CN103554063A - Preparation method of cardanol glycidyl ether with high epoxy value - Google Patents
Preparation method of cardanol glycidyl ether with high epoxy value Download PDFInfo
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- CN103554063A CN103554063A CN201310543462.3A CN201310543462A CN103554063A CN 103554063 A CN103554063 A CN 103554063A CN 201310543462 A CN201310543462 A CN 201310543462A CN 103554063 A CN103554063 A CN 103554063A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
- C07D303/28—Ethers with hydroxy compounds containing oxirane rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
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Abstract
The invention provides a preparation method of cardanol glycidyl ether with a high epoxy value. The preparation method comprises the following steps: a. preparation of hydroxy epoxidized cardanol, namely, reacting 100 parts by weight of cardanol, 60-200 parts by weight of epoxy chloropropane and 1-3 parts by weight of benzyltriethylammonium chloride serving as a catalyst at the temperature of 70-90 DEG C for 3-4 hours, cooling to 50-60 DEG C, dropwise adding 40-60 parts by weight of sodium hydroxide solution with the mass fraction of 30%, and carrying out ring-closure reaction for 2-4 hours, thus obtaining the hydroxy epoxidized cardanol; b. the side chain double-bond epoxidation of the hydroxy epoxidized cardanol, taking 100 parts by weight of the hydroxy epoxidized cardanol, 15-45 parts by weight of glacial acetic acid, 30-70 parts by weight of strong acid catalyst and 100-300 parts by weight of methylbenzene, controlling the temperature at 50-70 DEG C, dropwise adding 70-120 parts by weight of hydrogen peroxide with the mass fraction of 30%, and reacting for 6-8 hours to oxidize side chain double bonds of hydroxy epoxidized cardanol into an oxygen-bearing three-membered ring, thus obtaining cardanol glycidyl ether with the high epoxy value in the end.
Description
Technical field
The present invention relates to the preparation method of thermo-stabilizer for a kind of clorafin, relate to specifically a kind of preparation method of high epoxy value cardanol glycidyl ether.
Background technology
Clorafin is the chlorinated derivatives of straight-chain paraffin, as fire retardant and extender plasticizer, be widely used in production CABLE MATERIALS, the goods such as plate, flexible pipe, leatheroid, rubber, thermostability is the important indicator of clorafin quality, finds a kind of cheapness, thermal stability is good, oxirane value is high thermo-stabilizer has been the task of top priority.
Summary of the invention
Object of the present invention is just in order to provide a kind of for the preparation of desirable clorafin thermo-stabilizer---the preparation method of high epoxy value cardanol glycidyl ether.
Object of the present invention can realize by following technique measures:
High epoxy value cardanol glycidyl ether of the present invention adopts following step preparation method:
The preparation of a, hydroxyl epoxidation cardanol:
Getting cardanol, epoxy chloropropane, catalyzer benzyltriethylammoinium chloride according to parts by weight meter proportioning is: 100 parts of cardanols, 60 ~ 200 parts of epoxy chloropropane, 1 ~ 3 part of catalyzer benzyltriethylammoinium chloride, 70 ~ 90 ℃ of temperature controls, react 3 ~ 4 hours, then be cooled to 50 ~ 60 ℃, 40 ~ 60 parts of sodium hydroxide solutions that add the massfraction 30% of getting according to ratio of weight and number in the mode dripping, carry out ring-closure reaction 2 ~ 4 hours, obtain hydroxyl epoxidation cardanol, oxirane value is 0.22 ~ 0.28mol/100g;
The pendant double bonds epoxidation of b, cardanol glycidyl ether:
Get hydroxyl epoxidation cardanol, glacial acetic acid, the hydrogen peroxide of massfraction 30%, strongly acidic catalyst, toluene according to parts by weight meter proportioning is: 100 parts of hydroxyl epoxidation cardanols, 15 ~ 45 parts of glacial acetic acids, 30 ~ 70 parts of strongly acidic catalysts, 100 ~ 300 parts of toluene, 50 ~ 70 ℃ of temperature controls, 70 ~ 120 parts, the hydrogen peroxide that adds the massfraction 30% of getting according to ratio of weight and number in the mode dripping, react 6 ~ 8 hours, hydroxyl epoxidation cardanol pendant double bonds is oxidized to containing oxygen triatomic ring, finally obtain the cardanol glycidyl ether of high epoxy value, oxirane value reaches 0.5 ~ 0.65mol/100g.
beneficial effect of the present invention is as follows:
(1) cardanol is extracted by cashew nut shell, belongs to renewable resources, and source is abundant, cheap;
(2) the molten point of cardanol is low, boiling point is high, nontoxic;
(3) cardanol molecular weight is larger, the oxirane value of the cardanol of the high epoxy value of preparation is higher, as the thermo-stabilizer of clorafin qualitative good (by weight: in 1000 parts of clorafins, add 1 part of high epoxy value cardanol, the use temperature of clorafin can reach 180 ℃, heatproof effect than the diglycidyl ether of ethylene glycol of interpolation equal quality is good, and price is relatively cheap).
