CN101143919A - Method for synthesizing alicyclic epoxy resin by catalyzing unsaturated alicyclic compound - Google Patents
Method for synthesizing alicyclic epoxy resin by catalyzing unsaturated alicyclic compound Download PDFInfo
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- CN101143919A CN101143919A CNA2007100127178A CN200710012717A CN101143919A CN 101143919 A CN101143919 A CN 101143919A CN A2007100127178 A CNA2007100127178 A CN A2007100127178A CN 200710012717 A CN200710012717 A CN 200710012717A CN 101143919 A CN101143919 A CN 101143919A
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Abstract
The invention relates to a method by which an unsaturated alicyclic compound is catalyzed to synthesize alicyclic epoxy resin. Metal compound with an oxygenation effect is used as catalyst (I), hydrogen peroxide or alkyl hydrogen peroxide is used as oxygen source, and in organic solution, the unsaturated alicyclic compound is selectively catalyzed to synthesize alicyclic epoxy resin by epoxidation; the reaction temperature is 0 to ninety DEG C; reaction lasts over twenty hours; the molar ratio between the C=C in the unsaturated alicyclic compound and the hydrogen peroxide or the alkyl hydrogen peroxide is 0.01 to 20:1; the catalyst accounts for zero point zero five to ten percent of the molar dosage of the unsaturated alicyclic compound. The reaction system of the invention has the advatages of high selectivity on alicyclic epoxy resin, environment protection and low cost, and moreover, the invention can meet the requirements of technical economy and is applied to the large-scale industrialized production of alicyclic epoxy resin.
Description
Technical field
The present invention relates to the synthetic of cycloaliphatic epoxy resin, the method for the synthetic cycloaliphatic epoxy resin of specifically a kind of catalysis unsaturated cycloaliphatic compound epoxidation.
Background technology
The class epoxy compounds that cycloaliphatic epoxy resin normally obtains with the corresponding unsaturated cycloaliphatic compound of peroxidation organic acid oxidation, its constructional feature is to contain alicyclic ring, epoxy group(ing) directly is connected on the alicyclic ring.This resinoid has arc resistance and excellent electrical properties such as high volume resistance and surface resistivity, and suitable to the insulating material in the hyperbaric environment.Simultaneously strong, ultraviolet resistance of its cured article degree of crosslinking height of this resinoid, good heat resistance, weathering resistance and electron-irradiation resisting and be suitable for outdoor use are done the anti-ultraviolet paint of high-temperature resistance adhesive and long-term outdoor use.As cycloaliphatic epoxy resin ERL-4221 is to adopt the acid system synthetic by U.S. associating C.-Chem AG [US 2,716,123].Also have other cycloaliphatic epoxy resins such as following table:
Summary of the invention
The object of the present invention is to provide a kind of method of synthesizing alicyclic epoxy resin by catalyzing unsaturated alicyclic compound, this method reaction system is simple, and post-reaction treatment is easy, product is single epoxy compounds, production cost is low, and the no hidden danger of safety is relatively more friendly to environment.
For achieving the above object, the present invention adopts technical scheme to be:
A kind of method of synthesizing alicyclic epoxy resin by catalyzing unsaturated alicyclic compound,
With the metallic compound with oxygenizement is catalyzer (I), is oxygen source with hydrogen peroxide or alkyl peroxide, in organic solvent, and unsaturated cycloaliphatic compound selective ground catalysis epoxidation synthesis of alicyclic epoxy resin; Temperature of reaction is at 0 to 100 ℃; Reaction is more than 20 minutes;
Wherein the mol ratio of the C=C in the unsaturated cycloaliphatic compound and hydrogen peroxide or alkyl peroxide is 0.01-20: 1; Catalyzer (I) is the 0.05-10% of unsaturated cycloaliphatic compound mole dosage;
Catalyzer (I) is the heteropllyacids compound Q
mH
nXM
pO
4+3p, M is a central metal atom, can be Mo, W or V; Q is a cationic moiety, can use [R
1R
2R
3R
4N
+] expression, wherein R
1, R
2, R
3, R
4Can be H-, C
1-C
20The alkyl of straight or branched, cycloalkyl, benzyl, or R
1R
2R
3N is pyridine and homologue thereof; X is a heteroatoms, can be P or As; 2≤m≤7, n=0 or 1; P=2,3 or 4.
