CN103172777A - Method for preparing polybutadiene epoxy resin - Google Patents

Method for preparing polybutadiene epoxy resin Download PDF

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CN103172777A
CN103172777A CN2011104358657A CN201110435865A CN103172777A CN 103172777 A CN103172777 A CN 103172777A CN 2011104358657 A CN2011104358657 A CN 2011104358657A CN 201110435865 A CN201110435865 A CN 201110435865A CN 103172777 A CN103172777 A CN 103172777A
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reaction
polyhutadiene
polybutadiene
ionic liquid
hydrogen peroxide
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高爽
吕迎
李军
张恒耘
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Abstract

The invention discloses a novel method for preparing polybutadiene epoxy resin through direct catalysis and epoxidation with hydrogen peroxide, and belongs to the technical field of polymer resin preparation. The method is characterized in that phosphotungstic heteropoly acid quaternary ammonium salt is served as a catalytic agent, an acid ionic liquid is served as a reaction medium, and the catalytic agent and the reaction medium can be recycled together through simple separation. The epoxide number of cis-1, 4-polybutadiene with low molecular weight is about 0.45, and the epoxide number of hydroxyl-terminated polybutadiene is about 0.42. Compared with the existing method, the method has the advantages of moderate oxidizability, simple reaction operation, high selectivity, environment friendliness, low cost, small potential safety hazards and the like; and the method can satisfy technical and economic requirements and is a novel method for synthesizing the polybutadiene epoxy resin.