Embodiment
The present invention is further described below with reference to embodiment:
embodiment 1
step 1
The preparation of hydroxyl epoxidation cardanol: take cardanol 30g, epoxy chloropropane 19g and benzyltriethylammoinium chloride 0.6g in 250mL four-hole boiling flask, add a magneton, nitrogen protection, magnetic agitation, 70 ℃ of temperature controls, reaction 3h, be cooled to 60 ℃, drip the sodium hydroxide solution of 16mL massfraction 30%, continue reaction 3h, pour upper strata oily liquids into separating funnel, hot wash is to neutral, vacuum rotary steam goes out solvent, obtains orange red oily transparent liquid, and oxirane value is 0.241mol/100g;
step 2
The pendant double bonds epoxidation of hydroxyl epoxidation cardanol: take above-mentioned hydroxyl epoxidation cardanol 20g, strongly acidic catalyst 10g, toluene 20g, glacial acetic acid 6g and a magneton in 250mL there-necked flask, magnetic agitation, be heated to 50-60 ℃, drip the hydrogen peroxide 18.6g of massfraction 30%, drip and finish, 60 ℃ of temperature controls, reaction 7h, pour upper strata oily liquids into separating funnel, hot wash is to neutral, vacuum rotary steam goes out solvent, finally obtains orange red oily transparent liquid, and oxirane value is 0.518 mol/100g.
embodiment 2
step 1
The preparation of hydroxyl epoxidation cardanol: take cardanol 30g, epoxy chloropropane 19g and benzyltriethylammoinium chloride 0.6g in 250mL four-hole boiling flask, add a magneton, nitrogen protection, magnetic agitation, 80 ℃ of temperature controls, reaction 3h, be cooled to 70 ℃, drip the sodium hydroxide of 16mL massfraction 30%, continue reaction 3h, with separating funnel, separate upper strata oily liquids, hot wash is to neutral, vacuum rotary steam goes out solvent, obtains orange red oily transparent liquid, and oxirane value is 0.263mol/100g;
step 2
The pendant double bonds epoxidation of hydroxyl epoxidation cardanol: take above-mentioned hydroxyl epoxidation cardanol 20g, strongly acidic catalyst 10g, toluene 20g, glacial acetic acid 5.5g and a magneton in 250mL there-necked flask, magnetic agitation, be heated to 50-60 ℃, drip the hydrogen peroxide 17.4g of massfraction 30%, drip and finish, 60 ℃ of temperature controls, reaction 7h, pour upper strata oily liquids into separating funnel, hot wash is to neutral, vacuum rotary steam goes out solvent, finally obtains orange red oily transparent liquid, and oxirane value is 0.549 mol/100g.
embodiment 3
step 1
The preparation of hydroxyl epoxidation cardanol: take cardanol 30g, epoxy chloropropane 28g and benzyltriethylammoinium chloride 0.6g in 250mL four-hole boiling flask, add a magneton, nitrogen protection, magnetic agitation, 80 ℃ of temperature controls, reaction 4h, be cooled to 60 ℃, drip the sodium hydroxide of 16mL massfraction 30%, continue reaction 3h, with separating funnel, separate upper strata oily liquids, hot wash is to neutral, vacuum rotary steam goes out solvent, obtains orange red oily transparent liquid, and oxirane value is 0.276mol/100g;
step 2
The pendant double bonds epoxidation of hydroxyl epoxidation cardanol: take above-mentioned hydroxyl epoxidation cardanol 20g, strongly acidic catalyst 12g, toluene 20g, glacial acetic acid 5g and a magneton in 250mL there-necked flask, magnetic agitation, be heated to 50-60 ℃, drip the hydrogen peroxide 15.8g of massfraction 30%, drip and finish, 60 ℃ of temperature controls, reaction 7h, pour upper strata oily liquids into separating funnel, hot wash is to neutral, vacuum rotary steam goes out solvent, finally obtains orange red oily transparent liquid, and oxirane value is 0.579 mol/100g.
