CN101735052B - Method for preparing dibutyl itaconate - Google Patents
Method for preparing dibutyl itaconate Download PDFInfo
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- CN101735052B CN101735052B CN200910231146.6A CN200910231146A CN101735052B CN 101735052 B CN101735052 B CN 101735052B CN 200910231146 A CN200910231146 A CN 200910231146A CN 101735052 B CN101735052 B CN 101735052B
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- dibutyl itaconate
- methylene
- succinic acid
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Abstract
The invention discloses a method for preparing dibutyl itaconate. In particular, the method comprises the following steps of: adopting a novel high-efficiency catalysis-polymerization inhibition combined system to catalyze the reaction of itaconic acid and normal butyl alcohol at normal pressure and a temperature of between 90 and 130 DEG C for 2 to 8 hours to form the dibutyl itaconate, wherein the catalysis-polymerization inhibition combined system comprises a catalyst of strong acid ion exchange resin and a polymerization inhibitor of hydroquinone. Compared with the conventional acid catalytic method, the method of the invention has the characteristics that: 1, the reaction time is short, and the energy consumption is low; 2, in a process of esterification, polymers are hardly generated, and the selectivity is high; 3, the product of the dibutyl itaconate is automatically separated from the catalyst, and the separating process is easier; and 4, the used catalyst in the reaction can be directly reused without treatment.
Description
Technical field
The present invention relates to a kind of method of preparing dibutyl itaconate, be specifically related to a kind of method of preparing dibutyl itaconate by strong-acid ion exchange resin catalysis methylene-succinic acid and propyl carbinol esterification.
background technology
Dibutyl itaconate is water white oily liquids, and low toxicity is the intermediate of a kind of important reactive monomer, comonomer and organic synthesis, or the internal plasticizer of multiple plastics; It can autohemagglutination and copolymerization, and the resulting product of copolymerization is widely used in formed material, coating material, fiber and film treatment agent, lubricating oil and additive thereof, binding agent ion exchange resin etc.The multipolymer that contains dibutyl itaconate and vinyl-acetic ester, has good effect of heat insulation; Dibutyl itaconate joins in washing composition, can improve washing effect; Dibutyl itaconate also can be used as solvent for the preparation of color photography latex, extraordinary ink etc.In addition, dibutyl itaconate can also be as the linking agent of gelation promotor, rust-inhibiting additive, tackiness agent and unsaturated polyester.Along with the development of the industries such as coating, paint, rubber, agricultural chemicals, washing composition, plastics, dibutyl itaconate has more and more wider purposes.Preparing the easiest method of dibutyl itaconate is to adopt the vitriol oil to make the direct esterification of catalyzer, but because strong oxidizing property feature and the production technique of the vitriol oil are perfect not, so there is more side reaction, and then cause that products obtained therefrom color is dark, purity is low, and in production process, produce the problems such as the three wastes (especially waste water).
summary of the invention
The object of the invention is to replace traditional protonic acid catalysis methylene-succinic acid and propyl carbinol esterification and prepare the method for dibutyl itaconate, a kind of new and effective catalysis, inhibition compound system are provided, catalysis methylene-succinic acid and propyl carbinol esterification are prepared the novel method of dibutyl itaconate, the method has not etching apparatus, three wastes discharge amount few and under gentle reaction conditions product yield advantages of higher.
Its technical scheme is:
Adopt a kind of new and effective catalysis, inhibition compound system catalysis methylene-succinic acid and propyl carbinol reaction to generate dibutyl itaconate; In described catalysis, inhibition compound system, comprise catalyzer, described catalyzer is strong-acid ion exchange resin.
In above-mentioned catalysis, inhibition compound system, comprise stopper, described stopper is Resorcinol.
The mass ratio of above-mentioned strong-acid ion exchange resin and methylene-succinic acid is 1: 20～1: 5, and Resorcinol is 1: 200～1: 100 with the ratio of methylene-succinic acid quality, and the mass ratio of methylene-succinic acid and propyl carbinol is 1: 1.4～1: 3.
The above-mentioned method of preparing dibutyl itaconate specifically comprises the following steps:
A chooses methylene-succinic acid, propyl carbinol, strong-acid ion exchange resin and Resorcinol, adds successively in reactor, stirs, and at 90 ℃～130 ℃, reacts 2～8 hours, obtains dibutyl itaconate crude product;
B, to dibutyl itaconate filtration of crude product, obtains filtrate and filter cake, and filtrate obtains dibutyl itaconate finished product through washing, underpressure distillation successively.
In above-mentioned steps a, also choose band aqua, band aqua joins in reactor before reaction or in reaction process, and the described mass ratio with aqua and methylene-succinic acid is 1: 10～1: 5.
Above-mentioned is a kind of in benzene, toluene or dimethylbenzene with aqua.
