CN101704730A - Ring opening etherification reaction method in two-step approach for synthesizing glycidol ether - Google Patents
Ring opening etherification reaction method in two-step approach for synthesizing glycidol ether Download PDFInfo
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- CN101704730A CN101704730A CN200910308798A CN200910308798A CN101704730A CN 101704730 A CN101704730 A CN 101704730A CN 200910308798 A CN200910308798 A CN 200910308798A CN 200910308798 A CN200910308798 A CN 200910308798A CN 101704730 A CN101704730 A CN 101704730A
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Abstract
The invention discloses a ring opening etherification reaction method in a two-step approach for synthesizing glycidol ether, comprising the following steps: taking alcohol and epoxy chloropropane as raw materials, wherein the ratio of the molar number of hydroxide radical of the alcohol to the molar number of hydroxide radical of the epoxy chloropropane is 1:1-5; and performing ring opening etherification reaction under the action of catalyst to generate o-chlorohydrine ether intermediate. The invention is characterized in that the used catalyst is fluoboric acid, and the usage amount thereof accounts for 0.01-1.0% of the alcohol matter mass, and the temperature of the catalytic reaction is 10-90 DEG C. Compared with the prior art, the used catalyst fluoboric acid has the advantages of small toxicity, convenient operation, mild reaction, low cost, high reaction selectivity and the like.
Description
Technical field
The present invention relates to the ring opening etherification reaction method in a kind of two-step approach for synthesizing glycidol ether.
Background technology
Glycidyl ether is the compound that contains one or more active epoxy bases in a kind of molecule, has the low and strong characteristics of dilution capacity of viscosity, is widely used in epoxide resin reactive diluent, muriate stablizer and textile finshing agent.The method of existing synthesizing glycidol ether has single stage method and two kinds of processing methodes of two-step approach, and using more at present is two-step approach.The existing synthesis technique of glycidyl ether two-step approach is under an acidic catalyst effect, and alcohol or phenol and epoxy chloropropane carry out ring opening etherification reaction, generate corresponding glycidyl ether with sodium hydroxide closed loop etherification reaction again.Acid catalyst commonly used has the complex compound of Lewis acid and ether, as boron trifluoride (antimony) and complex compounds such as dme, diethyl ether thereof; Metal-salt and strong acid such as the vitriol oil, perchloric acid etc. such as tin chloride, titanium, iron.But boron trifluoride (antimony) complex compound catalyst, its high volatility, toxicity are big, strong to equipment corrosion, have brought inconvenience to production operation.Boron trifluoride (antimony) complex compound is met water and then decomposed variable color etc. water sensitive in addition, and is high to the water-content requirement of reaction raw materials.Boron trifluoride (antimony) complex compound price is higher than 30 yuan/kilogram simultaneously, has increased product cost.Chinese patent 200610096426.7 discloses a kind of synthetic method of glycidyl allyl ether, and this method is a catalyzer with the solid acid perchlorate, is 0.05～0.5% of reactant quality at its consumption; The mole proportioning that vinyl carbinol and epoxy chloropropane feed intake is a vinyl carbinol: epoxy chloropropane=1～5: 1, and ring opening etherification reaction is synthetic chloropharin ether under 60～130 ℃ of conditions, again through adding the alkali closed loop, refining product glycidyl allyl ether.This solid acid catalyst is easy to use, low to equipment corrosion, but because catalyzer exists with solid-state, causes its temperature of reaction higher, has increased energy consumption.
Chinese patent 200810230035.9 discloses a kind of C
12/14The synthetic method of alkyl glycidyl ether, this method adopt lewis acid catalyst AlCl earlier in the open loop etherification step
3, SnCl
4, ZnCl
21～2 kind make catalyzer, its add-on is 0.05%～5% of a Fatty Alcohol(C12-C14 and C12-C18) quality, under temperature to 40 ℃～80 ℃ condition, drips epoxy compounds, continues reaction 1～7 hour; The boron trifluoride ethyl ether complex catalyzer that adds Fatty Alcohol(C12-C14 and C12-C18) quality 0.05%～1.5% again reacted 1～4 hour under 30～100 ℃ of conditions.This method steps is various, and the boron trifluoride ethyl ether complex catalyst toxicity that adopts is big.
