A method of preparing bis- (dimethoxyethoxy) methane
阅读说明：本技术 一种制备双（二甲氧基乙氧基）甲烷的方法 (A method of preparing bis- (dimethoxyethoxy) methane ) 是由 熊东路 莫志文 杨轩 徐涛 肖增均 于 2019-09-09 设计创作，主要内容包括：本发明公开了一种制备双(二甲氧基乙氧基)甲烷的方法,涉及化工合成技术领域。所述方法包括步骤：将乙二醇单甲醚与甲醛在酸催化剂的作用下,进行醇醛缩合反应制得双(二甲氧基乙氧基)甲烷；其中,甲醛与乙二醇单甲醚的摩尔比为1:2-4；所述酸催化剂的用量为0.1-10％；反应温度为60-140℃,反应时间为0.5-24小时。本发明用酸催化乙二醇单甲醚与甲醛反应生成双(二甲氧基乙氧基)甲烷,属于经济反应,产物包括水,不含副产物,且催化剂对设备腐蚀很小,是一种能重复利用催化剂的清洁的双(二甲氧基乙氧基)甲烷合成方法,适宜工业上的连续生产。(The invention discloses a kind of methods for preparing bis- (dimethoxyethoxy) methane, are related to technical field of chemical synthesis.The method includes the steps: by glycol monoethyl ether and formaldehyde under the action of acid catalyst, carries out aldol reaction and bis- (dimethoxyethoxy) methane are made；Wherein, the molar ratio of formaldehyde and glycol monoethyl ether is 1:2-4；The dosage of the acid catalyst is 0.1-10%；Reaction temperature is 60-140 DEG C, and the reaction time is 0.5-24 hours.The present invention, which is reacted with acid catalysis glycol monoethyl ether with formaldehyde, generates bis- (dimethoxyethoxy) methane, belong to economic response, product includes water, without by-product, and catalyst corrodes very little to equipment, it is a kind of clean bis- (dimethoxyethoxy) methane synthetic methods that can reuse catalyst, is suitable for industrial continuous production.)
1. a kind of method for preparing bis- (dimethoxyethoxy) methane, which is characterized in that comprising steps of
By glycol monoethyl ether and formaldehyde under the action of acid catalyst, carries out aldol reaction and bis- (dimethoxy second are made Oxygroup) methane；
Wherein, the molar ratio of formaldehyde and glycol monoethyl ether is 1:2-4；The dosage of the acid catalyst is reactant quality 0.1-10%；Reaction temperature is 60-140 DEG C, and the reaction time is 0.5-24 hours.
2. the method for bis- (dimethoxyethoxy) methane of preparation as described in claim 1, which is characterized in that reaction system Middle addition water entrainer, the dosage of the water entrainer are equivalent to 0.5-1.5 times of reactant quality.
3. the method for bis- (dimethoxyethoxy) methane of preparation as claimed in claim 2, which is characterized in that the water entrainer For at least one of toluene, thiacyclohexane, hexahydrotoluene.
4. the method for bis- (dimethoxyethoxy) methane of preparation as claimed in claim 2, which is characterized in that further include product Separating-purifying step, specifically:
The aldol reaction is filtered to after generating there is no water, neutralizes, water entrainer is evaporated off, obtains containing residual reactant And the mixture of bis- (dimethoxyethoxy) methane；
Water is added into the mixture, oily phase is collected after layering；The oil is mutually removed water, 24mm mercury column is collected in vacuum distillation Under pressure, 100-101 DEG C of fraction is to get bis- (dimethoxyethoxy) methane for arriving high-purity.
5. the method for bis- (dimethoxyethoxy) methane of preparation as described in claim 1, which is characterized in that the formaldehyde is Paraformaldehyde, the formalin of metaformaldehyde or 25% or more.
6. the method for bis- (dimethoxyethoxy) methane of preparation as described in claim 1, which is characterized in that the acid catalysis Agent includes solid acid catalyst, molecular sieve or ionic liquid.
7. the method for bis- (dimethoxyethoxy) methane of preparation as claimed in claim 6, which is characterized in that the solid acid Catalyst includes alkyl-substituted benzene sulfonic acid, alkyl-substituted naphthalene sulfonic acids, non-alkyl-substituted benzene sulfonic acid, non-alkyl-substituted naphthalene Sulfonic acid, poly- sulfonic resin, poly- perfluorosulfonic acid type resin, heteropoly acid and heteropolyacid salt, single or complex carrier SO4 2-/MXOY Solid super-strong acid, single or complex carrier S2O8 2-/MXOYAt least one of solid super-strong acid, wherein MXOYFor NiO, TiO2, ZrO2, SiO2, SnO2, Fe2O3, Al2O3, WO3And MoO3At least one of.
Technical field
The present invention relates to technical field of chemical synthesis more particularly to a kind of sides for preparing bis- (dimethoxyethoxy) methane Method.
Background technique
Bis- (dimethoxyethoxy) methane IUPAC are named as 2,5,7,10- tetra- oxygen hendecanes, are a kind of colorless and transparent liquid Body, smell is mild, and 201.5 DEG C of boiling point, density 0.9921g/cm3, 88 DEG C of flash-point, freezing point is less than -65 DEG C, soluble easily in water, category In the acetal compound of degradable green.
Bis- (dimethoxyethoxy) methane can be used as solvent for coating, ink, adhesive, the industries such as pesticide.It has High Cetane number has extremely low freezing point, therefore can also be used as addition of the fuel oil additive for diesel oil.Bis- (diformazans Oxygroup ethyoxyl) methane can also reduce the discharge of harmful substance as diesel fuel additives, it is particularly conducive to reduce diesel engine The discharge of PM2.5 in tail gas.
