CN101550069A - Method for synthesizing propylene glycol methyl ether - Google Patents
Method for synthesizing propylene glycol methyl ether Download PDFInfo
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- CN101550069A CN101550069A CNA2009100721184A CN200910072118A CN101550069A CN 101550069 A CN101550069 A CN 101550069A CN A2009100721184 A CNA2009100721184 A CN A2009100721184A CN 200910072118 A CN200910072118 A CN 200910072118A CN 101550069 A CN101550069 A CN 101550069A
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- propylene glycol
- glycol monomethyl
- monomethyl ether
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- synthetic method
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Abstract
A method for synthesizing propylene glycol methyl ether relates to a method for synthesizing propylene glycol methyl ether. The method of the invention settles the problems of high reaction temperature, high pressure, low activity of catalyst and low selectivity existing in the prior method for preparing propylene glycol methyl ether. The method comprises the following steps: 1. preparing a compound A; 2. preparing a compound B; and 3. after naturally cooling the mixed solution B to a room temperature, atmospherically distilling and obtaining the propylene glycol methyl ether. The method of the invention has the advantages of simple process, applicable whole reaction in the condition of normal pressure and low-temperature, 93.3%-94.2% of epoxy propane conversion rate, 98.1%-99.1% of product selectivity, and no environment pollution as the whole reaction process is executed under the condition of no dissolvent. The propylene glycol methyl ether (1-methoxy-2-propanol or 2-methoxy-1-propanol) synthesized according to the invention can be synthesized by regulating the mixed liquid of acetate methyl glyoxaline hydroxide or acetate methyl glyoxaline chloride and ferric trichloride.
Description
Technical field
The present invention relates to a kind of synthetic method of propylene glycol monomethyl ether.
Background technology
The solvent that propylene glycol monomethyl ether (PM) is a kind of excellent property, toxicity is lower, it is strong to have dissolving power, volatility is low, flash-point is high, advantages such as smell gentleness, be widely used in fields such as coating, printing and dyeing and agricultural chemicals, it also can be used as fuel antifreezing agent, washing composition, extraction agent and organic synthesis intermediate simultaneously.The molecular structure of propylene glycol monomethyl ether, physicochemical property and glycol ether are close, so be considered to the desirable substitute products of the bigger gylcol ether of toxicity.But but there is temperature of reaction height (more than at least 100 ℃) in the existing method for preparing propylene glycol monomethyl ether, the problem of pressure height, catalyst activity low (activity only is 60%～90%) and selectivity low (selectivity only is 82%～90%).
Summary of the invention
The present invention seeks to have the temperature of reaction height in order to solve the existing method for preparing propylene glycol monomethyl ether, pressure height, the problem that catalyst activity is low and selectivity is low, and the synthetic method of propylene glycol monomethyl ether is provided.
The synthetic method of propylene glycol monomethyl ether realizes according to the following steps: one, be that 0.5～0.6mol, volume are the anhydrous methanol of 20～24.3mL with amount of substance, amount of substance is that 0.015～0.025mol, volume are that the propylene oxide of 1.05～6mL and catalyst mix that amount of substance is 0.004～0.02mol are even, mixed solution A; Two, with mixed solution A heating in water bath to 60～70 ℃, and magnetic agitation 3～5h, mixing solutions B; Three, carry out air distillation again after mixing solutions B being naturally cooled to room temperature, the solvent among the mixing solutions B is all steamed, promptly get propylene glycol monomethyl ether; Wherein catalyzer is an acetate ylmethyl imidazolium hydroxide in the step 1, or the ionic liquid formed by 1: 1～3 mol ratio of acetoxyl Methylimidazole muriate and iron trichloride.
It is gentle that synthesizing propanediol monomethyl ether method of the present invention has reaction conditions, is can finish whole process of preparation under the non-pressurized situation at pressure; Technology of the present invention is simple, temperature of reaction can be controlled in below 70 ℃, reaction times short (only being 4h), processing ease, and the propylene oxide transformation efficiency is 93.3%～94.2%, and product selectivity is 98.1%～99.1%; Entire reaction course is carried out under condition of no solvent, can not cause environmental pollution.