embodiment 4
step 1
The preparation of hydroxyl epoxidation cardanol: take cardanol 30g, epoxy chloropropane 35g and benzyltriethylammoinium chloride 0.6g in 250mL four-hole boiling flask, add a magneton, nitrogen protection, magnetic agitation, 80 ℃ of temperature controls, reaction 4h, heat to 60 ℃, drip the sodium hydroxide of 16mL massfraction 30%, continue reaction 3h, with separating funnel, separate upper strata oily liquids, hot wash is to neutral, vacuum rotary steam goes out solvent, obtains orange red oily transparent liquid, and oxirane value is 0.280mol/100g;
step 2
The pendant double bonds epoxidation of hydroxyl epoxidation cardanol: take above-mentioned hydroxyl epoxidation cardanol 20g, strongly acidic catalyst 12g, toluene 30g, glacial acetic acid 5g and a magneton in 250mL there-necked flask, magnetic agitation, be heated to 50-60 ℃, drip the hydrogen peroxide 15.8g of massfraction 30%, drip and finish, 60 ℃ of temperature controls, reaction 7h, pour upper strata oily liquids into separating funnel, hot wash is to neutral, vacuum rotary steam goes out solvent, finally obtains orange red oily transparent liquid, and oxirane value is 0.610 mol/100g.
Claims (1)
1. a preparation method for high epoxy value cardanol glycidyl ether, is characterized in that: described method realizes by following step:
The preparation of a, hydroxyl epoxidation cardanol:
According to ratio of weight and number, get: 100 parts of cardanols, 60 ~ 200 parts of epoxy chloropropane, 1 ~ 3 part of catalyzer benzyltriethylammoinium chloride, 70 ~ 90 ℃ of temperature controls, react 3 ~ 4 hours, then be cooled to 50 ~ 60 ℃, 40 ~ 60 parts of sodium hydroxide solutions that add the massfraction 30% of getting according to ratio of weight and number in the mode dripping, carry out ring-closure reaction 2 ~ 4 hours, obtain hydroxyl epoxidation cardanol, oxirane value is 0.22 ~ 0.28mol/100g;
The pendant double bonds epoxidation of b, cardanol glycidyl ether:
According to ratio of weight and number, get: 100 parts of hydroxyl epoxidation cardanols, 15 ~ 45 parts of glacial acetic acids, 30 ~ 70 parts of strongly acidic catalysts, 100 ~ 300 parts of toluene, 50 ~ 70 ℃ of temperature controls, 70 ~ 120 parts, the hydrogen peroxide that adds the massfraction 30% of getting according to ratio of weight and number in the mode dripping, react 6 ~ 8 hours, hydroxyl epoxidation cardanol pendant double bonds is oxidized to containing oxygen triatomic ring, the cardanol glycidyl ether that finally obtains high epoxy value, oxirane value reaches 0.5 ~ 0.65mol/100g.
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Cited By (15)
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| CN104109141A (en) * | 2014-07-18 | 2014-10-22 | 苏州保力瑞生物材料科技开发有限公司 | Preparation method of plant monophenol glycidyl ether |
| CN104557791A (en) * | 2014-12-01 | 2015-04-29 | 苏州保力瑞生物材料科技开发有限公司 | Method for preparing plant bisphenol glycidyl ether |
| CN104710388A (en) * | 2015-03-03 | 2015-06-17 | 中国林业科学研究院林产化学工业研究所 | Epoxy cardanol-based glycidyl ether as well as preparation method and application thereof |
| WO2015168771A1 (en) * | 2014-05-05 | 2015-11-12 | Centre De Technologie Minerale Et De Plasturgie Inc. | Cardanol glycidyl ether derivatives |
| CN105237734A (en) * | 2015-11-08 | 2016-01-13 | 福建师范大学 | Synthesis method of cardanol-based epoxy resin |
| CN105254844A (en) * | 2015-10-21 | 2016-01-20 | 复旦大学 | Cardanol based epoxy resin containing maleimide structure and preparation method of cardanol based epoxy resin |
| CN105669936A (en) * | 2016-03-29 | 2016-06-15 | 中国林业科学研究院林产化学工业研究所 | Phosphorus-containing cardanol-base polyurethane prepolymer modified phenolic foam plastic and preparation method thereof |
