CN1927851A - Synthesis method of allyl glycidyl ether - Google Patents
Synthesis method of allyl glycidyl ether Download PDFInfo
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- CN1927851A CN1927851A CN 200610096426 CN200610096426A CN1927851A CN 1927851 A CN1927851 A CN 1927851A CN 200610096426 CN200610096426 CN 200610096426 CN 200610096426 A CN200610096426 A CN 200610096426A CN 1927851 A CN1927851 A CN 1927851A
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- epoxy chloropropane
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- sodium hydroxide
- vinyl carbinol
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Abstract
The present invention relates to synthesis process of allyl glycidyl ether. The synthesis process includes the ring opening reaction of materials allyl alcohol and epoxy chloropropane under the action of solid acid catalyst to prepare the intermediate allyl chlorohydrin; and the subsequent ring closing reaction with sodium hydroxide to prepare allyl glycidyl ether. The synthesis process features the solid acid catalyst of perchlorate in the amount of 0.05-0.5 wt% of the reactants, the molar ratio between allyl alcohol and epoxy chloropropane of 1-5 to 1, the molar ratio between epoxy chloropropane and sodium hydroxide of 1 to 1-1.3, the ring opening reaction temperature of 60-130 deg.c, and the ring closing reaction temperature of 30-60 deg.c. The present invention adopts solid acid catalyst and has the advantages of use convenience, less corrosion to the apparatus, high ring opening reaction selectivity, high epoxy number and low organic chloride content of the product, etc.
Description
One, technical field
The present invention relates to a kind of synthetic method of glycidyl allyl ether, relate in particular to a kind of two step method glycidyl allyl ether synthetic method.
Two, technical background
Glycidyl allyl ether chemical name propylene oxide allyl ethers, be that vinyl carbinol and epoxy chloropropane carry out ring-closure reaction through the open loop etherificate and then with sodium hydroxide and make, it is a kind of single epoxy group(ing) thinner of aliphatics of line style, in the molecule of glycidyl allyl ether, existing carbon-carbon double bond has epoxy bond again, is important polymerization single polymerization monomer and organic synthesis intermediate; In Resins, epoxy, man-made fiber, plastics and rubber production, also be widely used as additive, solvent, catalyzer, linking agent and chain-transfer agent, in the organic chemical industry, have important purposes.
The synthetic method of glycidyl allyl ether mainly contains single stage method and two kinds of processing methodes of two-step approach.Synthesis of allyl glycidyl ether mainly adopts two-step process both at home and abroad at present; The two-step approach synthesis technique is under an acidic catalyst effect, vinyl carbinol and epoxy chloropropane carry out ring-opening reaction, carry out ring-closure reaction with sodium hydroxide again and generate corresponding glycidyl allyl ether, be that raw material vinyl carbinol and epoxy chloropropane carry out ring-opening reaction under an acidic catalyst effect, generate the chlorallylene alcohol intermediate, carry out the ring-closure reaction reaction with sodium hydroxide again and make glycidyl ether, open loop of carrying out and ring-closure reaction formula are as follows:
(R is CH in the formula
2=CHCH
2)
Ring-opening reaction is a two-step approach synthetic key, and an acidic catalyst of ring-opening reaction mainly contains the strong acid catalyst vitriol oil, perchloric acid and lewis acid catalyst BF in the synthesis technique at present
3O (C
2H
5)
2, tin chloride, aluminum chloride, titanium chloride and iron(ic) chloride etc.; The shortcoming of such an acidic catalyst for to the production unit seriously corroded, to production unit have relatively high expectations, use very inconvenient, such an acidic catalyst can cause the two key open loops of the bright base of alkene simultaneously, cause the product double bond content to reduce, make the ring-opening reaction selectivity relatively poor relatively, cause the by product in the chlorallylene alcohol intermediate more, thereby make the oxirane value of final product low, content of organic chloride is high.
Three, technology contents
The object of the present invention is to provide a kind of synthetic method of glycidyl allyl ether at above-mentioned shortcoming, that the solid acid catalyst that uses in this synthetic method has is easy to use, low and little to equipment corrosion to the two keys influences of the bright base of alkene, can improve the ring-opening reaction selectivity, make final product oxirane value height, content of organic chloride low.