The regulation of ionic liquid that synthetic propylene glycol monomethyl ether of the present invention (1-methoxyl group 2-propyl alcohol or 2-methoxyl group 1-propyl alcohol) can use acetate ylmethyl imidazolium hydroxide or acetoxyl Methylimidazole muriate and iron trichloride to form by 1: 1～3 mol ratio synthesizes.
Embodiment
Embodiment one: the synthetic method of present embodiment propylene glycol monomethyl ether realizes according to the following steps: one, be that 0.5～0.6mol, volume are the anhydrous methanol of 20～24.3mL with amount of substance, amount of substance is that 0.015～0.025mol, volume are that the propylene oxide of 1.05～6mL and catalyst mix that amount of substance is 0.004～0.02mol are even, mixed solution A; Two, with mixed solution A heating in water bath to 60～70 ℃, and magnetic agitation 3～5h, mixing solutions B; Three, carry out air distillation again after mixing solutions B being naturally cooled to room temperature, the solvent among the mixing solutions B is all steamed, promptly get propylene glycol monomethyl ether; Wherein catalyzer is an acetate ylmethyl imidazolium hydroxide in the step 1, or the ionic liquid formed by 1: 1～3 mol ratio of acetoxyl Methylimidazole muriate and iron trichloride.
Employed chemical reagent is analytical pure in the present embodiment.
Acetate ylmethyl imidazolium hydroxide is a basic catalyst in the present embodiment, and the ionic liquid that acetoxyl Methylimidazole muriate and iron trichloride are formed by 1: 1～3 mol ratio is an an acidic catalyst.
The ionic liquid that acetoxyl Methylimidazole muriate and iron trichloride are formed by 1: 1～3 mol ratio in the present embodiment is to mix and stir according to routine to form.
Reaction equation according to present embodiment synthesizing propanediol monomethyl ether:
Embodiment two: what present embodiment and embodiment one were different is that the anhydrous methanol amount of substance is that 0.52～0.58mol, volume are 21～23mL in the step 1.Other step and parameter are identical with embodiment one.
Embodiment three: what present embodiment and embodiment one were different is that the anhydrous methanol amount of substance is that 0.56mol, volume are 22mL in the step 1.Other step and parameter are identical with embodiment one.
Embodiment four: what present embodiment and embodiment one to three were different is that the propylene oxide amount of substance is that 0.018～0.022mol, volume are 2.4～4.6mL in the step 1.Other step and parameter are identical with embodiment one to three.
Embodiment five: what present embodiment and embodiment one to three were different is that the propylene oxide amount of substance is that 0.020mol, volume are 3.5mL in the step 1.Other step and parameter are identical with embodiment one to three.
Embodiment six: present embodiment is different with embodiment four or five is that the amount of step 1 catalyst substance is 0.011mol.Other step and parameter are identical with embodiment four or five.
Embodiment seven: present embodiment is different with embodiment four or five is that the amount of step 1 catalyst substance is 0.016mol.Other step and parameter are identical with embodiment four or five.
Embodiment eight: what present embodiment and embodiment one, two, three, six or seven were different is in the step 2 mixed solution A to be heated to 65 ℃ from room-temperature water bath.Other step and parameter are identical with embodiment one, two, three, six or seven.
Embodiment nine: present embodiment and embodiment eight are different be in the step 2 magnetic agitation time be 4h.Other step and parameter are identical with embodiment eight.
Embodiment ten: what present embodiment and embodiment one were different is that acetate ylmethyl imidazolium hydroxide is to be prepared in accordance with the following methods: one, take by weighing 1-acyl group-3-Methochloride and KOH, NaOH, LiOH or NH by 1: 2 mol ratio
3H
2O, and soluble in water, under the condition of cooling bath, stir 5h then, get mixed solution C; Two, mixed solution C is warming up to 50 ℃, and the rotary evaporation that reduces pressure removes the water in the mixed solution C, then with anhydrous methanol washing 1 time and leave standstill 2h, mixing solutions D; Three, be the rotary evaporation 0.5h that reduces pressure under 40 ℃ the condition with mixing solutions D, get rid of the dehydrated alcohol among the mixing solutions D, promptly get acetate ylmethyl imidazolium hydroxide in temperature.
The acetate ylmethyl imidazolium hydroxide that present embodiment obtains is confirmed by the FT-IR infrared spectra.