Description

A kind of method for preparing polybutadiene epoxy resin
Technical field
The invention belongs to the macromolecule resin preparing technical field, particularly provide a class polyhutadiene to be produced the new reaction system of POLYBUTADIENE EPOXY RESIN with the phosphorus heteropoly tungstic acid catalyzer catalysis epoxidation.
Background technology
Epoxidized polybutadiene is the important resin of a class, can be widely used in the Chemicals such as synthetic paint, ion exchange resin, sizing agent, fire retardant by modification.Along with continually developing of its purposes, also will grow with each passing day to its demand.At present, produce the operational path of epoxidized polybutadiene, all adopted traditionally acid system, but owing to there being intermediate reaction product acid in this system, therefore can produce side reaction, and peroxy acid self is expensive, has simultaneously potential safety hazard, the problems such as equipment corrosion make it be limited in industrial application.
Also there is in the recent period report to make the oxygenant epoxidized polybutadiene with ketone peroxide, because generated in-situ ketone peroxide concentration is low, can produce a large amount of salt in reaction process, bring very large trouble to post-reaction treatment, thereby make it be difficult to realize in scale production.Gerbase etc. have reported with Vo (acac) 2As catalyzer, be organic oxygen source but this system adopts tertbutyl peroxide (TBHP), preparation cost is high and be unfavorable for environmental protection.The present invention is take quaternary ammonium salt phosphor-tungstic heteropoly acid as catalyzer, hydrogen peroxide is oxygen source, take acidic ionic liquid as reaction medium, successful catalysis the liquid polybutadiene epoxidation, and catalyzer and reaction medium ionic liquid can repeatedly recycle jointly, maintain very high selectivity and oxirane value preferably.Therefore, if use our this new reaction system instead, come the catalysis epoxidation polyhutadiene to clean green hydrogen peroxide as oxygen source, both can simplify reaction process, environmental contamination reduction, significant to realizing cleaner production again.
Summary of the invention
The object of the present invention is to provide a kind of highly selective, the highly active catalytic polyhutadiene prepares the method for POLYBUTADIENE EPOXY RESIN.
It is the catalyst epoxidized polybutadiene that the present invention has used a series of quaternary ammonium salt phosphor-tungstic heteropoly acids, take acidic ionic liquid as reaction medium, the hydrogen peroxide that has adopted green cleaning is oxygen source, and the epoxidation of several dissimilar polyhutadiene of catalysis epoxidation, this catalystic converter system has good selectivity and activity, and catalyzer and ionic liquid can recycle jointly.Lower molecular weight cis-1, the oxirane value of 4-polyhutadiene are 0.45 left and right, and the oxirane value of hydroxy-terminated polybutadienes is 0.42 left and right.
Temperature of reaction is 46 hours at 80～125 ℃, reaction times.
Reaction medium is: acidic ionic liquid comprises: quaternary ammonium salt, or imidazole salt ionic liquid.Organic solvent comprises: methylene dichloride, toluene, hexanaphthene.Reaction medium is acidic ion liquid or acidic ion liquid and organic solvent mixed solution.
Catalyzer is: described catalyzer is the phosphorus heteropoly tungstic acid compounds of mentioning in patent ZL 01123653.1, at least a in dodecyl Trimethylamine phospho heteropoly tungstate, cetyl trimethyl amine phospho heteropoly tungstate, Octadecyl trimethylamine phospho heteropoly tungstate or two octadecyl dimethyl amine phospho heteropoly tungstate, catalyst molecule forms Q mH nPW xO y, Q is the alkyl cationic moiety, 1≤m≤7,1≤x≤12,0≤n≤Isosorbide-5-Nitrae≤y≤25.
