CN100532418C - Synthesis process of epoxy resin with anionic catalyst - Google Patents
Synthesis process of epoxy resin with anionic catalyst Download PDFInfo
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- CN100532418C CN100532418C CNB2006100964375A CN200610096437A CN100532418C CN 100532418 C CN100532418 C CN 100532418C CN B2006100964375 A CNB2006100964375 A CN B2006100964375A CN 200610096437 A CN200610096437 A CN 200610096437A CN 100532418 C CN100532418 C CN 100532418C
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Abstract
The synthesis process of epoxy resin with anionic catalyst includes the following steps: the etherification of diphenol propane and epoxy chloropropane in the presence of quaternary ammonium salt at 75-125 deg.c for 1-8 hr to produce etherate; the ring closing reaction of treated alkaline anionic exchange resin and the etherate at 35-65 deg.c for 1-6; filtering the resultant to obtain filtrate and vacuum distilling the filtrate to obtain the epoxy resin product. The synthesis process has no waste water and sodium chloride and is environment friendly, and the multiple times of catalysis with alkaline anionic exchange resin promote the ring closing reaction and results in raised epoxy resin yield.
Description
Technical field
The present invention relates to a kind of preparation method of resin, relate in particular to a kind of method that adopts the anionic catalyst synthetic epoxy resin.
Background technology
Usually the preparation method of Resins, epoxy be by diphenylol propane under the effect of catalyzer with equivalent or excessive slightly epoxy chloropropane generation ring-opening reaction; carry out ring-closure reaction with alkali metal hydroxide again, again through extraction, washing; desolventizing can obtain Resins, epoxy.When adopting this method synthetic epoxy resin, can use a large amount of alkali metal hydroxides, produce a large amount of waste water and sodium-chlor, bring certain environmental pollution and economic attrition.
Summary of the invention
The purpose of this invention is to provide a kind of method that adopts the anionic catalyst synthetic epoxy resin, this method can improve the transformation efficiency of Resins, epoxy, saves the use of alkali metal hydroxide, can obviously reduce the discharging of pollutent.
The present invention realizes by following technical solution:
A kind of method that adopts the anionic catalyst synthetic epoxy resin comprises following a few step:
(1) handle strong anion-exchange resin, concrete measure comprises:
A) be the strong anion-exchange resin mass concentration that 1%～15% metabisulfite solution carries out salt and washes, be washed till neutrality with deionized water afterwards, wherein, the metabisulfite solution quality be the strong anion-exchange resin quality 2-5 doubly,
B) step a) being washed to neutral strong anion-exchange resin mass concentration is that 1%～15% aqueous sodium hydroxide solution carries out alkali cleaning, is washed till neutrality with deionized water afterwards, the quality of aqueous sodium hydroxide solution be strong anion-exchange resin 2-5 doubly,
C) step b) is washed to the neutral strong anion-exchange resin, extracts surperficial moisture content in the strong anion-exchange resin with dehydrated alcohol,
D) will handling the back strong alkali ion exchange resin, to carry out heating, vacuum training oven dry dry, and temperature 40-75 ℃, time 12-24 hour,
Thereby the strong anion-exchange resin after obtaining handling;
(2) diphenylol propane and epoxy chloropropane are mixed, and add the catalyzer quaternary ammonium salt,, generate etherate 75～125 ℃ of following etherification reactions 1～8 hour;
(3) strong anion-exchange resin after will handling joins in the above-mentioned etherate, carries out ring-closure reaction under 35～65 ℃, and the reaction times is 1～6 hour, and reaction product is filtered, and obtains filtrate, with the filtrate decompression distillation, obtains the Resins, epoxy finished product,
Above-mentioned diphenylol propane, epoxy chloropropane, quaternary ammonium salt are respectively 10%-50%, the 20%-150%, 0.275%～1.5% of the strong anion-exchange resin weight after the processing.