| CN106749385A (en) * | 2016-11-30 | 2017-05-31 | 中国林业科学研究院林产化学工业研究所 | A kind of siliceous glycidol ether of cashew nut phenolic group and preparation method thereof |
| CN108384057A (en) * | 2018-02-25 | 2018-08-10 | 李嘉顺 | A kind of flame retardant of magnesium hydroxide, flame-retardant composition and its cable |
| CN108660613A (en) * | 2018-05-17 | 2018-10-16 | 安徽工程大学 | The composite nano-fiber membrane and preparation method of a kind of modified by cardanol and its application on enzyme immobilization |
| CN109456678A (en) * | 2018-11-19 | 2019-03-12 | 福建师范大学泉港石化研究院 | A kind of graphene modification method for preparing suitable for epoxy resin |
| CN109517141A (en) * | 2018-10-11 | 2019-03-26 | 安徽大学 | Cardanol modified waterborne epoxy curing agent and preparation method thereof |
| CN109867915A (en) * | 2019-01-31 | 2019-06-11 | 泉州师范学院 | A kind of application based on anacardol photosensitive resin composition and its in 355nm3D printing |
| CN111909357A (en) * | 2019-05-08 | 2020-11-10 | 王镇 | Preparation method of water-based cardanol active emulsifier |
| CN113651846A (en) * | 2021-09-13 | 2021-11-16 | 清远高能结加改性材料科技有限公司 | Method for modifying rubber by cardanol derivative |
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Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015168771A1 (en) * | 2014-05-05 | 2015-11-12 | Centre De Technologie Minerale Et De Plasturgie Inc. | Cardanol glycidyl ether derivatives |
| CN104109141A (en) * | 2014-07-18 | 2014-10-22 | 苏州保力瑞生物材料科技开发有限公司 | Preparation method of plant monophenol glycidyl ether |
| CN104557791B (en) * | 2014-12-01 | 2017-05-03 | 苏州保力瑞生物材料科技开发有限公司 | Method for preparing plant bisphenol glycidyl ether |
| CN104557791A (en) * | 2014-12-01 | 2015-04-29 | 苏州保力瑞生物材料科技开发有限公司 | Method for preparing plant bisphenol glycidyl ether |
| CN104710388A (en) * | 2015-03-03 | 2015-06-17 | 中国林业科学研究院林产化学工业研究所 | Epoxy cardanol-based glycidyl ether as well as preparation method and application thereof |
| CN105254844A (en) * | 2015-10-21 | 2016-01-20 | 复旦大学 | Cardanol based epoxy resin containing maleimide structure and preparation method of cardanol based epoxy resin |
| CN105237734B (en) * | 2015-11-08 | 2017-06-09 | 福建师范大学 | A kind of synthetic method of anacardol base epoxy |
| CN105237734A (en) * | 2015-11-08 | 2016-01-13 | 福建师范大学 | Synthesis method of cardanol-based epoxy resin |
| CN105669936A (en) * | 2016-03-29 | 2016-06-15 | 中国林业科学研究院林产化学工业研究所 | Phosphorus-containing cardanol-base polyurethane prepolymer modified phenolic foam plastic and preparation method thereof |
| CN105669936B (en) * | 2016-03-29 | 2018-07-13 | 中国林业科学研究院林产化学工业研究所 | A kind of phosphorous anacardol based polyurethanes performed polymer modified phenolic foam plastic and preparation method thereof |
| CN106749385A (en) * | 2016-11-30 | 2017-05-31 | 中国林业科学研究院林产化学工业研究所 | A kind of siliceous glycidol ether of cashew nut phenolic group and preparation method thereof |
| CN106749385B (en) * | 2016-11-30 | 2019-03-19 | 中国林业科学研究院林产化学工业研究所 | A kind of siliceous glycidol ether of cashew nut phenolic group and preparation method thereof |
| CN108384057A (en) * | 2018-02-25 | 2018-08-10 | 李嘉顺 | A kind of flame retardant of magnesium hydroxide, flame-retardant composition and its cable |
| CN108660613A (en) * | 2018-05-17 | 2018-10-16 | 安徽工程大学 | The composite nano-fiber membrane and preparation method of a kind of modified by cardanol and its application on enzyme immobilization |
| CN108660613B (en) * | 2018-05-17 | 2021-02-23 | 安徽工程大学 | Cardanol modified composite nanofiber membrane, preparation method and application thereof in enzyme immobilization |
| CN109517141A (en) * | 2018-10-11 | 2019-03-26 | 安徽大学 | Cardanol modified waterborne epoxy curing agent and preparation method thereof |