Described raw material comprises: low-molecular-weight cis-1,4-polyhutadiene, low-molecular-weight hydroxy-terminated polybutadienes, the cis-1 of high molecular, 4-polyhutadiene.The preferential less hydroxy-terminated polybutadienes of low-molecular-weight viscosity of selecting of polyhutadiene in aforesaid method.
Described oxygen source comprises: concentration is the aqueous hydrogen peroxide solution of 20%-50% left and right.
Polyhutadiene and hydrogen peroxide mol ratio are 1: 1-1: 1.5.
The mol ratio of polyhutadiene and quaternary ammonium salt phosphor-tungstic heteropoly acid catalyzer is 250: 1-25: 1.
Compare with prior art, the present invention has following useful result:
1. epoxidization reaction process of the present invention is simple, can high reactivity, highly selective catalysis polyhutadiene epoxidation prepares the polyhutadiene epoxy compounds, and in the method, catalyst recovery is easy, and catalystic converter system can be recycled.
2. just polyhutadiene, the hydrogen peroxide that consume in whole process, with low cost, in the method, catalyst recovery is easy, aftertreatment is simple, more friendly to environment, and product can satisfy industrial technical indicator, is a new way that is suitable for the industrial production POLYBUTADIENE EPOXY RESIN.
3. the advantages such as the method is compared with existing method, has the oxidation susceptibility gentleness, and operation is simple, and is more friendly to environment, inexpensive, and potential safety hazard is less; Make it have very large potentiality in industrial production.
Embodiment
Embodiment one:
0.02mo l (two key) hydroxy-terminated polybutadienes (M=1500～2100) is dissolved in acidic ionic liquid (N-(2-(2-methoxy ethoxy) ethyl-N of 100ml, N-dimethyl-2-(2-(octyloxy) oxyethyl group) methylsulphonic acid ammonium) in, add 0.1mmol catalyzer ([π-C 5H 5NC 16H 33] 3PW 4O 16), the aqueous hydrogen peroxide solution of 1.2 molar equivalents (hydrogen peroxide mass concentration 50%) (with respect to the two keys of polyhutadiene), temperature of reaction is 110 ℃, the reaction times is 5h.Above-mentioned reaction formula is as follows:
Figure BDA0000123786810000021
Reaction product by 1H-NMR, 13C-NMR and FT-IR detect and analyze, and the oxirane value of hydroxy-terminated polybutadienes is 0.42 left and right, and side reaction is less, and the conclusion under other systems, epoxidation activity: cis-1,4-＞trans-1,4-＞1,2-have equally also been verified in experiment.
After reaction, at room temperature, the reaction system layering, the reaction product natural separation, ionic liquid and catalyzer bonding in reaction process, catalyzer is not separated out in the ion liquid layer, secondary response under can participating in ionic liquid is common.
Embodiment two:
0.06mol (two key) hydroxy-terminated polybutadienes (M=1500～2100) is dissolved in acidic ionic liquid N-(2-(2-methoxy ethoxy) ethyl-N of 30ml, N-dimethyl-2-(2-(octyloxy) oxyethyl group) methylsulphonic acid ammonium) and in 20ml hexanaphthene mixed solution, add 0.2mmol catalyzer ([π-C 5H 5NC 16H 33] 3PW 4O 16), the aqueous hydrogen peroxide solution of 1.2 molar equivalents (hydrogen peroxide mass concentration 30%) (with respect to the two keys of polyhutadiene), temperature of reaction is 120 ℃, the reaction times is 5h.Above-mentioned reaction formula is as follows:
Figure BDA0000123786810000031
Reaction product by 1H-NMR, 13C-NMR and FT-IR detect and analyze, and the oxirane value of hydroxy-terminated polybutadienes is 0.43 left and right, and side reaction is less, and the conclusion under other systems, epoxidation activity: cis-1,4-＞trans-1,4-＞1,2-have equally also been verified in experiment.
Embodiment three:
0.1mol (two key) hydroxy-terminated polybutadienes (M=1500～2100) is dissolved in acidic ionic liquid N-(2-(2-methoxy ethoxy) ethyl-N of 80ml, N-dimethyl-2-(2-(octyloxy) oxyethyl group) Methylimidazole chlorine) and in 10ml methylene dichloride mixed solution, add 0.5mmo l catalyzer ([π-C 5H 5NC 16H 33] 3PW 4O 16), the aqueous hydrogen peroxide solution of 1.2 molar equivalents (hydrogen peroxide mass concentration 25%) (with respect to the two keys of polyhutadiene), temperature of reaction is 100 ℃, the reaction times is 5h.Above-mentioned reaction formula is as follows:
Figure BDA0000123786810000032
Reaction product by 1H-NMR, 13C-NMR and FT-IR detect and analyze, and the oxirane value of hydroxy-terminated polybutadienes is 0.43 left and right, and side reaction is less, and the conclusion under other systems, epoxidation activity: cis-1,4-＞trans-1,4-＞1,2-have equally also been verified in experiment.
Embodiment four:
With 0.02mol (two key) cis-1,4-polyhutadiene (M=2000, cis 86%, trans 12%, 1,2-:2%) be dissolved in the acidic ionic liquid N-(2-(2-methoxy ethoxy) ethyl-N, N-dimethyl-2-(2-(octyloxy) oxyethyl group) Methylimidazole fluorine) and 10ml toluene mixture liquid of 30ml, add catalyzer ([π-C of 0.1mmol 5H 5NC 16H 33] 3PW 4O 16), the aqueous hydrogen peroxide solution of 1.5 molar equivalents (hydrogen peroxide mass concentration 50%) (with respect to the two keys of polyhutadiene), temperature of reaction is 95 ℃, the reaction times is 5h.Above-mentioned reaction formula is as follows:
Figure BDA0000123786810000033
Reaction product by 1H-NMR, 13C-NMR and FT-IR detect and analyze, lower molecular weight cis-1, and the oxirane value of 4-polyhutadiene is 0.45, and side reaction is less, and the conclusion under other systems, epoxidation activity: cis-1,4-＞trans-1,4-＞1,2-have equally also been verified in experiment.
Embodiment five,
With 0.06mol (two key) cis-1,4-polyhutadiene (M=2000, cis 86%, trans 12%, 1,2-:2%) be dissolved in the acidic ionic liquid N-(2-(2-methoxy ethoxy) ethyl-N, N-dimethyl-2-(2-(octyloxy) oxyethyl group) Methylimidazole chlorine) of 20ml, add catalyzer ([π-C of 0.3mmol 5H 5NC 16H 33] 3PW 4O 16), the aqueous hydrogen peroxide solution of 1.5 molar equivalents (hydrogen peroxide mass concentration 50%) (with respect to the two keys of polyhutadiene), temperature of reaction is 120 ℃, the reaction times is 5h.Above-mentioned reaction formula is as follows:
Figure BDA0000123786810000041
Reaction product by 1H-NMR, 13C-NMR and FT-IR detect and analyze, lower molecular weight cis-1, and the oxirane value of 4-polyhutadiene is 0.45, and side reaction is less, and the conclusion under other systems, epoxidation activity: cis-1,4-＞trans-1,4-＞1,2-have equally also been verified in experiment.
Embodiment six:
With 0.1mol (two key) cis-1,4-polyhutadiene (M=2000, cis 86%, trans 12%, 1,2-:2%) be dissolved in the acidic ionic liquid N-(2-(2-methoxy ethoxy) ethyl-N, N-dimethyl-2-(2-(octyloxy) oxyethyl group) methylsulphonic acid ammonium) of 20ml, add catalyzer ([π-C of 0.4mmol 5H 5NC 16H 33] 3PW 4O 16), the aqueous hydrogen peroxide solution of 1.5 molar equivalents (hydrogen peroxide mass concentration 30%) (with respect to the two keys of polyhutadiene), temperature of reaction is 100 ℃, the reaction times is 5h.Above-mentioned reaction formula is as follows:
Figure BDA0000123786810000042
Reaction product by 1H-NMR, 13C-NMR and FT-IR detect and analyze, lower molecular weight cis-1, and the oxirane value of 4-polyhutadiene is 0.45 left and right, and side reaction is less, and the conclusion under other systems, epoxidation activity: cis-1,4-＞trans-1,4-＞1,2-have equally also been verified in experiment.
Embodiment seven:
0.02mol (two key) hydroxy-terminated polybutadienes (M=1500～2100) is dissolved in embodiment one after reaction in the reaction system (100ml) after separated product, the aqueous hydrogen peroxide solution (hydrogen peroxide mass concentration 50%) (with respect to the two keys of polyhutadiene) that adds 1.2 molar equivalents, temperature of reaction is 110 ℃, and the reaction times is 6h.Above-mentioned reaction formula is as follows:
Figure BDA0000123786810000043
Reaction product by 1H-NMR, 13C-NMR and FT-IR detect and analyze, and the oxirane value of hydroxy-terminated polybutadienes is 0.41.