In the technical program, the adding weight of diphenylol propane is preferably the 20%-30% of exchange resin weight, the adding weight of epoxy chloropropane is preferably the 30%-125% of exchange resin weight, in the filtrate that step (3) obtains, add the strong anion-exchange resin after handling, under 35～65 ℃, carry out further ring-closure reaction, reaction times is 1-6 hour, wherein, the quality of the strong anion-exchange resin after the processing is 0.5-3 a times of filtrate quality, the ring-closure reaction temperature of step (3) is preferably 45～55 ℃, reaction times is preferably 2-5 hour, reacts this step and can repeat multiplicity 2-5 time.
The present invention obtains following technique effect:
1. the strong base anion catalyzer synthetic epoxy resin (diphenolic propane diglycidol ether) after the processing adopted of the present invention, make in process of production, no waste water and sodium-chlor exist in the whole reaction system, have reduced the discharging of pollutent, have reduced the environmental protection cost.
2. the present invention adopts repeatedly catalysis process of strong anion-exchange resin, has promoted ring-closure reaction greatly, makes the transformation efficiency of Resins, epoxy further improve.
3. the adding weight of diphenylol propane is preferably the 20%-30% of the strong anion-exchange resin weight after the processing, the adding weight of epoxy chloropropane is preferably the 30%-125% of exchange resin weight, by optimizing proportioning, its transformation efficiency and oxirane value are significantly improved.
Description of drawings
Fig. 1 process flow diagram of the present invention
Embodiment
Embodiment 1
A kind of method that adopts the anionic catalyst synthetic epoxy resin comprises following a few step:
(1) handle strong anion-exchange resin, concrete measure comprises:
A) strong anion-exchange resin (is floated the 201# that Lai Te (China) company limited (purolite (china) co.LTD) produces, 301# anionite-exchange resin) be that 1%～15% metabisulfite solution carries out salt and washes (sodium ion in the commentaries on classics) with mass concentration, be washed till neutrality (the pH value is 7) with deionized water afterwards, wherein, the metabisulfite solution quality is 2-5 a times of strong anion-exchange resin quality, for example can be chosen for 3,4 times, b) step a) being washed to neutral strong anion-exchange resin mass concentration is that 1%～15% aqueous sodium hydroxide solution carries out alkali cleaning, be washed till neutrality (pH value is 7) with deionized water afterwards, the quality of aqueous sodium hydroxide solution is 2-5 a times of strong anion-exchange resin, for example can be chosen for 2.5,3,4 times, c) step b) is washed to the neutral strong anion-exchange resin, extract surperficial moisture content in the strong anion-exchange resin with dehydrated alcohol, each extraction is 2-5 times of strong anion-exchange resin with the quality of dehydrated alcohol, for example can be chosen for 2.6,3.2,4.5 doubly, extraction times is 2-4 time, d) will handling the back strong alkali ion exchange resin, to carry out heating, vacuum training oven dry dry, temperature 40-75 ℃, time 12-24 hour, vacuum tightness is to remove the conventional vacuum tightness of moisture, can be that gauge outfit pressure is-0.085Mpa, thus the strong anion-exchange resin after obtaining handling;
(2) diphenylol propane and epoxy chloropropane are mixed, and add the catalyzer quaternary ammonium salt, 75～125 ℃ of following etherification reactions 1～8 hour, generate etherate, wherein temperature can be chosen for 80 ℃, 90 ℃, 105 ℃, 112 ℃, the reaction times can be 1 hour, 3 hours, 5 hours, 6 hours, 7 hours;
(3) strong anion-exchange resin after will handling joins in the above-mentioned etherate, carries out ring-closure reaction under 35～65 ℃, and temperature can be chosen for 40 ℃, 45 ℃, 52 ℃, 60 ℃, reaction times is 1～6 hour, can be chosen for 1,3,4,5.5 hours, reaction product is filtered, obtain filtrate, with filtrate decompression distillation, underpressure distillation condition: temperature: 120-140 ℃, gauge outfit pressure is-0.085MPa to obtain the Resins, epoxy finished product