Its catalyst for oxidation reaction that adopts is open in Chinese patent [00123339.4], it shows the characteristics of homogeneous catalyst fully in reaction process, the catalytic activity height, unsaturated cycloaliphatic conversion of compounds rate is greater than 85%, and the selectivity of epoxidation reaction is greater than 90%.
This class catalyst themselves is insoluble in the reaction medium, but under the effect of hydrogen peroxide, can form the active specy that dissolves in the reaction medium, so with the unsaturated cycloaliphatic compound effects, make its optionally homogeneous catalysis epoxidation reaction; The unsaturated cycloaliphatic compound ratio transformation is greater than 95%, and greater than 90%, catalyzer embodies the characteristics of homogeneous catalyst to its corresponding epoxy compounds fully in reaction process to the selectivity of unsaturated cycloaliphatic compound.
Described hydrogen peroxide (H
2O
2) can be the hydrogen peroxide of generated in-situ hydrogen peroxide or the direct weight concentration 5-90% that drops into; Described alkyl peroxide (ROOH) is tertbutyl peroxide, ethylbenzene hydroperoxide, isopropyl benzene hydroperoxide or cyclohexane aqueous hydrogen peroxide solution.
Described generated in-situ hydrogen peroxide is meant the hydrogen peroxide that produces by the oxidizing reaction original position, utilizes the oxygen acceptor H with reversible oxidation, reducing property
2A is a reductive agent, under the condition that reaction medium exists, and in-situ hydrogen peroxide under air effect, the product A after the reductive agent oxidation can reset into original texture through catalyzer (II) shortening, and recirculation is used;
The used reductive agent that can be recycled is to contain oxygen or nitrogenous compound in the epoxidation reaction, and wherein A is that quinones comprises benzoquinones class, naphthoquinones class or anthraquinone class, azophenlyene class or azo compound;
Used catalyzer (II) is to contain Ni, Pt, Pd, Cr, Rh, Ru transistion metal compound;
Described reaction medium is alkane solvents straight-chain paraffin, branched paraffin or naphthenic hydrocarbon; Aromatic hydrocarbon solvent benzene, toluene, ethylbenzene or have substituent alkylbenzene; Halogenated hydrocarbon solvent halogenated alkane or halogenated aryl hydrocarbon; Esters solvent fatty acid ester, aromatic esters or trialkylphosphate; Alcoholic solvent methyl alcohol, ethanol or the trimethyl carbinol; Employed reaction medium can be a single solvent, also can be the solvent of above-mentioned several solvent compositions.
Oxygen source used in the present invention, oxygen source can all consume by epoxidation reaction; If there is superfluous oxygen source after the epoxidation reaction, unnecessary oxygen source can all consume oxygen source by the solution that rising system temperature or adding have a reductibility.
Described by the rising system temperature to consume superfluous oxygen source, temperature is between 60-100 ℃.Temperature is between 70-90 ℃ preferably; The solution of described reductibility is Na
2SO
3, Na
2S
2O
3Or NaHSO
3The aqueous solution.
Described unsaturated cycloaliphatic compound is 3,4-epoxy group(ing) heptanaphthenic acid-3,4-epoxy group(ing) cyclohexyl, 3,4-epoxy group(ing)-6-methyl cyclohexane formic acid-3,4-epoxy group(ing)-6-methyl cyclohexane ester, dimethyl are for vinyl cyclohexene dioxide, vinyl cyclohexene dioxide or bicyclopentadiene dioxide.Reaction conditions gentleness in epoxidation reaction, temperature of reaction is between 0 to 100 ℃.Temperature of reaction is between 30 to 80 ℃ preferably.