The acetate ylmethyl imidazolium hydroxide reaction equation of present embodiment preparation is (is 1-acyl group-3-Methochloride and KOH according to reactant):
Embodiment 11: the synthetic method of present embodiment propylene glycol monomethyl ether realizes according to the following steps: one, be that 0.5mol, volume are the anhydrous methanol of 20mL with amount of substance, amount of substance is that 0.025mol, volume are that the propylene oxide of 5.8mL and acetate ylmethyl imidazolium hydroxide that amount of substance is 0.016mol mix, mixed solution A; Two, with mixed solution A heating in water bath to 60 ℃, and magnetic agitation 4h, mixing solutions B; Three, carry out air distillation again after mixing solutions B being naturally cooled to room temperature, the solvent among the mixing solutions B is all steamed, promptly get propylene glycol monomethyl ether.
It is 1-methoxyl group 2-propyl alcohol that present embodiment obtains propylene glycol monomethyl ether, analyzes and the transformation efficiency of GC-MS analysis propylene oxide is 94.2% through GC, and the selectivity of 1-methoxyl group 2-propyl alcohol is 99.1%.
Reaction equation according to present embodiment synthesizing propanediol monomethyl ether:
Embodiment 12: the synthetic method of present embodiment propylene glycol monomethyl ether realizes according to the following steps: one, be that 0.6mol, volume are the anhydrous methanol of 24.3mL with amount of substance, amount of substance is that 0.015mol, the volume ionic liquid that to be the propylene oxide of 1.05mL form by 1: 3 mol ratio with acetoxyl Methylimidazole muriate that amount of substance is 0.016mol and iron trichloride mixes, mixed solution A; Two, with mixed solution A heating in water bath to 70 ℃, and magnetic agitation 4h, mixing solutions B; Three, carry out air distillation again after mixing solutions B being naturally cooled to room temperature, the solvent among the mixing solutions B is all steamed, promptly get propylene glycol monomethyl ether.
It is 2-methoxyl group 1-propyl alcohol that present embodiment obtains propylene glycol monomethyl ether, analyzes and the transformation efficiency of GC-MS analysis propylene oxide is 93.3% through GC, and the selectivity of 2-methoxyl group 1-propyl alcohol is 98.1%.
Reaction equation according to present embodiment synthesizing propanediol monomethyl ether:
Embodiment 13: the synthetic method of present embodiment propylene glycol monomethyl ether realizes according to the following steps: one, be that 0.6mol, volume are the anhydrous methanol of 24.3mL with amount of substance, amount of substance is that 0.015mol, the volume ionic liquid that to be the propylene oxide of 1.05mL form by 1: 2 mol ratio with acetoxyl Methylimidazole muriate that amount of substance is 0.016mol and iron trichloride mixes, mixed solution A; Two, with mixed solution A heating in water bath to 70 ℃, and magnetic agitation 4h, mixing solutions B; Three, carry out air distillation again after mixing solutions B being naturally cooled to room temperature, the solvent among the mixing solutions B is all steamed, promptly get propylene glycol monomethyl ether.
It is 2-methoxyl group 1-propyl alcohol that present embodiment obtains propylene glycol monomethyl ether, analyzes and the transformation efficiency of GC-MS analysis propylene oxide is 93.8% through GC, and the selectivity of 2-methoxyl group 1-propyl alcohol is 98.6%.
Reaction equation according to present embodiment synthesizing propanediol monomethyl ether:
Claims (7)
1, the synthetic method of propylene glycol monomethyl ether, the synthetic method that it is characterized in that propylene glycol monomethyl ether realizes according to the following steps: one, be that 0.5～0.6mol, volume are the anhydrous methanol of 20～24.3mL with amount of substance, amount of substance is that 0.015～0.025mol, volume are that the propylene oxide of 1.05～6mL and catalyst mix that amount of substance is 0.004～0.02mol are even, mixed solution A; Two, with mixed solution A heating in water bath to 60～70 ℃, and magnetic agitation 3～5h, mixing solutions B; Three, carry out air distillation again after mixing solutions B being naturally cooled to room temperature, the solvent among the mixing solutions B is all steamed, promptly get propylene glycol monomethyl ether; Wherein catalyzer is an acetate ylmethyl imidazolium hydroxide in the step 1, or the ionic liquid formed by 1: 1～3 mol ratio of acetoxyl Methylimidazole muriate and iron trichloride.