A kind of synthetic method of glycidyl allyl ether comprises that with vinyl carbinol, epoxy chloropropane be raw material, carries out ring-opening reaction under the solid acid catalyst effect, makes intermediate allyl group chloropharin; Carry out ring-closure reaction with sodium hydroxide again and make glycidyl allyl ether, it is characterized by solid acid catalyst is perchlorate, and its consumption is 0.05～0.5% of a reactant quality; The mole proportioning that vinyl carbinol and epoxy chloropropane feed intake is a vinyl carbinol: epoxy chloropropane=1～5: 1; The mole proportioning of epoxy chloropropane and sodium hydroxide is an epoxy chloropropane: sodium hydroxide=1: 1～1.3; The temperature of reaction of ring-opening reaction is 60～130 ℃; The temperature of reaction of ring-closure reaction is 30～60 ℃.
The present invention is to be raw material with vinyl carbinol, epoxy chloropropane and sodium hydroxide, adopts two-step process to prepare glycidyl allyl ether under the novel solid acid catalyst effect.The first step is a ring-opening reaction, and vinyl carbinol and epoxy chloropropane react under the solid acid catalyst effect, makes intermediate allyl group chloropharin; The second step ring-closure reaction, the pure and mild sodium hydroxide of intermediate chlorallylene carries out ring-closure reaction, makes glycidyl allyl ether by refinement treatment.
In above-mentioned synthetic method, the perchlorate solid acid catalyst is magnesium perchlorate, zinc perchlorate and aluminum perchlorate, is preferably zinc perchlorate; Suitable catalyst levels is 0.1～0.3% of a reactant quality, and the solid acid catalyst consumption is many, and speed of response increases not obvious, also can cause side reaction to increase; Speed of response is slow at least and catalyst levels is crossed.The perchlorate solid acid catalyst prepares with common process, is promptly made by perchloric acid and corresponding oxyhydroxide or oxide compound reaction.
In above-mentioned synthetic method, the suitable mole proportioning that vinyl carbinol and epoxy chloropropane feed intake is a vinyl carbinol: epoxy chloropropane=1～3: 1, optimum mole proportioning is a vinyl carbinol: epoxy chloropropane=1～1.5: 1, vinyl carbinol is excessive many, can suppress unwanted side reaction and take place, the oxirane value height of product, but vinyl carbinol is excessive many simultaneously, the output of unit equipment is just few, and the energy consumption that reclaims vinyl carbinol is big.
In above-mentioned synthetic method, the suitable temperature of reaction of ring-opening reaction is 70～100 ℃, and optimum temperature of reaction is 80～90 ℃, and this temperature is low excessively, and speed of reaction is then low excessively; The suitable temperature of reaction of ring-closure reaction is 35～45 ℃, and this temperature is low excessively, and then speed of reaction is slow, and temperature is too high, and side reaction easily takes place, and causes the product oxirane value to reduce.
In above-mentioned synthetic method, the suitable mole proportioning of epoxy chloropropane and sodium hydroxide is an epoxy chloropropane: sodium hydroxide=1: 1～1.1; Sodium hydroxide is excessive, helps the carrying out of ring-closure reaction, and the organochlorine of product is low, the oxirane value height; But sodium hydroxide concentration is too much, and the pH height of waste water is big for environment pollution.
In above-mentioned synthetic method, for helping the carrying out of ring-closure reaction, in ring-closure reaction, use quaternary ammonium salt-type phase transfer catalyst, the use of phase-transfer catalyst helps the carrying out of ring-closure reaction, and the hydrolyzable chlorine of product is low, the oxirane value height; The quaternary ammonium salt catalyst levels is 0.05～0.1% of a reactant quality.
The solid acid catalyst that in ring-opening reaction, uses among the present invention, has advantage easy to use, low to equipment corrosion, simultaneously because the perchlorate solid acid catalyst is little to the two key influences of the bright base of alkene, can improve the ring-opening reaction selectivity, make product oxirane value height, the content of organic chloride of final product low.
Four, specific embodiment
Further describe the present invention below in conjunction with embodiment: the raw material epoxy chloropropane among the embodiment is a technical grade, is produced by petrochemical complex limited-liability company of Shandong petrochemical complex limited-liability company; Vinyl carbinol is a chemical pure, is produced by Shanghai chemical reagents corporation of Chinese Medicine group; 32% sodium hydroxide is technical grade, is produced by Wuhu Ronghui Chemical Co., Ltd..
The oxirane value of glycidyl allyl ether detects with hydrochloric acid-acetone method and detects.
Example 1
In the 1000ml four-hole boiling flask of mechanical stirrer, reflux exchanger and thermometer that band mechanical seal is housed, add vinyl carbinol 116g respectively, zinc perchlorate 0.6g, turn on agitator is warming up to 80 ℃, drips epoxy chloropropane 189g, 80～100 ℃ of control reaction temperature, 6h finishes; Be cooled to 35 ℃, drip 32%NaOH263g again, 35～45 ℃ of control reaction temperature, 7h finishes; Filter out by product NaCl, refinement treatment gets glycidyl allyl ether product 144g, oxirane value 0.391eq/100g.
