CN101671318B - Cycloaliphatic epoxy resin and preparation method thereof - Google Patents
Cycloaliphatic epoxy resin and preparation method thereof Download PDFInfo
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- CN101671318B CN101671318B CN200810139433XA CN200810139433A CN101671318B CN 101671318 B CN101671318 B CN 101671318B CN 200810139433X A CN200810139433X A CN 200810139433XA CN 200810139433 A CN200810139433 A CN 200810139433A CN 101671318 B CN101671318 B CN 101671318B
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Abstract
The invention relates to cycloaliphatic epoxy resin and a preparation method thereof. The method comprises the following steps of: taking dicycloacrylate as a raw material, hydrogen peroxide solution as an oxidizing agent and halocarbon or halogenated hydrocarbon as a catalyst and synthesizing the cycloaliphatic epoxy resin under the action of a heteropolyacid catalyst, wherein the main reaction product of the cycloaliphatic epoxy resin, namely epoxy cyclohexane-4-carboxylic epoxycyclohexane-4-methylene ester accounts for over 90 weight percent and the epoxy equivalent weight is between 120 and 140. Each quality index of the cycloaliphatic epoxy resin of the invention is the same as that of the cycloaliphatic epoxy resin prepared by using a peroxyacetic acid as the oxidizing agent. The cycloaliphatic epoxy resin of the invention can be used as an automobile paint, a metal surface paint and an insulative substrate resin in the field of electronic and electric appliances.
Description
Technical field
The present invention relates to a kind of cycloaliphatic epoxy resin and preparation method thereof, belong to the Resins, epoxy technical field.
Background technology
Cycloaliphatic epoxy resin (main component is epoxy cyclohexane-4-carboxylic acid epoxy cyclohexane-4-methylene radical ester) has good insulation performance, thermotolerance, chemicals-resistant corrodibility, mechanical property is solidified the low volumetric shrinkage in back and various base materials is all had good adhesive property.Pretend resin, be widely used in automobile finish, metal surface coating, field of electronics for a kind of excellent combination property.Yet the production of this cycloaliphatic epoxy resin uses Peracetic Acid as oxygenant, and there is bigger danger in production process; Therefore select new oxidant production oxygen hexanaphthene-4-carboxylic acid for use, the research of epoxy cyclohexane-4-methylene radical ester is the problem of this domain experts' primary study and concern always.
From present worldwide research situation, the production main route of cycloaliphatic epoxy resin: be to do raw material with dicyclo alkene ester { α-(4 ' cyclohexenyl) 4 ' cyclohexenecarboxylic acid methyl esters }, (1) makes to produce under the condition of oxygenant oxygen hexanaphthene-4-carboxylic acid, epoxy cyclohexane-4-methylene radical ester in Peracetic Acid; The patent DE3723843 of example such as Germany; (2) make catalyzer with the organic salt of metallic nickel, make oxygenant, as the patent JP05032647 of Japan with oxygen; (3) use propionic acid, 50% the hydrogen peroxide and the vitriol oil are made oxygenant at the mixed solvent of benzene, carry out epoxidation, for example De Guo patent DE3528002; The oxygenant that the cyclic aliphatic epoxy resins of these designs is used all exists different shortcomings, and is relatively more dangerous as Peracetic Acid and oxygen, propionic acid, and 50% the hydrogen peroxide and the vitriol oil are very complicated at the mixed solvent system of benzene, and the recovery that is difficult for solvent is used etc. again.
Summary of the invention
At the technical problem that prior art exists, the invention provides that a kind of technology is simple, processing ease, be easy to the preparation method of the cyclic aliphatic epoxy resins of industrial amplification production.
The present invention is a raw material with dicyclo alkene ester, and hydrogen peroxide as oxidant is selected halocarbon or halogenated hydrocarbon solvent for use, under the effect of heteropolyacid catalyst, synthetic cycloaliphatic epoxy resin.
The preparation method of cycloaliphatic epoxy resin of the present invention, step is as follows:
(1) hydrogen peroxide, aliphatics halocarbon or aromatic series halogenated hydrocarbon solvent and the heteropolyacid catalyst with concentration 15～50%wt adds in the container, regulates the pH value to 1-5, stirs 80-90 minute, solution is mixed into the milky solution of homogeneous; The oxidizing agent solution that must contain catalyzer.