Epoxidization reaction process of the present invention is simple, can high-level efficiency, highly selective prepares cycloaliphatic epoxy resin.Just unsaturated cycloaliphatic compound, hydrogen peroxide or air, hydrogen and the little amount of catalyst that are consumed in the whole process, reaction system is simple, low production cost, product is single epoxy compounds, do not have joint product, aftertreatment is simple, and is relatively more friendly to environment, can satisfy the requirement of Technological Economy, be a new way that is suitable for the large-scale commercial production cycloaliphatic epoxy resin.
Embodiment
Give further instruction below by example to the present invention.
Following catalysts is open in Chinese patent [00123339.4], and its preparation process is carried out with reference to CN00123339.4;
The dicyclopentadiene diepoxide is made through epoxidation reaction by dicyclopentadiene, be white solid, the material thermal resistance made from it is good, hardness is high and good weathering resistance and electrical insulation capability are arranged, and can be used for the adhesive glue of casting glue, structural part tackiness agent, glass reinforced plastic and the stratified plastics etc. of high temperature resistant mutual inductor and micromotor.Domestic can only small serial production because of process technology limit, cost an arm and a leg.Along with the development of petrochemical complex, dicyclopentadiene can obtain by separating in petroleum cracking product C 5 cuts, and the China's oil reserves are abundant, possess the condition of developing significantly.
Reaction formula is as follows:
The epoxidation of embodiment 1 dicyclopentadiene
The 40mmol dicyclopentadiene is dissolved in 40mL and mixes in the trimethylbenzene, adds 27.5% aqueous hydrogen peroxide solution (w/w) of 90mmol, the catalyzer [(C of 0.2mmol
2H
5)
3NCH
2Ph]
2HA
sMo
2O
10Under 65 ℃, react after 1 hour, the transformation efficiency of dicyclopentadiene is 98.3%, and the selectivity of bicyclopentadiene dioxide is 96.3%.The reaction back adds Na
2S
2O
3The aqueous solution is removed unnecessary hydrogen peroxide, and the solvent that evaporates in the organic layer obtains the bicyclopentadiene dioxide crystal.Resulting solvent distillation adds oxide catalyst, dicyclopentadiene and hydrogen peroxide again, the same circulating reaction.
Alicyclic diepoxides ERL-4221 is a U.S. combinating carbide company development product, is a kind of Resins, epoxy that special purpose is arranged, and molecular formula is
It is by intermediate
At present, the domestic industrial installation of also not producing alicyclic diepoxides ERL-4221, U.S. associating C.-Chem AG [US 2,716,123] adopted acid system, had potential safety hazard owing to cross acid system, and commercial run is difficult to control.In addition, use the chlorohydrination synthesizing epoxy compound, chlorohydrination itself is with regard to there being a lot of urgency problem to be solved, and is serious as equipment corrosion, the production process complexity, and environmental pollution is serious etc.
Reaction formula is as follows:
R＝H，alkyl
The epoxidation of embodiment 2 unsaturated cycloaliphatic compd As (3-tetrahydrobenzene methyl, 3-cyclohexenecarboxylic acid ester)
The 80mmol raw material A is dissolved in 40mL and mixes in the trimethylbenzene, adds 30% aqueous hydrogen peroxide solution (w/w) of 180mmol, the catalyzer [(C of 0.4mmol
2H
5)
3NCH
2Ph]
2HAsMo
2O
10Under 65 ℃, react after 1 hour, the transformation efficiency of raw material A is 90.0%, and the selectivity of epoxy product is 95.7%.Add Na
2S
2O
3The aqueous solution.Remove unnecessary hydrogen peroxide, distill out unreacted raw material polyenic compounds A and epoxy product in the organic layer.
