 g (0.5% by weight based on the resin) of polyethylene glycol having a molecular weight of 400 and the solution was heated to 80 ℃ with stirring. 0.84 g of 45% aqueous potassium hydroxide (2 equivalents caustic to 1 equivalent chloride) was added simultaneously and the reaction mixture was maintained at 80 ℃ for 2 hours (7200 seconds) with good stirring.
The reaction mixture was diluted to a solid concentration of 20% with a butanone MEK/toluene mixed solvent, neutralized with CO 2, and then washed several times with water to remove NaCl.
The organic phase, washed with water, was placed on a rotary evaporator under high vacuum and 170 ℃ conditions, and the solvent was completely removed. A diglycidyl ether epoxy resin of purified bisphenol a containing 3ppm hydrolyzable chloride and 540ppm tethered chloride (total chloride content 543 ppm) was obtained.
Example 7
In a stainless steel pressure reactor vessel having a capacity of 2 liters, 625 g of cresol epoxy novolac containing 553ppm hydrolyzable chloride and 930ppm bound chloride (total chloride content of 1483 ppm) were dissolved in 625 g of a butanone MEK/toluene solvent mixture having a weight ratio of 75/25. To this solution was added 1.875 g (0.3% by weight based on the resin) of polyethylene glycol having an average molecular weight of 400, and the solution was heated to 120 ℃ with stirring. 3.9 g of 45% potassium hydroxide solution (1.2 equivalents of caustic solution to 1 equivalent of chloride) were added simultaneously and the reaction mixture was kept at 120℃for 1 hour (3600 seconds) with sufficient stirring.
The reaction mixture was diluted to a solid concentration of 20% with a butanone MEK/toluene mixed solvent, neutralized with CO 2, and washed several times with water to remove NaCl.
The washed organic phase was placed on a rotary evaporator under high vacuum and 170 ℃ conditions and the solvent was completely removed to give a purified cresol epoxy novolac containing 8ppm hydrolyzable chloride and 260ppm bound chloride (total chloride content 268 ppm).
Claims (6)
1. A process for reducing the total halide content of an epoxy resin containing hydrolyzable and/or bound halides, characterized by:
(A) Dissolving the epoxy resin in a solvent system comprising
(1) At least one ketone selected from the group consisting of acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, in an amount of 25 to 75% by weight,
(2) At least one aromatic hydrocarbon selected from benzene, toluene and xylene in an amount of 75 to 25% by weight,
(B) At least 0.1 to 5% by weight, based on the epoxy resin, of a compound having at least one aliphatic group per molecule,
(C) Heating the obtained solution to 50-200deg.C,
(D) 0.25 to 10 molar alkali metal hydroxide is added in the equivalent of the total halogenide,
(E) Heating continuously for a period of time to substantially reduce the total halide content of the epoxy resin,
(F) Washing the product of step (E) with water, a dilute aqueous solution of a weak mineral acid, a salt of an acid or a mixture thereof,
(G) Recovering the final epoxy resin with reduced total halide content from the product of step (F).
2. The process of claim 1 wherein in step (i) (A) said solvent system comprises 50 to 75 weight percent ketone and said aromatic hydrocarbon is present in an amount of 50 to 25 weight percent,
(Ii) The cosolvent amount in the step (B) is 0.2-1% by weight based on the weight of the epoxy resin.
(Iii) The heating mentioned in step (C) is carried out at a temperature of from 100 to 130 ℃,
(Iv) The amount of alkali metal hydroxide in step (D) is 1 to 5 molar equivalents based on the total halide.
3. The process of claim 2 wherein:
(i) The ketone is butanone or methyl isobutyl ketone,
(Ii) The aromatic hydrocarbon is benzene, toluene or xylene,
(Iii) The cosolvent is polyoxyethylene glycol or polyoxypropylene glycol with the average molecular weight of 100-600,
(Iv) The alkali metal hydroxide is sodium hydroxide or potassium hydroxide,
(V) The amount of alkali metal hydroxide in step (D) is 1 to 3 molar equivalents based on the total halide.
4. The process of claim 3, wherein
(I) The ketone is butanone, and the ketone is butanone,
(Ii) The aromatic hydrocarbon is toluene, and the aromatic hydrocarbon is toluene,
(Iii) The cosolvent is polyoxyethylene glycol with an average molecular weight of 200-400,
(Iv) The alkali metal hydroxide is potassium hydroxide.
5. The process of claim 4, wherein the product from (E) in step (F) is washed at least once with a dilute aqueous solution of a weak mineral acid.