(2) dicyclo alkene ester and aliphatics halocarbon or aromatic series halogenated hydrocarbon solvent are joined in the container of taking back stream, stir, when being warming up to 40～65 ℃, occur refluxing; Begin to drip the oxidizing agent solution that contains catalyzer that step (1) makes, temperature maintenance was finished the dropping of oxidizing agent solution at 40～65 ℃ in 60～90 minutes; Control reaction temperature continues reaction 40-60 minute at 40-90 ℃.Static 20-30 minute, tell lower floor's organic phase, upper aqueous layer is done discarded the processing.
(3) organic phase solution that step (2) is told joins in the apparatus container of band water condensation, oil bath heating, temperature be controlled at 80 ℃～below 120 ℃, carry out air distillation, steaming desolventizes, recovered solvent can be reused after moisture is gone out;
(4) step (3) is steamed solution after desolventizing, underpressure distillation under 180～220 ℃, vacuum tightness 1.0 mmhg conditions, product of distillation is cycloaliphatic epoxy resin.
Product yield can reach more than 83%, and gas-chromatography GC detects (area normalization method) principal product: epoxy cyclohexane-4-carboxylic acid epoxy cyclohexane-4-methylene radical ester is more than 90%wt, and epoxy equivalent (weight) is between 120～140.
The mol ratio of the dicyclo alkene ester of the hydrogen peroxide of the concentration 15-50%wt in the step (1) and step (2) is 1:2～6, and the catalyzer dosage of step (1) is 4～4.5% of a reactant gross weight.
Aliphatics halocarbon solvent in step (1) and the step (2) is selected from methylene dichloride, chloroform, and ethylene dichloride or ethylene dibromide, the aromatic series halohydrocarbon is selected from chlorobenzene, bromobenzene or dichlorobenzene.The amount of solvent is according to routine techniques, being advisable by the solubilizing reaction thing.
The additive of regulating pH in the step (1) is selected from sodium hydrogen phosphate, SODIUM PHOSPHATE, MONOBASIC, sodium phosphate, yellow soda ash, sodium bicarbonate or Potassium Hydrogen Phthalate.
Preferably, hydrogen peroxide concentration is 30～40%wt in the step (1).Preferably, concentration is the hydrogen peroxide of 30～40%wt and mol ratio with the dicyclo alkene ester of step (2) is 1:2～3 in the step (1).
The used heteropolyacid catalyst of the present invention is tungstate and quaternary amine synthetic prior art products, referring to CN1900071, but market purchasing, this heteropolyacid is a kind of catalyzer that can be widely used in epoxidation reaction.
Main component (more than the 90%wt) is epoxy cyclohexane-4-carboxylic acid epoxy cyclohexane-4-methylene radical ester in the cycloaliphatic epoxy resin of the present invention's preparation, and its structural formula is:
Method of the present invention can be finished reaction at short notice smoothly, has the color and luster of light color for making final Resins, epoxy, and the finished product have adopted the distillatory method.Hydrogen peroxide (hydrogen peroxide) is a kind of eco-friendly oxygenant, and the technical maturity of producing, and security will be got well relatively.
Cycloaliphatic epoxy resin of the present invention and preparation method thereof has changed with Peracetic Acid as the oxidant production cycloaliphatic epoxy resin; Its every quality index is identical with the cycloaliphatic epoxy resin of making oxidant production with Peracetic Acid (main component is epoxy cyclohexane-4-carboxylic acid epoxy cyclohexane-4-methylene radical ester), is the cycloaliphatic epoxy resin that can be used as automobile finish, metal surface coating, the use of field of electronics insulativity matrix resin.
Embodiment
Embodiment 1: a kind of preparation method of cycloaliphatic epoxy resin, and step is as follows:
(1) contains the preparation of the oxidizing agent solution of catalyzer
Take by weighing 46.0 hydrogen peroxide (content is 35%) and 30.0g chloroform respectively, 2.2g catalyzer heteropolyacid; Join in the 250ml single port flask, install agitator,, regulate pH value to 2.4-3.0 scope with 0.5g～1.0 sodium hydrogen phosphates; Stirred 90 minutes, and solution was mixed into the milky solution of homogeneous; Be poured in the dropping funnel stand-by.
(2) take by weighing dicyclo alkene ester 44g, chloroform 80g respectively, join in the 500ml four-hole boiling flask, install agitator,, thermometer, dropping funnel and branch water condensing unit.Stir, be warming up to when getting over 60～65 ℃, occur refluxing; Oxidizing agent solution in the beginning addition funnel, system temperature maintains about 60～65 ℃, is added dropwise to complete at 60～90 minutes; Continue reaction 60 minutes.Static 30 minutes, tell lower floor's organic phase, upper aqueous layer is done discarded the processing.