Above-mentioned diphenylol propane, epoxy chloropropane, quaternary ammonium salt is respectively the 10%-50% of the strong anion-exchange resin weight after the processing, 20%-150%, 0.275%～1.5%, diphenylol propane can be 10%, 15% of the strong anion-exchange resin weight after handling, 22%, 35%, 42%, 48%, epoxy chloropropane can be 25%, 35% of the strong anion-exchange resin weight after handling, 45%, 53%, 68%, 74%, 82%, 90%, 115%, 120%, 130%, 140%, quaternary ammonium salt can be 0.375% of the strong anion-exchange resin weight after handling, 0.414%, 0.52%, 0.61%, 0.73%, 0.82%, 0.90%, 0.95%, 1.1%, 1.25%, 1.32%, 1.44%, quaternary ammonium salt is a benzyl trimethyl ammonium chloride, benzyltriethylammoinium chloride, tetramethyl ammonium chloride, the mixture of one or more in the 4 bromide, the proportioning of mixture can be any proportioning; In the present embodiment, the adding weight of diphenylol propane is preferably the 20%-30% of exchange resin weight, the adding weight of epoxy chloropropane is preferably the 30%-125% of exchange resin weight, in the filtrate that step (3) obtains, add the strong anion-exchange resin after handling, under 35～65 ℃, carry out further ring-closure reaction, reaction times is 1-6 hour, and wherein, the quality of the strong anion-exchange resin after the processing is 0.5-3 a times of filtrate quality.The ring-closure reaction temperature of step (3) is preferably 45～55 ℃, and the reaction times is preferably 2-5 hour.This reactions steps can repeat, multiplicity 2-5 time.
Embodiment 2
The highly basic exchange resins of 1000 grams are taken off with the aqueous sodium persulfate solution of mass concentration 2% wash, be washed to neutrality with deionized water afterwards.Handle with the potassium hydroxide aqueous solution of mass concentration 2% being washed to the neutral exchange resin, be washed to neutrality with deionized water afterwards, go out surperficial moisture content in the ion exchange resin with alcohol extraction.Anionite-exchange resin after handling is carried out the heating, vacuum training accompany oven dry dry, 40 ℃ of temperature, the time is 12 hours, and 100 diphenylol propanes that restrain and 200 gram epoxy chloropropane are added 15 gram benzyl trimethyl ammonium chlorides, carries out etherification reaction 1 hour between 75 ℃.Anionite-exchange resin after handling 100 grams are added the etherifying agent that above-mentioned reaction generates, carry out ring-closure reaction under 35 ℃, the reaction times is 1 hour.After the reaction reactant is filtered, the liquid that filters out is added 250 gram anionite-exchange resin again, under 35 ℃, carry out ring-closure reaction, reaction times is 1 hour, afterwards reactant is filtered, carries out reclaim under reduced pressure and go out excessive epoxy chloropropane filtering the afterreaction thing, temperature 110 ℃/-0.085Mpa, just obtain the Resins, epoxy finished product, oxirane value Ev=0.30.
Embodiment 3
The highly basic exchange resins of 1000 grams are taken off with the sodium sulfate of mass concentration 15% wash, the metabisulfite solution quality is 2000 to restrain, and is washed to neutrality with deionized water afterwards.Handle with the aqueous sodium hydroxide solution of mass concentration 15% being washed to the neutral exchange resin, the quality of aqueous sodium hydroxide solution is 2500 grams, is washed to neutrality with deionized water afterwards.Go out surperficial moisture content in the ion exchange resin with alcohol extraction, the alcoholic acid quality is 3000 grams.Anionite-exchange resin after handling is carried out the heating, vacuum training accompanies oven dry dry, vacuum tightness is-0.085Mpa, 75 ℃ of temperature, and the time is 24 hours, the diphenylol propane and the 1500 gram epoxy chloropropane of 500 grams are added 2.75 gram 4 bromides, between 125 ℃, carried out etherification reaction 8 hours.Anionite-exchange resin after handling 500 grams are added the etherifying agent that above-mentioned reaction generates, carry out ring-closure reaction under 65 ℃, holding time is 6 hours.After the reaction reactant is filtered.The liquid that filters out is added 500 gram anionite-exchange resin again, under 65 ℃, carry out ring-closure reaction, hold time is 6 hours, afterwards reactant is filtered, filtration afterreaction thing is carried out reclaim under reduced pressure go out excessive epoxy chloropropane, temperature 150 ℃/-0.085Mpa, just obtain the Resins, epoxy finished product, oxirane value Ev=0.28.