2, the synthetic method of propylene glycol monomethyl ether according to claim 1 is characterized in that the anhydrous methanol amount of substance is that 0.52～0.58mol, volume are 21～23mL in the step 1.
3, the synthetic method of propylene glycol monomethyl ether according to claim 1 and 2 is characterized in that the propylene oxide amount of substance is that 0.018～0.022mol, volume are 2.4～4.6mL in the step 1.
4, the synthetic method of propylene glycol monomethyl ether according to claim 3, the amount that it is characterized in that catalyst substance in the step 1 is 0.016mol.
5,, it is characterized in that in the step 2 mixed solution A being heated to 65 ℃ from room-temperature water bath according to the synthetic method of claim 1,2 or 4 described propylene glycol monomethyl ethers.
6, the synthetic method of propylene glycol monomethyl ether according to claim 5 is characterized in that the magnetic agitation time is 4h in the step 2.
7, the synthetic method of propylene glycol monomethyl ether according to claim 1 is characterized in that acetate ylmethyl imidazolium hydroxide is to be prepared in accordance with the following methods: one, take by weighing 1-acyl group-3-Methochloride and KOH, NaOH, LiOH or NH by 1: 2 mol ratio
3H
2O, and soluble in water, under the condition of cooling bath, stir 5h then, get mixed solution C; Two, mixed solution C is warming up to 50 ℃, and the rotary evaporation that reduces pressure removes the water in the mixed solution C, then with anhydrous methanol washing 1 time and leave standstill 2h, mixing solutions D; Three, be the rotary evaporation 0.5h that reduces pressure under 40 ℃ the condition with mixing solutions D, get rid of the dehydrated alcohol among the mixing solutions D, promptly get acetate ylmethyl imidazolium hydroxide in temperature.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102964223A (en) * | 2012-11-13 | 2013-03-13 | 宁波杭州湾新区珠峰企业管理服务有限公司 | Preparation method of propylene glycol monomethyl ether |
| CN105921172A (en) * | 2016-05-20 | 2016-09-07 | 中国科学院过程工程研究所 | Application of ionic liquid in synthesis of propylene glycol ether and propylene glycol ether synthesis method |
| WO2017197857A1 (en) * | 2016-05-20 | 2017-11-23 | 中国科学院过程工程研究所 | Application of ionic liquid in propylene glycol ether synthesis and method for synthesizing propylene glycol ether |
| CN109867589A (en) * | 2017-12-01 | 2019-06-11 | 万华化学集团股份有限公司 | A kind of preparation method of propylene-glycol monoalky lether |
-
2009
- 2009-05-25 CN CN2009100721184A patent/CN101550069B/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102964223A (en) * | 2012-11-13 | 2013-03-13 | 宁波杭州湾新区珠峰企业管理服务有限公司 | Preparation method of propylene glycol monomethyl ether |
| CN105921172A (en) * | 2016-05-20 | 2016-09-07 | 中国科学院过程工程研究所 | Application of ionic liquid in synthesis of propylene glycol ether and propylene glycol ether synthesis method |
| WO2017197857A1 (en) * | 2016-05-20 | 2017-11-23 | 中国科学院过程工程研究所 | Application of ionic liquid in propylene glycol ether synthesis and method for synthesizing propylene glycol ether |
| CN107400043A (en) * | 2016-05-20 | 2017-11-28 | 中国科学院过程工程研究所 | Application and propylene glycol synthetic method of the ionic liquid in propylene glycol synthesis |
| US10604468B2 (en) * | 2016-05-20 | 2020-03-31 | Institute Of Process Engineering, Chinese Academy Of Sciences | Application of ionic liquid in propylene glycol ether synthesis and method for synthesizing propylene glycol ether |
| CN107400043B (en) * | 2016-05-20 | 2020-12-29 | 中国科学院过程工程研究所 | Application of ionic liquid in synthesis of propylene glycol ether and synthesis method of propylene glycol ether |
| CN109867589A (en) * | 2017-12-01 | 2019-06-11 | 万华化学集团股份有限公司 | A kind of preparation method of propylene-glycol monoalky lether |
| CN109867589B (en) * | 2017-12-01 | 2022-04-19 | 万华化学集团股份有限公司 | Preparation method of propylene glycol monoalkyl ether |
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