Example 2
In the 1000ml four-hole boiling flask of mechanical stirrer, reflux exchanger and thermometer that band mechanical seal is housed, add vinyl carbinol 116g respectively, magnesium perchlorate 0.6g, turn on agitator is warming up to 80 ℃, drips epoxy chloropropane 189g, 80～100 ℃ of control reaction temperature, 6h finishes; Be cooled to 35 ℃, drip 32%NaOH263g again, 35～45 ℃ of control reaction temperature, 7h finishes; Filter out by product NaCl, refinement treatment gets glycidyl allyl ether product 103g, oxirane value 0.357eq/100g.
Example 3
In the 1000ml four-hole boiling flask of mechanical stirrer, reflux exchanger and thermometer that band mechanical seal is housed, add vinyl carbinol 116g respectively, aluminum perchlorate 0.5g, turn on agitator is warming up to 70 ℃, drips epoxy chloropropane 189g, 70～90 ℃ of control reaction temperature, 6h finishes; Be cooled to 35 ℃, drip 32%NaOH263g again, 35～45 ℃ of control reaction temperature, 7h finishes; Filter out by product NaCl, refinement treatment gets glycidyl allyl ether product 157g, oxirane value 0.394eq/100g.
Example 4
In the 1000ml four-hole boiling flask of mechanical stirrer, reflux exchanger and thermometer that band mechanical seal is housed, add vinyl carbinol 348g respectively, zinc perchlorate 1.1g, turn on agitator is warming up to 70 ℃, drips epoxy chloropropane 189g, 70～90 ℃ of control reaction temperature, 6h finishes, and air distillation removes unreacted vinyl carbinol 298g; Be cooled to 35 ℃, drip 32%NaOH263g again, 35～45 ℃ of control reaction temperature, 7h finishes; Filter out by product NaCl, refinement treatment gets glycidyl allyl ether product 148g, oxirane value 0.472eq/100g.
Example 5
In the 1000ml four-hole boiling flask of mechanical stirrer, reflux exchanger and thermometer that band mechanical seal is housed, add vinyl carbinol 116g respectively, zinc perchlorate 0.9g, turn on agitator is warming up to 70 ℃, drips epoxy chloropropane 189g, 60～80 ℃ of control reaction temperature, 6h finishes; Be cooled to 35 ℃, drip 32%NaOH263g again, 35～45 ℃ of control reaction temperature, 7h finishes; Filter out by product NaCl, refinement treatment gets glycidyl allyl ether product 193g, oxirane value 0.414eq/100g.
Claims (4)
1, a kind of synthetic method of glycidyl allyl ether comprises that with vinyl carbinol, epoxy chloropropane be raw material, carries out ring-opening reaction under the solid acid catalyst effect, makes intermediate allyl group chloropharin; Carry out ring-closure reaction with sodium hydroxide again and make glycidyl allyl ether; It is characterized by solid acid catalyst is perchlorate, and its consumption is 0.05～0.5% of a reactant quality; The mole proportioning that vinyl carbinol and epoxy chloropropane feed intake is a vinyl carbinol: epoxy chloropropane=1～5: 1; The mole proportioning of epoxy chloropropane and sodium hydroxide is an epoxy chloropropane: sodium hydroxide=1: 1～1.3; The temperature of reaction of ring-opening reaction is 60～130 ℃; The temperature of reaction of ring-closure reaction is 30～60 ℃.
2, the synthetic method of glycidyl allyl ether according to claim 1, it is characterized by the perchlorate solid acid catalyst is magnesium perchlorate, zinc perchlorate and aluminum perchlorate, is preferably zinc perchlorate; Suitable consumption is 0.1～0.3% of a reactant quality.
3, the synthetic method of glycidyl allyl ether according to claim 2, it is characterized by the suitable mole proportioning that vinyl carbinol and epoxy chloropropane feed intake is vinyl carbinol: epoxy chloropropane=1～3: 1; The mole proportioning of epoxy chloropropane and sodium hydroxide is an epoxy chloropropane: sodium hydroxide=1: 1～1.1; The suitable temperature of reaction of ring-opening reaction is 70～100 ℃, and optimum temperature of reaction is 80～90 ℃; The suitable temperature of reaction of ring-closure reaction is 35～45 ℃.