| CN109517141B (en) * | 2018-10-11 | 2021-01-01 | 安徽大学 | Cardanol modified waterborne epoxy curing agent and preparation method thereof |
| CN109456678A (en) * | 2018-11-19 | 2019-03-12 | 福建师范大学泉港石化研究院 | A kind of graphene modification method for preparing suitable for epoxy resin |
| CN109456678B (en) * | 2018-11-19 | 2021-03-16 | 福建师范大学泉港石化研究院 | Graphene modification preparation method suitable for epoxy resin |
| CN109867915A (en) * | 2019-01-31 | 2019-06-11 | 泉州师范学院 | A kind of application based on anacardol photosensitive resin composition and its in 355nm3D printing |
| CN109867915B (en) * | 2019-01-31 | 2021-08-06 | 泉州师范学院 | Photosensitive resin composition based on cardanol and application of photosensitive resin composition in 355nm3D printing |
| CN111909357A (en) * | 2019-05-08 | 2020-11-10 | 王镇 | Preparation method of water-based cardanol active emulsifier |
| CN113651846A (en) * | 2021-09-13 | 2021-11-16 | 清远高能结加改性材料科技有限公司 | Method for modifying rubber by cardanol derivative |
| CN113651846B (en) * | 2021-09-13 | 2022-08-02 | 清远高能结加改性材料科技有限公司 | Method for modifying rubber by cardanol derivative |
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Inventor after: Wang Hongli Inventor after: Hu Mei Inventor after: Bao Haifang Inventor after: Zhuang Xinsheng Inventor after: He Xiaosheng Inventor after: Wu Zhen Inventor after: Gu Zhongming Inventor after: Yuan Lin Inventor after: Yuan Zhuqing Inventor after: Chai Yongli Inventor after: Wang Hongzhuan Inventor after: Chen Weihang Inventor after: Meng Baoxun Inventor after: Huang Bei Inventor after: Duan Wenrui Inventor after: Gao Mingliang Inventor after: Tian Qianqian Inventor after: Han Juan Inventor after: Geng Feng Inventor after: Zhang Chen Inventor after: Jia Jiangong Inventor after: Wen Shiqian Inventor after: Li Yingchun Inventor after: Liu Huiwan Inventor after: Qiao Guifang Inventor after: Li Jiake Inventor after: Chen Jie Inventor after: Zhang Yongjie Inventor after: Guo Xinyu Inventor after: Li Changlin Inventor after: Liu Yi Inventor after: Sheng Erqiang Inventor after: Zhou Xianguo Inventor after: Zhang Chunling Inventor after: Wei Xinjun Inventor after: Lu Yanxia Inventor after: Zhang Jie Inventor after: Zhang Mingwei Inventor before: Wang Hongli Inventor before: Feng Yujun Inventor before: Zhang Chen Inventor before: Zhao Yili Inventor before: Wen Shiqian Inventor before: Bao Haifang Inventor before: Geng Feng Inventor before: Liu Huiwan Inventor before: Qiao Guifang Inventor before: Li Jiake Inventor before: Chen Jie Inventor before: Zhang Mingwei Inventor before: Zhang Yongjie Inventor before: Guo Xinyu Inventor before: Sheng Erqiang Inventor before: Xie Yunman Inventor before: Wu Zhen Inventor before: Wang Jingheng Inventor before: Hu Mei Inventor before: Guo Ge Inventor before: Tian Qianqian Inventor before: Yue Yanrong |
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Free format text: CORRECT: INVENTOR; FROM: WANG HONGLI ZHANG MINGWEI XIE YUNMAN WU ZHEN WANG JINGHENG HU MEI GUO GE TIAN QIANQIAN YUE YANRONG FENG YUJUN ZHANG CHEN ZHAO YILI WEN SHIQIAN BAO HAIFANG GENG FENG LIU HUIWAN QIAO GUIFANG LI JIAKE CHEN JIE ZHANG YONGJIE GUO XINYU SHENG ERQIANG TO: WANG HONGLI CHEN WEIHANG LI YINGCHUN ZHOU XIANGUO ZHANG CHUNLING WEI XINJUN LU YANXIA ZHANG JIE ZHANG MINGWEI HU MEI BAO HAIFANG ZHUANG XINSHENG HE XIAOSHENG WU ZHEN GU ZHONGMING YUAN LIN YUAN ZHUQING CHAI YONGLI WANG HONGZHUAN MENG BAOXUN HUANG BEI DUAN WENRUI GAO MINGLIANG TIAN QIANQIAN HAN JUAN GENG FENG ZHANG CHEN JIA JIANGONG WEN SHIQIAN LIU HUIWAN QIAO GUIFANG LI JIAKE CHEN JIE ZHANG YONGJIE GUO XINYU LI CHANGLIN LIU |
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