Summary of the invention
The object of the present invention is to provide the ring opening etherification reaction method in a kind of two-step approach for synthesizing glycidol ether.With realize that catalyzer is easy to use, toxicity is little, ring-opening reaction mild condition selectivity height, cost be low.
Technical scheme of the present invention is: comprise that with pure and mild epoxy chloropropane be raw material, the hydroxyl mole number of alcohol and the proportioning of epoxy chloropropane mole number are 1: 0.2～5, under catalyst action, carry out ring opening etherification reaction, generate adjacent chloropharin ether intermediate, it is characterized in that catalyst system therefor is a fluoroboric acid, consumption is 0.01～1.0% of an alcohols material quality, temperature of reaction is 10～90 ℃, reaction times 2-20h.
Described alcohol comprises monohydroxy-alcohol, dibasic alcohol or polyvalent alcohol.
The hydroxyl mole number of described alcohol and the optimum ratio of epoxy chloropropane mole number are 1: 0.5～2.
Described catalyzer preferable amount is 0.03～0.3% of an alcohols material quality, preferred 35～75 ℃ of temperature of reaction, preferred 4-10h of reaction times.
In the described method, the mode that adopts epoxy chloropropane to drip in alcohols feedstock adds.
The present invention compared with the prior art, the fluoroboric acid catalyzer has had both that toxicity is little, easy to operate, reaction temperature and, cost is low, and reaction preference advantages of higher.
Embodiment
Embodiment 1:
In reactor, add the 370g propyl carbinol, and the 0.06g massfraction is 80% fluoborate aqueous solution catalyzer, stirs.Drip epoxy chloropropane 101.8g in 35 ℃ of downhill reaction devices, 2h dropwises.Be warming up to 50 ℃ afterwards, promptly get the n-butyl chloride alcohol ether behind the insulation reaction 18h.Detecting n-butyl chloride alcohol ether content is 78.5%.
Embodiment 2:
In reactor, add 62g ethylene glycol, and the 0.31g massfraction is 30% fluoborate aqueous solution catalyzer, stirs.Drip epoxy chloropropane 203.5g in 40 ℃ of downhill reaction devices, 4h dropwises.Be warming up to 60 ℃ afterwards, promptly get ethylene glycol chloropharin ether behind the insulation reaction 3h.Detecting ethylene glycol chloropharin ether content is 67.8%.
Embodiment 3:
In reactor, add the 81g glycerol, and the 0.81g massfraction is 10% fluoborate aqueous solution catalyzer, stirs.Drip epoxy chloropropane 305.2g in 60 ℃ of downhill reaction devices, 4h dropwises.Be warming up to 75 ℃ afterwards, promptly get glycerol chloropharin ether behind the insulation reaction 4h.Detecting glycerol chloropharin ether content is 53.4%.
Embodiment 4:
In reactor, add the 100g hexalin, and the 0.05g massfraction is 60% fluoborate aqueous solution catalyzer, stirs.Drip epoxy chloropropane 138.8g in 50 ℃ of downhill reaction devices, 2h dropwises.Be warming up to 65 ℃ afterwards, promptly get the cyclohexyl chloride alcohol ether behind the insulation reaction 2h.Detection ring hexyl chloride alcohol ether content is 76.3%.
Embodiment 5:
In reactor, add the 116g cyclohexanediol, and the 0.23g massfraction is 49% fluoborate aqueous solution catalyzer, stirs.Drip epoxy chloropropane 231.3g in 65 ℃ of downhill reaction devices, 6h dropwises.Be warming up to 90 ℃ afterwards, promptly get cyclohexanediol chloropharin ether behind the insulation reaction 1h.Detection ring hexylene glycol chloropharin ether content is 60.7%.