4, the synthetic method of glycidyl allyl ether according to claim 3, it is characterized by the optimum mole of vinyl carbinol and epoxy chloropropane proportioning is vinyl carbinol: epoxy chloropropane=1～1.5: 1.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103333137A (en) * | 2013-06-25 | 2013-10-02 | 湖北恒鑫化工有限公司 | Method for synthesizing allyl glycidyl ether |
| CN104592166A (en) * | 2014-12-31 | 2015-05-06 | 湖北绿色家园精细化工有限责任公司 | Immobilized catalytic synthesis method of allyl glycidyl ether molecular sieve |
| CN105111420A (en) * | 2015-10-09 | 2015-12-02 | 上海浦央新材料科技有限公司 | Preparation method of polyester resin |
| CN105254594A (en) * | 2014-12-31 | 2016-01-20 | 湖北绿色家园精细化工股份有限公司 | High-selectivity epoxy glycidyl ether preparation method |
| CN111909301A (en) * | 2020-07-24 | 2020-11-10 | 广东科德环保科技股份有限公司 | Tertiary carbonate resin and preparation method and application thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL7605330A (en) * | 1975-06-05 | 1976-12-07 | Degussa | PROCESS FOR PREPARING GLYCIDYL METHA CRYLATE. |
| GB9027448D0 (en) * | 1990-12-18 | 1991-02-06 | Ciba Geigy Ag | Production of glycidyl compounds |
| JPH07133269A (en) * | 1993-11-10 | 1995-05-23 | Yotsukaichi Gosei Kk | Production of low-chlorine glycidyl ether |
| US6646102B2 (en) * | 2001-07-05 | 2003-11-11 | Dow Global Technologies Inc. | Process for manufacturing an alpha-dihydroxy derivative and epoxy resins prepared therefrom |
| JP4064883B2 (en) * | 2003-07-09 | 2008-03-19 | 三洋化成工業株式会社 | Glycidyl ether and process for producing the same |
-
2006
- 2006-09-26 CN CNB2006100964267A patent/CN100422165C/en active Active
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103333137A (en) * | 2013-06-25 | 2013-10-02 | 湖北恒鑫化工有限公司 | Method for synthesizing allyl glycidyl ether |
| CN103333137B (en) * | 2013-06-25 | 2015-08-12 | 湖北恒鑫化工有限公司 | The synthetic method of glycidyl allyl ether |
| CN104592166A (en) * | 2014-12-31 | 2015-05-06 | 湖北绿色家园精细化工有限责任公司 | Immobilized catalytic synthesis method of allyl glycidyl ether molecular sieve |
| CN105254594A (en) * | 2014-12-31 | 2016-01-20 | 湖北绿色家园精细化工股份有限公司 | High-selectivity epoxy glycidyl ether preparation method |
| CN104592166B (en) * | 2014-12-31 | 2016-04-20 | 湖北绿色家园精细化工股份有限公司 | A kind of Supported on Zeolite process for catalytic synthesis of glycidyl allyl ether |
| CN105111420A (en) * | 2015-10-09 | 2015-12-02 | 上海浦央新材料科技有限公司 | Preparation method of polyester resin |
| CN105111420B (en) * | 2015-10-09 | 2017-10-17 | 上海浦央新材料科技有限公司 | A kind of preparation method of polyester resin |
| CN111909301A (en) * | 2020-07-24 | 2020-11-10 | 广东科德环保科技股份有限公司 | Tertiary carbonate resin and preparation method and application thereof |
| CN111909301B (en) * | 2020-07-24 | 2023-03-21 | 广东科德环保科技股份有限公司 | Tertiary carbonate resin and preparation method and application thereof |
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| CN100422165C (en) | 2008-10-01 |
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Address after: Nanjing City, Jiangsu province 210037 Longpan Road No. 159 Patentee after: Nanjing Forestry University Patentee after: Anhui Xinyuan Chemical Co., Ltd. Address before: Nanjing City, Jiangsu province 210037 Longpan Road No. 159 Patentee before: Nanjing Forestry University Patentee before: New far Chemical Industry Co., Ltd. of Anhui |
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Effective date of registration: 20191212 Address after: 245061 No. 16 Zijin Road, Circular Economy Park, Huizhou District, Anhui, Huangshan City Patentee after: Anhui Xinyuan Chemical Co., Ltd. Address before: Nanjing City, Jiangsu province 210037 Longpan Road No. 159 Co-patentee before: Anhui Xinyuan Chemical Co., Ltd. Patentee before: Nanjing Forestry University |
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Address after: 245000 No.16 Zijin Road, Circular Economy Park, Huizhou District, Huangshan City, Anhui Province Patentee after: Anhui Xinyuan Technology Co., Ltd Address before: 245061 No. 16 Zijin Road, Circular Economy Park, Huizhou District, Huangshan City, Anhui Province Patentee before: ANHUI XINYUAN CHEMICAL Co.,Ltd. |
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