Embodiment 4
The highly basic exchange resins of 1000 grams are taken off with the sodium sulfate of mass concentration 7% wash, be washed to neutrality with deionized water afterwards.Handle with the aqueous sodium hydroxide solution of mass concentration 8% being washed to the neutral exchange resin, be washed to neutrality with deionized water afterwards.Go out surperficial moisture content in the ion exchange resin with alcohol extraction.Anionite-exchange resin after handling is carried out the heating, vacuum training accompany oven dry dry, 62 ℃ of temperature, the time is 18 hours, and 300 diphenylol propanes that restrain and 900 gram epoxy chloropropane are added 9.6 gram 4 bromides, carries out etherification reaction 7 hours between 101 ℃.Anionite-exchange resin after handling 300 grams are added the etherifying agent that above-mentioned reaction generates, carry out ring-closure reaction under 55 ℃, holding time is 5 hours.After the reaction reactant is filtered.The liquid that filters out is added 300 gram anionite-exchange resin again, under 55 ℃, carry out ring-closure reaction, hold time is 4 hours, afterwards reactant is filtered, filtration afterreaction thing is carried out reclaim under reduced pressure go out excessive epoxy chloropropane, temperature is at 131 ℃, and gauge outfit pressure is-0.085Mpa, just obtain the Resins, epoxy finished product, oxirane value Ev=0.29.
Embodiment 5
The highly basic exchange resins of 1000 grams are taken off with the sodium sulfate of mass concentration 9% wash, be washed to neutrality with deionized water afterwards.Handle with the aqueous sodium hydroxide solution of mass concentration 10% being washed to the neutral exchange resin, be washed to neutrality with deionized water afterwards.Go out surperficial moisture content in the ion exchange resin with alcohol extraction.It is dry that anionite-exchange resin after handling is carried out heating, vacuum training oven dry, 55 ℃ of temperature, and the time is 16 hours, and 200 diphenylol propanes that restrain and 800 gram epoxy chloropropane are added 12 gram benzyltriethylammoinium chlorides, carries out etherification reaction 4 hours between 95 ℃.Anionite-exchange resin after handling 180 grams are added the etherifying agent that above-mentioned reaction generates, carry out ring-closure reaction under 45 ℃, holding time is 3 hours.After the reaction reactant is filtered.The liquid that filters out is added 500 gram anionite-exchange resin again, under 45 ℃, carry out ring-closure reaction, reaction times is 4 hours, afterwards reactant is filtered, filtration afterreaction thing is carried out reclaim under reduced pressure go out excessive epoxy chloropropane, temperature 120 ℃/-0.085Mpa, just obtain the Resins, epoxy finished product, oxirane value Ev=0.27.Measure and all adopt volumetric precipitation method, wherein oxirane value adopts the titration of hydrochloric acid acetone method, and organochlorine, inorganic chlorine adopt silver nitrate titration.Softening temperature is measured and is adopted ring and ball method.
It is identical with embodiment 1 that embodiment 3,4,5 handles the used raw material of strong base anion resins.