Claims (10)

1. method for preparing polybutadiene epoxy resin, it is characterized in that: take the cleaning hydrogen peroxide as oxygen source, under the quaternary ammonium salt phosphor-tungstic heteropoly acid catalyst action, with acidic ionic liquid, or acidic ionic liquid and organic solvent be reaction medium, and the polyhutadiene catalysis epoxidation prepares POLYBUTADIENE EPOXY RESIN;
Described temperature of reaction is 80～125 ℃, and the reaction times is 4～6 hours.
2. according to the method for preparing polybutadiene claimed in claim 1, it is characterized in that:
Reaction medium is acidic ion liquid or acidic ion liquid and organic solvent mixed solution; In mixed solution, the volume content of organic solvent is less than 20%.
Described acidic ionic liquid comprises: contain N-(2-(2-methoxy ethoxy) ethyl-N, the quaternary ammonium salt of N-dimethyl-2-(2-(octyloxy) oxyethyl group) structure, or imidazole salt ionic liquid.
3. according to the method for preparing polybutadiene claimed in claim 1, it is characterized in that:
Described acidic ionic liquid N-(2-(2-methoxy ethoxy) ethyl-N, N-dimethyl-2-(2-(octyloxy) oxyethyl group) methylsulphonic acid ammonium, N-(2-(2-methoxy ethoxy) ethyl-N, N-dimethyl-2-(2-(octyloxy) oxyethyl group) Methylimidazole chlorine, N-(2-(2-methoxy ethoxy) ethyl-N, a kind of in N-dimethyl-2-(2-(octyloxy) oxyethyl group) Methylimidazole fluorine;
Organic solvent comprises: a kind of in methylene dichloride, toluene, hexanaphthene.
4. according to the method for preparing polybutadiene claimed in claim 1, it is characterized in that: described catalyzer is the phosphorus heteropoly tungstic acid compounds described in patent ZL 01123653.1, at least a in dodecyl Trimethylamine phospho heteropoly tungstate, cetyl trimethyl amine phospho heteropoly tungstate, Octadecyl trimethylamine phospho heteropoly tungstate or two octadecyl dimethyl amine phospho heteropoly tungstate, catalyst molecule forms Q mH nPW xO y, Q is the alkyl cationic moiety, 1≤m≤7,1≤x≤12,0≤n≤Isosorbide-5-Nitrae≤y≤25.
5. according to the method for preparing polybutadiene claimed in claim 1, it is characterized in that: described raw material comprises: the cis-1 of lower molecular weight (molecular weight is 500-2500), the 4-polyhutadiene, the hydroxy-terminated polybutadienes of lower molecular weight (molecular weight is 500-2500), the cis-1 of high molecular (molecular weight is greater than 2500), the 4-polyhutadiene.
6. according to the method for preparing polybutadiene claimed in claim 1, it is characterized in that: polyhutadiene and hydrogen peroxide mol ratio are 1: 1-1: 1.5.
7. according to the described method for preparing polybutadiene of claim 1 or 6, it is characterized in that: the hydrogen peroxide that uses is hydrogen peroxide, the mass concentration of hydrogen peroxide: 25～50%.
8. according to the described method for preparing polybutadiene of claim 1 or 4, it is characterized in that: the mol ratio of polyhutadiene and quaternary ammonium salt phosphor-tungstic heteropoly acid catalyzer is 250: 1-25: 1.
9. according to the described method for preparing polybutadiene of claim 1 or 2, it is characterized in that: during polyhutadiene 0.01-0.1mol, the amount of reaction medium is 10ml-500ml.
10. according to the method for preparing polybutadiene claimed in claim 1, it is characterized in that:
After reaction finished, when cooling to room temperature, reaction system was divided into two-layer naturally: (product is originally as organic liquid for ion liquid layer and organic layer; If add organic solvent, be organic solvent and product mixtures), product is present in organic layer, and product can be separated easily; Bonding occurs in catalyzer and ionic liquid in reaction process, catalyzer becomes a phase with ionic liquid, can recycle more than 2 times.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103977839A (en) * 2014-06-05 2014-08-13 江南大学 Ionic organic metal tungstate epoxidation catalyst and preparation method thereof
CN109467623A (en) * 2018-10-29 2019-03-15 浙江大学 A kind of epoxidizing method of high molecular weight conjugated diene polymer
CN109678991A (en) * 2018-12-10 2019-04-26 浙江大学 A method of epoxidation conjugated diene polymer is directly prepared with conjugated diene polymerisation in solution stoste

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CN101613424A (en) * 2008-06-25 2009-12-30 中国科学院大连化学物理研究所 A kind of method for preparing polybutadiene epoxy resin

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Publication number Priority date Publication date Assignee Title
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CN101613424A (en) * 2008-06-25 2009-12-30 中国科学院大连化学物理研究所 A kind of method for preparing polybutadiene epoxy resin

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103977839A (en) * 2014-06-05 2014-08-13 江南大学 Ionic organic metal tungstate epoxidation catalyst and preparation method thereof
CN103977839B (en) * 2014-06-05 2016-03-30 江南大学 A kind of ionic organic metal tungstates epoxidation catalyst and preparation method thereof
CN109467623A (en) * 2018-10-29 2019-03-15 浙江大学 A kind of epoxidizing method of high molecular weight conjugated diene polymer
CN109678991A (en) * 2018-12-10 2019-04-26 浙江大学 A method of epoxidation conjugated diene polymer is directly prepared with conjugated diene polymerisation in solution stoste
CN109678991B (en) * 2018-12-10 2020-07-14 浙江大学 Method for directly preparing epoxidized conjugated diene polymer from conjugated diene solution polymerization stock solution

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Application publication date: 20130626