(3) with the organic phase solution of telling, join in the 250ml four-hole boiling flask, install agitator,, thermometer and water condensing unit.The oil bath heating, temperature is carried out the air distillation chloroform below 80 ℃, and the chloroform of recovery can be reused after moisture is gone out;
(4) temperature is at 180～220 ℃, vacuum tightness 1.0 mmhg, and underpressure distillation, product is a cycloaliphatic epoxy resin.Product yield can reach more than 83%, and gas-chromatography GC detects (area normalization method) principal product: epoxy cyclohexane-4-carboxylic acid epoxy cyclohexane-4-methylene radical ester is more than 90%, and epoxy equivalent (weight) is between 130～135.
Embodiment 2:
Take by weighing 54.0 hydrogen peroxide (content is 30%) and 30.0g toluene respectively, 2.2g catalyzer heteropolyacid; Join in the 250ml single port flask, install agitator, with 0.5g～1.0gNH
2CH
2PO
3H
2, regulate pH value to 2.0-2.7 scope; Stirred 120 minutes, and solution was mixed into the milky solution of homogeneous; Take by weighing dicyclo alkene ester 44g, toluene 80g respectively, join in the 500ml four-hole boiling flask, install agitator,, thermometer, dropping funnel and branch water condensing unit.Stir, be warming up to when getting over 70～80 ℃; Oxidizing agent solution in the beginning addition funnel, system temperature maintains about 70～80 ℃, is added dropwise to complete at 60～90 minutes; Continue reaction 60 minutes.Static 30 minutes, tell lower floor's organic phase, upper aqueous layer is done discarded the processing.
With the organic phase solution of telling, join in the 250ml four-hole boiling flask, install agitator,, thermometer and water condensing unit.The oil bath heating, temperature is carried out air distillation toluene below 120 ℃, and the toluene of recovery can be reused after moisture is gone out;
Temperature is at 180～220 ℃, vacuum tightness 1.0 mmhg, and underpressure distillation, product is a cycloaliphatic epoxy resin.Product yield can reach more than 70%, and gas-chromatography GC detects (area normalization method) principal product: epoxy cyclohexane-4-carboxylic acid epoxy cyclohexane-4-methylene radical ester is more than 90%, and epoxy equivalent (weight) is 125～140
Embodiment 3:
Take by weighing 80.0 hydrogen peroxide (content is 15%) and 30.0gl respectively, 2 ethylene dichloride, 2.5g catalyzer heteropolyacid (1mol wolframic acid and 9 molybdic acid synthetic catalyst of compound heteropoly acid); Join in the single port flask, install agitator,, regulate pH value to 2.4-3.0 scope with 0.5g～1.0 sodium hydrogen phosphates; Stirred 60～90 minutes, and solution was mixed into the milky solution of homogeneous; Take by weighing dicyclo alkene ester 44g, 1 respectively, 2-ethylene dichloride 80g joins in the 500ml four-hole boiling flask, installs agitator,, thermometer, dropping funnel and branch water condensing unit.Stir, be warming up to when getting over 60～70 ℃; Oxidizing agent solution in the beginning addition funnel, system temperature maintains about 60～70 ℃, is added dropwise to complete at 60～90 minutes; Continue reaction 120 minutes.Static 30 minutes, tell lower floor's organic phase, upper aqueous layer is done discarded the processing.
With the organic phase solution of telling, join in the 250ml four-hole boiling flask, install agitator,, thermometer and water condensing unit.The oil bath heating, temperature is carried out air distillation 1,2 ethylene dichloride below 90 ℃, and 1,2 ethylene dichloride of recovery can be reused after moisture is gone out;
Temperature is at 180～220 ℃, vacuum tightness 1.0 mmhg, and underpressure distillation, product is a cycloaliphatic epoxy resin.Product yield can reach more than 60%, and gas-chromatography GC detects (area normalization method) principal product: epoxy cyclohexane-4-carboxylic acid epoxy cyclohexane-4-methylene radical ester is more than 95%, and epoxy equivalent (weight) is 130～140.
The above only is several concrete forms of implementation of the present invention, should be pointed out that to those skilled in the art, can also make many distortion and improvement.All do not exceed the described distortion of claim or improvement all should be considered as protection scope of the present invention.