Claims (4)
1, a kind of method that adopts the anionic catalyst synthetic epoxy resin is characterized in that comprising following a few step:
(1) handle strong anion-exchange resin, concrete measure comprises:
A) be the strong anion-exchange resin mass concentration that 1%～15% metabisulfite solution carries out salt and washes, be washed till neutrality with deionized water afterwards, wherein, the quality of metabisulfite solution be the strong anion-exchange resin quality 2-5 doubly,
B) step a) being washed to neutral strong anion-exchange resin mass concentration is that 1%～15% aqueous sodium hydroxide solution carries out alkali cleaning, is washed till neutrality with deionized water afterwards, the quality of aqueous sodium hydroxide solution be strong anion-exchange resin 2-5 doubly,
C) step b) is washed to the neutral strong anion-exchange resin, extracts surperficial moisture content in the strong anion-exchange resin with dehydrated alcohol,
D) will handling the back strong alkali ion exchange resin, to carry out heating, vacuum training oven dry dry, and temperature 40-75 ℃, time 12-24 hour,
Thereby the strong anion-exchange resin after obtaining handling;
(2) diphenylol propane and epoxy chloropropane are mixed, and add the catalyzer quaternary ammonium salt,, generate etherate 75～125 ℃ of following etherification reactions 1～8 hour;
(3) strong anion-exchange resin after will handling joins in the above-mentioned etherate, carries out ring-closure reaction under 35～65 ℃, and the reaction times is 1～6 hour, and reaction product is filtered, and obtains filtrate, with the filtrate decompression distillation, obtains the Resins, epoxy finished product,
The weight proportion of diphenylol propane, epoxy chloropropane and quaternary ammonium salt in the above-mentioned steps (2) is:
In the step (2) weight of diphenylol propane be after handling in the step (3) strong anion-exchange resin weight 100%, in the step (2) weight of epoxy chloropropane be after handling in the step (3) strong anion-exchange resin weight 300%, the weight of quaternary ammonium salt is 0.1375% of diphenylol propane and epoxy chloropropane weight sum in the step (2);
In the step (2) weight of diphenylol propane be after handling in the step (3) strong anion-exchange resin weight 100%, in the step (2) weight of epoxy chloropropane be after handling in the step (3) strong anion-exchange resin weight 300%, the weight of quaternary ammonium salt is 0.8% of diphenylol propane and epoxy chloropropane weight sum in the step (2); Or:
In the step (2) weight of diphenylol propane be after handling in the step (3) strong anion-exchange resin weight 200/180, in the step (2) weight of epoxy chloropropane be after handling in the step (3) strong anion-exchange resin weight 800/180, the weight of quaternary ammonium salt is 1.2% of diphenylol propane and epoxy chloropropane weight sum in the step (2).
2, the method for employing anionic catalyst synthetic epoxy resin according to claim 1, it is characterized in that, in the filtrate that step (3) obtains, add the strong anion-exchange resin after handling, under 35～65 ℃, carry out further ring-closure reaction, reaction times is 1-6 hour, wherein, the quality of the strong anion-exchange resin after the processing be the filtrate quality 0.5-3 doubly.
3, the method for employing anionic catalyst synthetic epoxy resin according to claim 1 is characterized in that, the ring-closure reaction temperature of step (3) is preferably 45～55 ℃, and the reaction times is preferably 2-5 hour.
4, the method for employing anionic catalyst synthetic epoxy resin according to claim 2 is characterized in that, this reactions steps can repeat, multiplicity 2-5 time.
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| CNB2006100964375A CN100532418C (en) | 2006-09-26 | 2006-09-26 | Synthesis process of epoxy resin with anionic catalyst |
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| CNB2006100964375A CN100532418C (en) | 2006-09-26 | 2006-09-26 | Synthesis process of epoxy resin with anionic catalyst |
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| JP5764140B2 (en) | 2009-12-16 | 2015-08-12 | ダウ グローバル テクノロジーズ エルエルシー | Production of epoxy resins using improved ion exchange resin catalysts. |
| CN102181040A (en) * | 2011-04-25 | 2011-09-14 | 苏州苏通树脂有限公司 | Medium molecular weight solid bisphenol A epoxy resin |
| CN102250314A (en) * | 2011-04-25 | 2011-11-23 | 苏州苏通树脂有限公司 | Low-molecular-weight liquid bisphenol A epoxy resin |
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Non-Patent Citations (4)
| Title |
|---|
| 二酚基丙烷环氧树脂的合成. 曹优明.渝西学院学报（自然科学版），第3卷第1期. 2004 |
| 二酚基丙烷环氧树脂的合成. 曹优明.渝西学院学报（自然科学版），第3卷第1期. 2004 * |
| 双酚A低分子环氧树脂的合成工艺研究. 杨东洁.四川师范大学学报（自然科学版），第24卷第2期. 2001 |
| 双酚A低分子环氧树脂的合成工艺研究. 杨东洁.四川师范大学学报（自然科学版），第24卷第2期. 2001 * |
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