Currently, the synthetic method of bis- (dimethoxyethoxy) methane has: (1) utilizing diiodomethane and glycol monoethyl ether Reaction generates bis- (dimethoxyethoxy) methane；(2) it is reacted using glycol monoethyl ether with 2- methoxvethoxvmethvl chlorine Generate bis- (dimethoxyethoxy) methane；(3) it is formed using acid catalysis glycol monoethyl ether with formaldehyde condensation.United States Patent (USP) US2036303, US2036304, which are reported, makees bis- (dimethoxyethoxy) methane of catalyst synthesis with iron chloride.Sidney D.ROS et al. and Sokolowski et al., which is reported, makees bis- (dimethoxyethoxy) first of catalyst synthesis with p-methyl benzenesulfonic acid Alkane, yield is up to 72% (Polish Journal of Chemistry1979vol.53p.905-912, Journal of the American Chemical Society1973vol.95p.2193–2198).In addition, United States Patent (USP) US2331367 is also reported Synthesize bis- (dimethoxyethoxy) methane with sulphur acid as catalyst.
However, the method for bis- (dimethoxyethoxy) methane of synthesis is all homogeneous catalytic reaction at present, need to use dense Sulfuric acid or p-methyl benzenesulfonic acid make catalyst, severe corrosion to equipment, and are difficult to be made into continuous production.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of catalyst, economical in reaction, height small to equipment corrosiveness The method of bis- (dimethoxyethoxy) methane of the preparation of effect.
To solve the above-mentioned problems, the present invention proposes following technical scheme:
A method of bis- (dimethoxyethoxy) methane are prepared, comprising steps of
By glycol monoethyl ether and formaldehyde under the action of acid catalyst, carries out aldol reaction and bis- (dimethoxies are made Base oxethyl) methane；
Wherein, the molar ratio of formaldehyde and glycol monoethyl ether is 1:2-4；The dosage of the acid catalyst is reactant quality 0.1-10%；Reaction temperature is 60-140 DEG C, and the reaction time is 0.5-24 hours.
It further further includes that water entrainer is added into reaction system, and the dosage of the water entrainer is equivalent to reactant 0.5-1.5 times of quality.
Its further, the water entrainer be at least one of toluene, thiacyclohexane, hexahydrotoluene.
It further includes further product separating-purifying step, specifically:
The aldol reaction is filtered to after generating there is no water, neutralizes, water entrainer is evaporated off, and is obtained containing remaining anti- Answer the mixture of object and bis- (dimethoxyethoxy) methane；
Water is added into the mixture, oily phase is collected after layering；The oil is mutually removed water, 24mm is collected in vacuum distillation Under mercurypressure, 100-101 DEG C of fraction is to get bis- (dimethoxyethoxy) methane for arriving high-purity.
Its further, the formaldehyde be paraformaldehyde, the formalin of metaformaldehyde or 25% or more.
Its further, the acid catalyst includes solid acid catalyst, molecular sieve or ionic liquid.
Its further, the solid acid catalyst includes alkyl-substituted benzene sulfonic acid, alkyl-substituted naphthalene sulfonic acids, non-alkane Benzene sulfonic acid that base replaces, non-alkyl-substituted naphthalene sulfonic acids, poly- sulfonic resin, poly- perfluorosulfonic acid type resin, heteropoly acid and miscellaneous more Hydrochlorate, single or complex carrier SO4 2-/MXOYSolid super-strong acid, single or complex carrier S2O8 2-/MXOYIn solid super-strong acid At least one, wherein MXOYFor NiO, TiO2, ZrO2, SiO2, SnO2, Fe2O3, Al2O3, WO3And MoO3At least one of.
Compared with prior art, the attainable technical effect of present invention institute includes: present invention acid catalysis ethylene glycol list first Ether is reacted with formaldehyde generates bis- (dimethoxyethoxy) methane, belongs to economic response, and product includes water, is free of by-product, and Catalyst corrodes very little to equipment, is a kind of clean bis- (dimethoxyethoxy) methane synthesis that can reuse catalyst Method is suitable for industrial continuous production.
Specific embodiment
The technical solution in embodiment will be clearly and completely described below.Obviously, it will be described below embodiment Only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field Art personnel every other embodiment obtained without creative efforts belongs to the model that the present invention protects It encloses.
It should be appreciated that ought use in this specification and in the appended claims, term " includes " and "comprising" instruction Described feature, entirety, step, operation, the presence of element and/or component, but one or more of the other feature, whole is not precluded Body, step, operation, the presence or addition of element, component and/or its set.
It is also understood that in this embodiment of the present invention term used in the description merely for the sake of description particular implementation Example purpose and be not intended to limit the embodiment of the present invention.Such as the institute in specification and appended book of the embodiment of the present invention As use, other situations unless the context is clearly specified, otherwise " one " of singular, "one" and "the" are intended to wrap Include plural form.
The embodiment of the present invention provides a kind of method for preparing bis- (dimethoxyethoxy) methane, comprising steps of
By glycol monoethyl ether and formaldehyde under the action of acid catalyst, carries out aldol reaction and bis- (dimethoxies are made Base oxethyl) methane；
Wherein, the molar ratio of formaldehyde and glycol monoethyl ether is 1:2-4；The dosage of the acid catalyst is reactant quality 0.1-10%；Reaction temperature is 60-140 DEG C, and the reaction time is 0.5-24 hours.
Reactive chemistry formula sees below formula (1):
By formula (1) it is found that including water in the obtained product of reaction, therefore, in specific implementation, above-mentioned steps further include, Water entrainer is added into reaction system, the dosage of the water entrainer is equivalent to 0.5-1.5 times of reactant quality.By in time will Water is taken out of, promotes reaction forward to carry out, conversion ratio can be improved, and obtains higher yield.