Claims (5)
1. the ring opening etherification reaction method in the two-step approach for synthesizing glycidol ether, comprise that with pure and mild epoxy chloropropane be raw material, the hydroxyl mole number of alcohol and the proportioning of epoxy chloropropane mole number are 1: 0.2～5, under catalyst action, carry out ring opening etherification reaction, generate adjacent chloropharin ether intermediate, it is characterized in that, catalyst system therefor is a fluoroboric acid, consumption is 0.01～1.0% of an alcohols material quality, and temperature of reaction is 10～90 ℃, reaction times 2-20h.
2. the ring opening etherification reaction method in the two-step approach for synthesizing glycidol ether according to claim 1 is characterized in that described alcohol comprises monohydroxy-alcohol, dibasic alcohol or polyvalent alcohol.
3. the ring opening etherification reaction method in the two-step approach for synthesizing glycidol ether according to claim 1 is characterized in that, the hydroxyl mole number of described alcohol and the proportioning of epoxy chloropropane mole number are 1: 0.5～2.
4. the ring opening etherification reaction method in the two-step approach for synthesizing glycidol ether according to claim 1 is characterized in that, described catalyst levels is 0.03～0.3% of an alcohols material quality, and temperature of reaction is 35～75 ℃, reaction times 4-10h.
5. according to the ring opening etherification reaction method in claim 1 or the 4 described two-step approach for synthesizing glycidol ether, it is characterized in that the mode that adopts epoxy chloropropane to drip adds in alcohols feedstock.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106749106A (en) * | 2016-12-23 | 2017-05-31 | 湖北绿色家园材料技术股份有限公司 | The synthetic method of ethylene glycol diglycidylether |
| CN109020925A (en) * | 2018-09-19 | 2018-12-18 | 江苏三木化工股份有限公司 | The preparation method of Polyethylene Glycol Bisglycidyl Ether |
| CN113429367A (en) * | 2021-06-23 | 2021-09-24 | 江苏扬农锦湖化工有限公司 | Preparation method of alkyl glycidyl ether |
| CN114276256A (en) * | 2021-12-29 | 2022-04-05 | 安庆北化大科技园有限公司 | Polyquaternary ammonium compound and preparation method and application thereof |
| CN115677517A (en) * | 2022-11-01 | 2023-02-03 | 南京林业大学 | Quaternary ammonium salt glycerol ether and preparation method and application thereof |
-
2009
- 2009-10-26 CN CN200910308798A patent/CN101704730A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106749106A (en) * | 2016-12-23 | 2017-05-31 | 湖北绿色家园材料技术股份有限公司 | The synthetic method of ethylene glycol diglycidylether |
| CN106749106B (en) * | 2016-12-23 | 2019-05-14 | 湖北绿色家园材料技术股份有限公司 | The synthetic method of ethylene glycol diglycidylether |
| CN109020925A (en) * | 2018-09-19 | 2018-12-18 | 江苏三木化工股份有限公司 | The preparation method of Polyethylene Glycol Bisglycidyl Ether |
| CN113429367A (en) * | 2021-06-23 | 2021-09-24 | 江苏扬农锦湖化工有限公司 | Preparation method of alkyl glycidyl ether |
| CN114276256A (en) * | 2021-12-29 | 2022-04-05 | 安庆北化大科技园有限公司 | Polyquaternary ammonium compound and preparation method and application thereof |
| CN115677517A (en) * | 2022-11-01 | 2023-02-03 | 南京林业大学 | Quaternary ammonium salt glycerol ether and preparation method and application thereof |
| CN115677517B (en) * | 2022-11-01 | 2024-03-01 | 南京林业大学 | Quaternary ammonium salt glycerol ether and preparation method and application thereof |
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Application publication date: 20100512 |