The present invention compares with the method that adopts traditional protonic acid catalysis methylene-succinic acid to prepare dibutyl itaconate with propyl carbinol reaction, has following features:
1. temperature of reaction is low, and the time is short, less energy consumption.
Product can with ion exchange resin layering voluntarily, make the separation of product and aftertreatment more easy.
3. the ion exchange resin that reaction was used, can be used for reaction next time, and catalytic performance has no reduction without any processing.
4. in reaction process, non-polymer generates, and products therefrom look shallow, matter good, yield is high.
5. overcome the liquid catalyst existing in background technology and can not recycle after reaction finishes, and the serious problem of environmental pollution.
Embodiment
The present invention adopts new and effective catalysis, inhibition compound system catalysis methylene-succinic acid to react with propyl carbinol, and the mass ratio of methylene-succinic acid and propyl carbinol is 1: 1.4～1: 3, preferably 1: 2; Catalysis, inhibition compound system comprise catalyzer strong-acid ion exchange resin, in order to prevent the generation of polymkeric substance, we preferably adopt catalysis, the inhibition compound system being comprised of catalyzer and stopper the yield of raising product, wherein catalyzer is strong-acid ion exchange resin, the preferred Resorcinol of stopper.The mass ratio of strong-acid ion exchange resin and methylene-succinic acid is 1: 20～1: 5 preferably 1: 15～1: 8, more preferably 1: 12～1: 10; The mass ratio of Resorcinol and methylene-succinic acid is 1: 200～1: 100, and preferably the mass ratio of Resorcinol and methylene-succinic acid is 1: 150.
The present invention is simultaneously the esterification of methylene-succinic acid and propyl carbinol, and esterification is reversible reaction, and in order to improve esterification yield, we can also add band aqua in reactor, in order to remove the water molecules producing in reaction process.Band aqua can join in reactor before reaction, also can visual response water outlet situation join in reactor in reaction process.The present invention preferentially selects a kind of for band aqua in benzene,toluene,xylene, sometimes according to the difference of reaction conditions, also can select wherein the mixture of the two or three's mixture.Consumption with belt transect aqua is suitable, and the weight ratio with aqua and methylene-succinic acid in the present invention is 1: 10～1: 5, preferably 1: 8～1: 6, is more preferably 1: 7.When with aqua consumption, be less than methylene-succinic acid weight 1/10th time, esterification yield is low, esterification temperature is also wayward; But when be greater than five of methylene-succinic acid weight/for the moment, cause the relative concentration of reactant to reduce with the consumption of aqua, also reduced esterification yield.
In above-mentioned steps b, filter cake composition is mainly strong-acid ion exchange resin, certainly also contain micro-stopper, so can collect, catalyzer as next esterification is standby, in addition, due to the premium properties of strong-acid ion exchange resin, we do not need that used strong-acid ion exchange resin is done to any processing and can be used for reaction next time during this period.
Feature due to above-mentioned strong-acid ion exchange resin, we can also adopt following step to come alternative steps b to carry out purifying to dibutyl itaconate crude product, that is: by standing for some time of dibutyl itaconate crude product, layering, directly pour out upper strata product and obtain mutually dibutyl itaconate finished product, in order further to improve the purity of dibutyl itaconate finished product, we can also simply wash and underpressure distillation removes the steps such as water and unreacted propyl carbinol mutually to the upper strata product of directly pouring out; Lower floor's strong-acid ion exchange resin can be used for next esterification without any processing.
Below by specific embodiment, the present invention is further described.
Embodiment 1
Buy from the market methylene-succinic acid, propyl carbinol, strongly-acid amberlite, Resorcinol, benzene, toluene and dimethylbenzene, take 100Kg methylene-succinic acid, 140Kg propyl carbinol, 5Kg strong-acid ion exchange resin, 1Kg Resorcinol, add successively in reactor, on reactor, be provided with agitator and thermometer, start agitator by the raw material blending in reactor, after being heated to 130 ℃, start timing, react 6 hours, obtain dibutyl itaconate crude product; Stop heating, be cooled to room temperature and then filter, obtain filtrate and filter cake, filtrate is washed, then underpressure distillation removes water and unreacted propyl carbinol, obtains dibutyl itaconate finished product, yield 85%.Filter cake reclaims, and does not need to be directly used in next esterification through any processing.
Embodiment 2
Raw material acquisition pattern is with embodiment 1, take 100Kg methylene-succinic acid, 300Kg propyl carbinol, 20Kg strong-acid ion exchange resin, 0.5Kg Resorcinol and 10Kg dimethylbenzene, drop in reactor, on reactor, be provided with agitator, thermometer and water trap, start agitator raw material is mixed, when stirring, reactor is heated, be heated to 90 ℃ and start timing, react 8 hours, obtain dibutyl itaconate crude product; Dibutyl itaconate crude product is carried out cooling, can naturally cooling, certainly in order to save time, also can adopt tap water cooling, the method for purification, with embodiment 1, obtains dibutyl itaconate finished product, yield 98.7%.