The epoxidation of embodiment 3 unsaturated cycloaliphatic compd As (3-tetrahydrobenzene methyl, 3-cyclohexenecarboxylic acid ester)
2 methyl naphthoquinone 40mmol is dissolved in the mixed solvent of 30mL dimethyl phthalate and 30mL diisobutyl carbinol(DIBC), adds 4% 5%Pd-C (W/W) catalyzer, 6atm hydrogen, 45 ℃ were reacted 6 hours, and made the 2 methyl naphthoquinone hydrogenation reach 50%.Stop hydrogenation, cross and filter out the Pd-C catalyzer.In filtrate, add raw material polyenic compounds A2mmol, catalyzer (NH then
4)
2HAsW
2O
100.09mmol, at 1atm O
2Down, 65 ℃ were reacted 2 hours, and the transformation efficiency of raw material A is 91.0%, and the selectivity of epoxy product is 93.5%.Distill out unreacted raw material A and epoxy product.
The epoxidation of embodiment 4 unsaturated cycloaliphatic compd As (3-tetrahydrobenzene methyl, 3-cyclohexenecarboxylic acid ester)
0.2mol raw material A is dissolved in the 100mL chloroform, adds catalyzer [μ-C of 0.8mmol
5H
5NC
12H
25]
3PW
4O
16, drip 30% aqueous hydrogen peroxide solution (w/w) of 0.5mol, under 60 ℃, react after 3 hours, the transformation efficiency of raw material A is 95.0%, the selectivity of epoxy product is 95.7%.Add Na
2S
2O
3The aqueous solution.Remove unnecessary hydrogen peroxide, distill out unreacted raw material polyenic compounds A and epoxy product in the organic layer.
Above-mentioned example shows, the catalyst for oxidation reaction that is provided in the patent of invention [00123339.4] is provided, in suitable reaction medium, according to condition provided by the present invention, can high-level efficiency, highly selective generates cycloaliphatic epoxy resin with raw material unsaturated cycloaliphatic compound for catalysis epoxidation.Oxygen source can be the hydrogen peroxide (H that directly drops into
2O
2); Also can produce, utilize oxygen acceptor H with reversible oxidation, reducing property by the oxidizing reaction original position
2A is a reductive agent, in-situ hydrogen peroxide under air effect, and the product A after the reductive agent oxidation is restored through simple shortening, can be recycled.Catalyst dissolution embodies the characteristics and the effect of homogeneous catalyst fully in reaction system in reaction process, thereby the reaction conditions gentleness.In total reaction process, just unsaturated cycloaliphatic compound, hydrogen peroxide or air, hydrogen and the little amount of catalyst that are consumed, low production cost, product is single epoxy compounds, does not have joint product, and is relatively more friendly to environment.Reaction process is simple, can satisfy the requirement of Technological Economy, is the new way that is fit to the large-scale commercial production epoxy compounds.
Claims (9)
1. the method for a synthesizing alicyclic epoxy resin by catalyzing unsaturated alicyclic compound is characterized in that:
With the metallic compound with oxygenizement is catalyzer (I), is oxygen source with hydrogen peroxide or alkyl peroxide, in organic solvent, and unsaturated cycloaliphatic compound selective ground catalysis epoxidation synthesis of alicyclic epoxy resin; Temperature of reaction is at 0 to 90 ℃; Reaction is more than 20 minutes;
Wherein the mol ratio of the C=C in the unsaturated cycloaliphatic compound and hydrogen peroxide or alkyl peroxide is 0.01-20: 1; Catalyzer (I) is the 1-15wt% of unsaturated cycloaliphatic compound amount;
Catalyzer (I) is the heteropllyacids compound Q
mH
nXM
pO
4+3p, M is a central metal atom, can be Mo, W or V; Q is a cationic moiety, can use [R
1R
2R
3R
4N
+] expression, wherein R
1, R
2, R
3, R
4Can be H-, C
1-C
20The alkyl of straight or branched, cycloalkyl, benzyl, or R
1R
2R
3N is pyridine and homologue thereof; X is a heteroatoms, can be P or As; 2≤m≤7, n=0 or 1; P=2,3 or 4.
