CN105693887A - Preparation method of epoxidised polybutadiene - Google Patents
Preparation method of epoxidised polybutadiene Download PDFInfo
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- CN105693887A CN105693887A CN201610131593.4A CN201610131593A CN105693887A CN 105693887 A CN105693887 A CN 105693887A CN 201610131593 A CN201610131593 A CN 201610131593A CN 105693887 A CN105693887 A CN 105693887A
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- polybutadiene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/04—Oxidation
- C08C19/06—Epoxidation
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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
- Y02P20/584—Recycling of catalysts
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Abstract
The invention discloses a preparation method of epoxidised polybutadiene. The preparation method comprises steps as follows: (1) with lipase as a catalyst and ethyl acetate as a reaction aid, polybutadiene and hydrogen peroxide are subjected to an epoxidation reaction; (2) a reaction product is separated, an organic phase is recovered, ethyl acetate is recovered under the reduced pressure, and epoxidised polybutadiene is obtained. According to the method, ethyl acetate serves as a reaction solvent to replace a toxic methylbenzene solvent and also can serve as the reaction aid to improve the epoxidation efficiency, and epoxidised polybutadiene is obtained. The used catalysis process conditions are mild, ring opening and other side reactions are not caused, and the product yield is higher.
Description
Technical field
The preparation method that the present invention relates to a kind of epoxidized polybutadiene。
Background technology
Containing activated double bonds on polybutadiene strand, therefore there is good reactivity, be a kind of important basic chemical industry raw material, be mainly used as synthetic rubber, normal and natural rubber, butadiene-styrene rubber use, it is applied to tire and rubber manufacturing industry。Polybutadiene is because of the characteristic of self full carbochain, and molecular-chain polarr is low, it is difficult to compatible with other polar materials to reach performance synergism。Polybutadiene after epoxidation, not only can be effectively improved molecular polarity, can be compatible with other polar polymer, and the epoxide group introduced is as reactive functional groups, can cross-link further with polyurethane, improve the mechanical property of polyurethane material, bonding strength and thermostability, to meet the specific demand in the fields such as space flight, aviation, machinery, electronics。
The preparation method of current epoxidized polybutadiene mainly has two kinds, and a kind of is the method that pre-formed peroxygen is sour, i.e. previously prepared peroxy acid, again polymer is carried out epoxidation modification, its advantage is that economy, technique are simple, but because peroxy acid has potential explosion hazard, institute's commercial production poor stability in this way；Another kind is the method that original position produces peroxy acid, namely organic acid and hydrogen peroxide are simultaneously introduced reaction system, directly polymer is carried out epoxidation modification, this method safety is high, is the epoxidation modification method mostly adopted at present, but the method makes catalyst with strong acid or organic metal, the seriously corroded of strong acid environmental pollution and equipment, and organic metal has high toxicity, it is easy to remain in the polymer, limit the range of application of synthetic material。Biological enzyme catalyst has reaction condition gentleness, the specificity of catalysis, and enzyme is again the environmentally friendly catalyst of a kind of green。Therefore, biological enzyme catalyst is applied to synthesis of polymer material have broad prospects。1998, Ann[AnnW.P.Jarvie.Enzymaticepoxidationofpolybutadiene.Ch em.Commun., 1998,177-178] the reported first epoxidation reaction of enzyme law catalysis polybutadiene, adopting toluene in this reaction is solvent, causes the problems such as environmental pollution；Simultaneously with acetic acid for auxiliary agent, and have research [Yang Keke etc. the synthesis of epoxy natural rubber and sign. Sichuan University's journal, 2001,38 (1): 82-85] show that adopting acetic acid isopolarity acid is that reaction promoter original position produces peroxy acid, its reaction environment acidity is too strong, causes the generation of the unfavorable factors such as side reaction generation and enzyme deactivation such as open loop。(C with middle polarity8-C16) for reaction promoter time, organic acid easily and polymer form stable emulsion, be not easy to the separation of subsequent products。