Claims (4)
1. the preparation method of a cycloaliphatic epoxy resin, principal product is the compound with following structural formula:
Raw material is formula (II) compound:
Step is as follows:
(1) hydrogen peroxide, aliphatics halocarbon or aromatic series halogenated hydrocarbon solvent and the heteropolyacid catalyst with concentration 30～40wt% adds in the container, regulates the pH value to 1-5, stirs 80-90 minute, solution is mixed into the milky solution of homogeneous; The oxidizing agent solution that must contain catalyzer;
(2) formula (II) compound and aliphatics halocarbon or aromatic series halogenated hydrocarbon solvent are joined in the container of taking back stream, stir, when being warming up to 40～65 ℃, occur refluxing; Begin to drip the oxidizing agent solution that contains catalyzer that step (1) makes, temperature maintenance was finished the dropping of oxidizing agent solution at 40～65 ℃ in 60～90 minutes; Control reaction temperature continues reaction 40-60 minute at 40-90 ℃; Static 20-30 minute, tell lower floor's organic phase, upper aqueous layer is done discarded the processing;
(3) organic phase solution that step (2) is told joins in the apparatus container of band water condensation, the oil bath heating, and temperature is controlled at 80 ℃～120 ℃, carries out air distillation, and steaming desolventizes, and recovered solvent can be reused after moisture is gone out;
(4) step (3) is steamed solution after desolventizing, underpressure distillation under 180～220 ℃, vacuum tightness 1.0 mmhg conditions, product of distillation is promptly;
The mol ratio of the hydrogen peroxide of 30～40wt% of step (1) and formula (II) compound is 1: 2～3; The catalyzer dosage of step (1) is 4～4.5% of a reactant gross weight.
2. the preparation method of cycloaliphatic epoxy resin as claimed in claim 1, it is characterized in that the aliphatics halocarbon solvent in step (1) and the step (2) is selected from methylene dichloride, chloroform, ethylene dichloride or ethylene dibromide, the aromatic series halohydrocarbon is selected from chlorobenzene, bromobenzene or dichlorobenzene.
3. the preparation method of cycloaliphatic epoxy resin as claimed in claim 1 is characterized in that the additive of regulating pH in the step (1) is selected from sodium hydrogen phosphate, SODIUM PHOSPHATE, MONOBASIC, sodium phosphate, yellow soda ash, sodium bicarbonate or Potassium Hydrogen Phthalate.
4. the cycloaliphatic epoxy resin of the described method preparation of claim 1 is characterized in that the principal product compound more than 90wt%, and epoxy equivalent (weight) is between 120～140.
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| CN200810139433XA CN101671318B (en) | 2008-09-10 | 2008-09-10 | Cycloaliphatic epoxy resin and preparation method thereof |
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| CN200810139433XA CN101671318B (en) | 2008-09-10 | 2008-09-10 | Cycloaliphatic epoxy resin and preparation method thereof |
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| CN101671318A CN101671318A (en) | 2010-03-17 |
| CN101671318B true CN101671318B (en) | 2011-07-20 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101943401B1 (en) * | 2010-08-11 | 2019-01-29 | 닛산 가가쿠 가부시키가이샤 | Liquid crystal orientation material |
| CN104327250A (en) * | 2014-09-27 | 2015-02-04 | 安徽华甬新材料有限公司 | Preparation method of alicyclic resin 4221 (ERL-4221) |
| CN111587267B (en) * | 2018-01-12 | 2023-11-07 | 株式会社大赛璐 | Alicyclic epoxy compound product |
| CN110591054B (en) * | 2019-09-17 | 2021-05-18 | 江苏泰特尔新材料科技股份有限公司 | Epoxide with low total chlorine content and no heavy metal residue and synthesis process thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4849532A (en) * | 1985-08-05 | 1989-07-18 | Degussa Aktiengesellschaft | Process for the preparation of a cycloaliphatic diepoxide |
| CN1880310A (en) * | 2005-06-17 | 2006-12-20 | 中国科学院大连化学物理研究所 | Method for preparing epoxy cyclohexane and cyclohexane |
| CN101205221A (en) * | 2006-12-22 | 2008-06-25 | 中国科学院大连化学物理研究所 | Method for preparing p-vinyl epoxy cyclohexane |
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2008
- 2008-09-10 CN CN200810139433XA patent/CN101671318B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4849532A (en) * | 1985-08-05 | 1989-07-18 | Degussa Aktiengesellschaft | Process for the preparation of a cycloaliphatic diepoxide |
| CN1880310A (en) * | 2005-06-17 | 2006-12-20 | 中国科学院大连化学物理研究所 | Method for preparing epoxy cyclohexane and cyclohexane |
| CN101205221A (en) * | 2006-12-22 | 2008-06-25 | 中国科学院大连化学物理研究所 | Method for preparing p-vinyl epoxy cyclohexane |
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