2. according to the described method of claim 1, it is characterized in that:
Described hydrogen peroxide (H
2O
2) can be the hydrogen peroxide of generated in-situ hydrogen peroxide or weight concentration 2-90%; Described alkyl peroxide (ROOH) is tertbutyl peroxide, ethylbenzene hydroperoxide, isopropyl benzene hydroperoxide or cyclohexane superoxol.
3. according to the described method of claim 2, it is characterized in that:
Described generated in-situ hydrogen peroxide is meant the hydrogen peroxide that produces by the oxidizing reaction original position, utilizes the oxygen acceptor H with reversible oxidation, reducing property
2A is a reductive agent, under the condition that reaction medium exists, and in-situ hydrogen peroxide under air effect, the product A after the reductive agent oxidation can reset into original texture through catalyzer (II) shortening, and recirculation is used;
The used reductive agent that can be recycled is to contain oxygen or nitrogenous compound in the epoxidation reaction, and wherein A is benzoquinones class in the quinones, naphthoquinones class or anthraquinone class, azophenlyene class or azo compound.
4. according to the described method of claim 3, it is characterized in that: used catalyzer (II) is to contain Ni, Pt, Pd, Cr, Rh and/or Ru transistion metal compound.
5. according to the described method of claim 3, it is characterized in that:
Described reaction medium is alkane solvents straight-chain paraffin, branched paraffin or naphthenic hydrocarbon; Aromatic hydrocarbon solvent benzene, toluene, ethylbenzene or dimethylbenzene; Halogenated hydrocarbon solvent halogenated alkane or halogenated aryl hydrocarbon; Esters solvent fatty acid ester, aromatic esters or trialkylphosphate; Alcoholic solvent methyl alcohol, ethanol or the trimethyl carbinol; Employed reaction medium can be above-mentioned single solvent, also can be the mixed solvent of above-mentioned more than one solvent compositions.
6. according to the described method of claim 1, it is characterized in that: oxygen source used in the present invention, oxygen source can all consume by epoxidation reaction; If there is superfluous oxygen source after the epoxidation reaction, unnecessary oxygen source can all consume oxygen source by the solution that rising system temperature or adding have a reductibility.
7. according to the described method of claim 6, it is characterized in that: described by the rising system temperature to consume superfluous oxygen source, temperature is between 60-100 ℃.
8. according to the described method of claim 6, it is characterized in that: the solution of described reductibility is Na
2SO
3, Na
2S
2O
3Or NaHSO
3The aqueous solution.
9. according to the described method of claim 1, it is characterized in that: described unsaturated cycloaliphatic compound is a 7-oxabicyclo [4,1,0] heptane-3-carboxylic acid, 7-oxabicyclo [4,1,0] heptan-3-methyl ester, 3,4-epoxy group(ing)-6-methyl cyclohexane formic acid-3 ', 4 '-epoxy group(ing)-6 '-methyl cyclohexane ester, dimethyl are for vinyl cyclohexene dioxide, vinyl cyclohexene dioxide or bicyclopentadiene dioxide.