Summary of the invention
And reaction condition energy consumption many for existing polybutadiene epoxidation technique side reaction does not correspond with the modernization theme of environmental protection nonhazardous greatly, and the present invention provides the enzyme law catalysis polybutadiene process for epoxidation of a kind of green。In the present invention, with polybutadiene and hydrogen peroxide for raw material, lipase is catalyst, ethyl acetate is reaction promoter, ethyl acetate also serves as solvent simultaneously increases the dissolubility of substrate, catalysis polybutadiene and hydrogen peroxide carry out epoxidation, prepare epoxidized polybutadiene by lipase-catalyzed epoxidation reaction。And, technological reaction product separating technique provided by the invention is simply easily operated。
For achieving the above object, technical scheme is as follows:
The preparation method of a kind of epoxidized polybutadiene, comprises the steps:
(1) with lipase for catalyst, ethyl acetate is as reaction promoter, and polybutadiene and hydrogen peroxide carry out epoxidation reaction；
(2) reaction product isolated, reclaims organic facies, recovered under reduced pressure ethyl acetate, namely obtains epoxidized polybutadiene。
Step (1) described hydrogen peroxide is 0.5～5 times of polybutadiene quality, and described ethyl acetate addition is 5～15 times of polybutadiene quality。Preferably, described hydrogen peroxide is 2～4 times of polybutadiene quality, and described ethyl acetate addition is 6～10 times of polybutadiene quality。
The addition of described lipase is the 1%～10% of polybutadiene quality。
The temperature of described epoxidation reaction is 25 DEG C～60 DEG C, more than stirring condition 400rpm, response time 12～24h。
The temperature of step (1) described epoxidation reaction is 25 DEG C～40 DEG C。
Step (1) described lipase be preferably derived from CandidaantarcticaB immobilized enzyme Novozyme435, derive from Rhizomucormiehei immobilized enzyme LipozymeRMIM, derive from the immobilized enzyme LipozymeTLIM of Thermomyceslanuginosus and derive from the LipaseG " Amano " 50 of Penicilliumcamembertii in one or more mixing。
Step (1) described hydrogen peroxide is at the uniform velocity to be added drop-wise in reaction system。
Step (1) described lipase is derive from one or more the mixture in Rhizopus, aspergillus, mucor, antibacterial, yeast and animal pancreas。
Step (2) described separation process is static layering, reclaims organic facies, and reduce pressure Distillation recovery ethyl acetate, obtains epoxidized polybutadiene。Temperature of charge is below 40 DEG C。
Compared with prior art, the beneficial effects of the present invention is:
(1) present invention carries out epoxidation with lipase-catalyzed polybutadiene, instead of the use of strong acid and organo-metallic catalyst, it is to avoid the problem of environmental pollution and product pollution；Avoid the generation of the side reactions such as open loop simultaneously, simplify the later separation of product, improve the yield of epoxidized polybutadiene。
(2) choose ethyl acetate both as reaction promoter, also serve as reaction dissolvent, not only instead of organic acid reaction auxiliary agent, it also avoid the use of toxic organic solvent (such as toluene etc.) simultaneously；Not only increase the conversion ratio of epoxidized polybutadiene, be also beneficial to the separation and recovery of product。
(3) the Catalytic processes mild condition that the present invention uses, it does not have the side reactions such as open loop occur, and product yield is higher。
Detailed description of the invention
Introduce the enforcement of the present invention by the following examples in more detail。
Embodiment 1
Reaction vessel adds polybutadiene 10g, ethyl acetate 100g, Novozyme435 (purchased from Novozymes Company) 1g, starts to add the hydrogen peroxide that mass concentration is 30% and carries out epoxidation reaction, at the uniform velocity drip 20g hydrogen peroxide in 2h after mix homogeneously。The temperature controlling reaction system is 40 DEG C, and mixing speed is 400rpm。After sustained response 24h, stop stirring termination ring oxidation reaction, reaction mixture sat 5min is layered, reclaim upper organic phase。Ethyl acetate in decompression Distillation recovery organic facies, namely obtains epoxidized polybutadiene。Product after testing, its epoxidized polybutadiene content is 71%。