6. The process of claim 5 wherein said weak mineral acid is phosphoric acid or carbonic acid.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US67277584A | 1984-11-19 | 1984-11-19 | |
| US627,775 | 1984-11-19 | ||
| US672,775 | 1984-11-19 | ||
| US76297185A | 1985-08-06 | 1985-08-06 | |
| US762,971 | 1985-08-06 | ||
| US06/773,500 US4585838A (en) | 1985-08-06 | 1985-09-09 | Process for preparing epoxy resins containing low levels of total halide |
| US773,500 | 1985-09-09 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85108970A CN85108970A (en) | 1986-07-09 |
| CN1004356B true CN1004356B (en) | 1989-05-31 |
Family
ID=27418256
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN85108970.4A Expired CN1004356B (en) | 1984-11-19 | 1985-11-08 | Process method for reducing total halide content in epoxy resin |
Country Status (12)
| Country | Link |
|---|---|
| EP (1) | EP0202277A4 (en) |
| KR (1) | KR900001943B1 (en) |
| CN (1) | CN1004356B (en) |
| AU (1) | AU560379B2 (en) |
| BR (1) | BR8507064A (en) |
| CA (1) | CA1257446A (en) |
| ES (1) | ES8701206A1 (en) |
| FI (1) | FI862961A7 (en) |
| IL (1) | IL77036A (en) |
| MY (1) | MY101828A (en) |
| NO (1) | NO165078C (en) |
| WO (1) | WO1986003210A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4785061A (en) * | 1987-08-13 | 1988-11-15 | The Dow Chemical Company | Method for reducing the aliphatic halide content of epoxy resins using a solvent mixture including a polar aprotic solvent |
| US7955498B2 (en) * | 2008-12-16 | 2011-06-07 | Chevron, U.S.A. Inc. | Reduction of organic halide contamination in hydrocarbon products |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE503550A (en) * | 1950-05-27 | |||
| BE546441A (en) * | 1955-03-28 | |||
| US2943095A (en) * | 1955-06-28 | 1960-06-28 | Union Carbide Corp | Process for preparing glycidyl polyethers of polyhydric phenols |
| NL270270A (en) * | 1960-10-17 | |||
| US3928288A (en) * | 1973-04-11 | 1975-12-23 | Dow Chemical Co | Epoxy novolac resins having a narrow molecular weight distribution and process therefor |
| US4447598A (en) * | 1983-04-07 | 1984-05-08 | The Dow Chemical Company | Method of preparing epoxy resins having low hydrolyzable chloride contents |
| US4485221A (en) * | 1983-11-03 | 1984-11-27 | Ciba-Geigy Corporation | Process for making epoxy novolac resins with low hydrolyzable chlorine and low ionic chloride content |
-
1985
- 1985-11-08 CN CN85108970.4A patent/CN1004356B/en not_active Expired
- 1985-11-12 AU AU50915/85A patent/AU560379B2/en not_active Ceased
- 1985-11-12 FI FI862961A patent/FI862961A7/en not_active Application Discontinuation
- 1985-11-12 KR KR1019860700472A patent/KR900001943B1/en not_active Expired
- 1985-11-12 WO PCT/US1985/002210 patent/WO1986003210A1/en not_active Ceased
- 1985-11-12 BR BR8507064A patent/BR8507064A/en unknown
- 1985-11-12 EP EP19850905721 patent/EP0202277A4/en not_active Ceased
- 1985-11-13 IL IL77036A patent/IL77036A/en not_active IP Right Cessation
- 1985-11-18 ES ES548999A patent/ES8701206A1/en not_active Expired
- 1985-11-18 CA CA000495522A patent/CA1257446A/en not_active Expired
-
1986
- 1986-07-18 NO NO862909A patent/NO165078C/en unknown
-
1987
- 1987-08-25 MY MYPI87001452A patent/MY101828A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| ES548999A0 (en) | 1986-11-16 |
| KR870700658A (en) | 1987-12-30 |
| FI862961L (en) | 1986-07-16 |
| CN85108970A (en) | 1986-07-09 |
| EP0202277A4 (en) | 1987-12-07 |
| FI862961A0 (en) | 1986-07-16 |
| NO862909D0 (en) | 1986-07-18 |
| FI862961A7 (en) | 1986-07-16 |
| MY101828A (en) | 1992-01-31 |
| AU5091585A (en) | 1986-06-18 |
| KR900001943B1 (en) | 1990-03-26 |
| AU560379B2 (en) | 1987-04-02 |
| WO1986003210A1 (en) | 1986-06-05 |
| IL77036A (en) | 1989-07-31 |
| BR8507064A (en) | 1987-05-05 |
| NO165078B (en) | 1990-09-10 |
| IL77036A0 (en) | 1986-04-29 |
| NO165078C (en) | 1990-12-19 |
| ES8701206A1 (en) | 1986-11-16 |
| EP0202277A1 (en) | 1986-11-26 |
| CA1257446A (en) | 1989-07-11 |
| NO862909L (en) | 1986-07-18 |
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