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|---|---|---|---|
| CNA2007100127178A CN101143919A (en) | 2007-09-05 | 2007-09-05 | Method for synthesizing alicyclic epoxy resin by catalyzing unsaturated alicyclic compound |
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|---|---|---|---|
| CNA2007100127178A CN101143919A (en) | 2007-09-05 | 2007-09-05 | Method for synthesizing alicyclic epoxy resin by catalyzing unsaturated alicyclic compound |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009088087A1 (en) * | 2008-01-10 | 2009-07-16 | Nipponkayaku Kabushikikaisha | Epoxidation catalyst, process for production of epoxidation catalyst, process for production of epoxy compounds, curable resin compositions, and products of curing of the compositions |
| JP2010018538A (en) * | 2008-07-10 | 2010-01-28 | Nippon Kayaku Co Ltd | Method for producing epoxy compound |
| JP2010070481A (en) * | 2008-09-18 | 2010-04-02 | Nippon Kayaku Co Ltd | Method for producing epoxy compound |
| JP2010070480A (en) * | 2008-09-18 | 2010-04-02 | Nippon Kayaku Co Ltd | Method for producing epoxy compound |
| JP2010090032A (en) * | 2008-10-03 | 2010-04-22 | Nippon Kayaku Co Ltd | Method of producing epoxy compound |
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| CN104162453A (en) * | 2014-07-17 | 2014-11-26 | 北京理工大学 | Polyacid catalyst wrapped by cadmium-based polypyridine macro ring and preparation method thereof |
| 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) |
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| CN108003328A (en) * | 2017-11-11 | 2018-05-08 | 江苏泰特尔新材料科技有限公司 | A kind of heat resistant type cycloaliphatic epoxy resin solidfied material and preparation method thereof |
| CN111100139A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Preparation method of dicyclopentadiene dioxide based on modified nano MgO supported heteropoly acid type catalyst |
| CN111100140A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Method for catalytic oxidation of dicyclopentadiene by solid acid |
| CN111100137A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Method for catalytic oxidation of dicyclopentadiene by supported heteropoly acid |
| CN111100138A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Preparation method of dicyclopentadiene dioxide based on modified nano-alumina-supported heteropoly acid type compound catalyst |
| CN111100136A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Preparation method of dicyclopentadiene dioxide |
-
2007
- 2007-09-05 CN CNA2007100127178A patent/CN101143919A/en active Pending
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| WO2009088087A1 (en) * | 2008-01-10 | 2009-07-16 | Nipponkayaku Kabushikikaisha | Epoxidation catalyst, process for production of epoxidation catalyst, process for production of epoxy compounds, curable resin compositions, and products of curing of the compositions |
| CN101909748B (en) * | 2008-01-10 | 2014-03-12 | 日本化药株式会社 | Epoxidation catalyst, process for production of epoxidation catalyst, process for production of epoxy compounds, curable resin compositions, and products of curing of compositions |
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| JP2010070481A (en) * | 2008-09-18 | 2010-04-02 | Nippon Kayaku Co Ltd | Method for producing epoxy compound |
| JP2010070480A (en) * | 2008-09-18 | 2010-04-02 | Nippon Kayaku Co Ltd | Method for producing epoxy compound |
| JP2010090032A (en) * | 2008-10-03 | 2010-04-22 | Nippon Kayaku Co Ltd | Method of producing epoxy compound |
| CN102858757B (en) * | 2010-03-18 | 2015-07-22 | 陶氏环球技术有限责任公司 | Process for preparing divinylarene dioxides |
| CN102858757A (en) * | 2010-03-18 | 2013-01-02 | 陶氏环球技术有限责任公司 | Process for preparing divinylarene dioxides |
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| 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) |
| CN106916414A (en) * | 2015-12-25 | 2017-07-04 | 广东生益科技股份有限公司 | A kind of compositions of thermosetting resin, the prepreg containing it, metal-clad laminate and printed circuit board |
| CN106916414B (en) * | 2015-12-25 | 2019-01-22 | 广东生益科技股份有限公司 | A kind of compositions of thermosetting resin, prepreg, metal-clad laminate and printed circuit board containing it |
| CN108003328A (en) * | 2017-11-11 | 2018-05-08 | 江苏泰特尔新材料科技有限公司 | A kind of heat resistant type cycloaliphatic epoxy resin solidfied material and preparation method thereof |
| CN108003328B (en) * | 2017-11-11 | 2020-04-24 | 江苏泰特尔新材料科技有限公司 | Heat-resistant alicyclic epoxy resin cured material and preparation method thereof |
| CN111100139A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Preparation method of dicyclopentadiene dioxide based on modified nano MgO supported heteropoly acid type catalyst |
| CN111100140A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Method for catalytic oxidation of dicyclopentadiene by solid acid |
| CN111100137A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Method for catalytic oxidation of dicyclopentadiene by supported heteropoly acid |
| CN111100138A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Preparation method of dicyclopentadiene dioxide based on modified nano-alumina-supported heteropoly acid type compound catalyst |
| CN111100136A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Preparation method of dicyclopentadiene dioxide |
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