Embodiment 2
Reaction vessel adds polybutadiene 10g, ethyl acetate 100g, LipozymeRMIM (purchased from Novozymes Company) 1g, starts to add the hydrogen peroxide that mass concentration is 30% and carries out epoxidation reaction, at the uniform velocity drip 20g hydrogen peroxide in 2h after mix homogeneously。The temperature controlling reaction system is 40 DEG C, and mixing speed is 400rpm。After sustained response 24h, stop stirring termination ring oxidation reaction, reaction mixture sat 5min is layered, reclaim upper organic phase。Ethyl acetate in decompression Distillation recovery organic facies, namely obtains epoxidized polybutadiene。Product after testing, its epoxidized polybutadiene content is 63%。
Embodiment 3
Reaction vessel adds polybutadiene 10g, ethyl acetate 100g, LipozymeTLIM (purchased from Novozymes Company) 1g, starts to add the hydrogen peroxide that mass concentration is 30% and carries out epoxidation reaction, at the uniform velocity drip 20g hydrogen peroxide in 2h after mix homogeneously。The temperature controlling reaction system is 40 DEG C, and mixing speed is 400rpm。After sustained response 24h, stop stirring termination ring oxidation reaction, reaction mixture sat 5min is layered, reclaim upper organic phase。Ethyl acetate in decompression Distillation recovery organic facies, namely obtains epoxidized polybutadiene。Product after testing, its epoxidized polybutadiene content is 66%。
Embodiment 4
Reaction vessel adds polybutadiene 10g, ethyl acetate 80g, LipaseG " Amano " 50 (purchased from amano pharmaceutical company of Japan) 1g, starts to add the hydrogen peroxide that mass concentration is 30% and carries out epoxidation reaction, at the uniform velocity drip 25g hydrogen peroxide in 2h after mix homogeneously。The temperature controlling reaction system is 40 DEG C, and mixing speed is 400rpm。After sustained response 24h, stop stirring termination ring oxidation reaction, reaction mixture sat 5min is layered, reclaim upper organic phase。Ethyl acetate in decompression Distillation recovery organic facies, namely obtains epoxidized polybutadiene。Product after testing, its epoxidized polybutadiene content is 59%。
Embodiment 5
Reaction vessel adds polybutadiene 10g, ethyl acetate 90g, Novozyme435 (purchased from Novozymes Company) 1g, starts to add the hydrogen peroxide that mass concentration is 30% and carries out epoxidation reaction, at the uniform velocity drip 40g hydrogen peroxide in 2h after mix homogeneously。The temperature controlling reaction system is 40 DEG C, and mixing speed is 400rpm。After sustained response 12h, stop stirring termination ring oxidation reaction, reaction mixture sat 5min is layered, reclaim upper organic phase。Ethyl acetate in decompression Distillation recovery organic facies, namely obtains epoxidized polybutadiene。Product after testing, its epoxidized polybutadiene content is 54%。
Comparative example 1
Reaction vessel adds polybutadiene 10g, formic acid 70g, starts to add the hydrogen peroxide that mass concentration is 30% after mix homogeneously and carry out epoxidation reaction, in 2h, at the uniform velocity drip 30g hydrogen peroxide。The temperature controlling reaction system is 40 DEG C, and mixing speed is 400rpm。After sustained response 24h, stop stirring termination ring oxidation reaction, add dehydrated alcohol and make solid precipitate out, after sedimentation, carry out sucking filtration, collect filtering residue, namely obtain epoxidized polybutadiene。Product after testing, its epoxidized polybutadiene content is 13%。
Comparative example 2
Reaction vessel adds polybutadiene 10g, Novozyme435 (purchased from Novozymes Company) 1g, then starts to add the hydrogen peroxide that mass concentration is 30% and carry out epoxidation reaction, in 2h, at the uniform velocity drip 20g hydrogen peroxide。The temperature controlling reaction system is 40 DEG C, and mixing speed is 400rpm。After sustained response 24h, stop stirring termination ring oxidation reaction, add methanol and make solid precipitate out, after sedimentation, carry out sucking filtration, collect filtering residue, after testing, product generates without epoxidized polybutadiene。
Comparative example 3
Reaction vessel adds polybutadiene 10g, oxolane 100g, Novozyme435 (purchased from Novozymes Company) 1g, then starts to add the hydrogen peroxide that mass concentration is 30% and carry out epoxidation reaction, in 2h, at the uniform velocity drip 25g hydrogen peroxide。The temperature controlling reaction system is 40 DEG C, and mixing speed is 400rpm。After sustained response 24h, stop stirring termination ring oxidation reaction, add methanol and make solid precipitate out, after sedimentation, carry out sucking filtration, collect filtering residue, after testing, product generates without epoxidized polybutadiene。
Claims (10)
1. the preparation method of an epoxidized polybutadiene, it is characterised in that comprise the steps:
(1) with lipase for catalyst, ethyl acetate is as reaction promoter, and polybutadiene and hydrogen peroxide carry out epoxidation reaction；
(2) reaction product isolated, reclaims organic facies, recovered under reduced pressure ethyl acetate, namely obtains epoxidized polybutadiene。
2. preparation method according to claim 1, it is characterised in that step (1) described hydrogen peroxide is 0.5～5 times of polybutadiene quality, described ethyl acetate addition is 5～15 times of polybutadiene quality。
3. preparation method according to claim 2, it is characterised in that described hydrogen peroxide is 2～4 times of polybutadiene quality, described ethyl acetate addition is 6～10 times of polybutadiene quality。
4. preparation method according to claim 1, it is characterised in that the addition of described lipase is the 1%～10% of polybutadiene quality。
5. the preparation method according to any one of Claims 1 to 4, it is characterised in that the temperature of described epoxidation reaction is 25 DEG C～60 DEG C, more than stirring condition 400rpm, response time 12～24h。
6. preparation method according to claim 5, it is characterised in that the temperature of step (1) described epoxidation reaction is 25 DEG C～40 DEG C。
7. the preparation method according to any one of Claims 1 to 4, it is characterized in that, step (1) described lipase is one or more the mixing in Novozyme435, LipozymeRMIM, LipozymeTLIM and LipaseG " Amano " 50。
8. the preparation method according to any one of Claims 1 to 4, it is characterised in that step (1) described hydrogen peroxide is at the uniform velocity to be added drop-wise in reaction system。
9. the preparation method according to any one of Claims 1 to 4, it is characterised in that step (1) described lipase is derive from one or more the mixture in Rhizopus, aspergillus, mucor, antibacterial, yeast and animal pancreas。
10. the preparation method according to any one of Claims 1 to 4, it is characterised in that step (2) described separation process is stratification, reclaims organic facies, and reduce pressure Distillation recovery ethyl acetate, obtains epoxidized polybutadiene。
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109467623A (en) * | 2018-10-29 | 2019-03-15 | 浙江大学 | A kind of epoxidizing method of high molecular weight conjugated diene polymer |
Citations (4)
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| CN101250565A (en) * | 2007-12-11 | 2008-08-27 | 中国科学院新疆理化技术研究所 | Method for preparing 1,2-epoxy cyclohexane by catalytic oxidation of cyclohexene by lipase |
| 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 |
| CN103740471A (en) * | 2014-01-02 | 2014-04-23 | 北京化工大学 | Method for preparing epoxy resin fatty acid short-chained alcohol ester in biological catalytic method |
| CN104561149A (en) * | 2014-12-13 | 2015-04-29 | 中国科学院嘉兴材料与化工技术工程中心 | Method for preparing epoxidized soybean oil by using lipase catalysis |
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- 2016-03-08 CN CN201610131593.4A patent/CN105693887A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101250565A (en) * | 2007-12-11 | 2008-08-27 | 中国科学院新疆理化技术研究所 | Method for preparing 1,2-epoxy cyclohexane by catalytic oxidation of cyclohexene by lipase |
| 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 |
| CN103740471A (en) * | 2014-01-02 | 2014-04-23 | 北京化工大学 | Method for preparing epoxy resin fatty acid short-chained alcohol ester in biological catalytic method |
| CN104561149A (en) * | 2014-12-13 | 2015-04-29 | 中国科学院嘉兴材料与化工技术工程中心 | Method for preparing epoxidized soybean oil by using lipase catalysis |
Non-Patent Citations (1)
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| 熊阳: "在α-蒎烯生物环氧化反应过程中酯对反应的影响及机理探讨", 《化工进展》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109467623A (en) * | 2018-10-29 | 2019-03-15 | 浙江大学 | A kind of epoxidizing method of high molecular weight conjugated diene polymer |
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Application publication date: 20160622 |