Embodiment 3
Raw material acquisition pattern is with embodiment 1, take 80Kg methylene-succinic acid, 160Kg propyl carbinol, 10Kg strong-acid ion exchange resin, 0.75Kg Resorcinol and 20Kg benzene, drop in reactor, on reactor, be provided with agitator, thermometer and water trap, start agitator raw material is mixed, when stirring, reactor is heated, be heated to 120 ℃ and start timing, react 6 hours, obtain dibutyl itaconate crude product; Dibutyl itaconate crude product is carried out to naturally cooling, cooled dibutyl itaconate crude product is standing, after layering, directly upper strata product is poured out mutually, obtain dibutyl itaconate finished product, yield 95.9%; Lower floor's strong-acid ion exchange resin can be used for next esterification without any processing.
Embodiment 4
Raw material acquisition pattern is with embodiment 1, take 60Kg methylene-succinic acid, 130Kg propyl carbinol, 3Kg strong-acid ion exchange resin, 0.4Kg Resorcinol and 8Kg toluene, drop in reactor, on reactor, be provided with agitator, thermometer and water trap, start agitator raw material is mixed, when stirring, reactor is heated, be heated to 125 ℃ and start timing, react 7 hours, obtain dibutyl itaconate crude product; Dibutyl itaconate crude product is carried out to naturally cooling, cooled dibutyl itaconate crude product is standing, after layering, directly upper strata product is poured out mutually, again the upper strata product of pouring out is removed to water and unreacted propyl carbinol and a small amount of residual dewatering agent toluene step through washing, underpressure distillation mutually successively, obtain dibutyl itaconate finished product, yield 97.8%; Lower floor's ion exchange resin can be used for next esterification without any processing.
Above-described embodiment is explained in detail the present invention, but the present invention is not limited to above-described embodiment, in the ken possessing, can also make many variations to it those of ordinary skills.For example, the feed way in above-described embodiment is not to add simultaneously but successively add, and as Resorcinol, benzene, dimethylbenzene etc. can add in reaction process, or even a kind of material adds several times.
Claims (2)
1. a method of preparing dibutyl itaconate, is characterized in that adopting a kind of new and effective catalysis, inhibition compound system catalysis methylene-succinic acid and propyl carbinol reaction to generate dibutyl itaconate;
In described catalysis, inhibition compound system, comprise catalyzer, described catalyzer is strong-acid ion exchange resin;
In described catalysis, inhibition compound system, comprise stopper, described stopper is Resorcinol;
Described strong-acid ion exchange resin and the mass ratio of methylene-succinic acid are 1: 20～1: 5;
Described stopper and the mass ratio of methylene-succinic acid are 1: 200～1: 100;
Described methylene-succinic acid and the mass ratio of propyl carbinol are 1: 1.4～1: 3;
Specifically comprise the following steps:
A chooses methylene-succinic acid, propyl carbinol, strong-acid ion exchange resin and Resorcinol, adds successively in reactor, stirs, and at 90 ℃～130 ℃, reacts 2～8 hours, obtains dibutyl itaconate crude product;
B, to dibutyl itaconate filtration of crude product, obtains filtrate and filter cake, and filtrate obtains dibutyl itaconate finished product through washing, underpressure distillation successively;
In described step a, also choose band aqua, band aqua joins in reactor before reaction or in reaction process, and the described mass ratio with aqua and methylene-succinic acid is 1: 10～1: 5.
2. a kind of method of preparing dibutyl itaconate according to claim 1, is characterized in that described band aqua is benzene, toluene or dimethylbenzene.
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| CN200910231146.6A CN101735052B (en) | 2009-12-10 | 2009-12-10 | Method for preparing dibutyl itaconate |
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| CN109485563A (en) * | 2017-09-12 | 2019-03-19 | 北京化工大学 | A method of dibutyl itaconate is prepared based on heterocatalysis efficient green |
| CN111321176B (en) * | 2020-03-11 | 2021-11-09 | 北京化工大学 | Method for preparing 4-monooctyl itaconate by enzymatic selective catalysis |
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Non-Patent Citations (6)
| Title |
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| H4SiW12O40催化合成衣康酸二甲酯;谷亚昕;《化工时刊》;20081231;第22卷(第1期);35-36 * |
| 于世涛.衣康酸二甲酯的合成.《精细化工》.2002,第19卷(第4期),238-240. |
| 候晓红.衣康酸二正丁酯的合成工艺研究.《化学与黏合》.2006,第28卷(第2期),99-100. |
| 衣康酸二正丁酯的合成工艺研究;候晓红;《化学与黏合》;20061231;第28卷(第2期);99-100 * |
| 衣康酸二甲酯的合成;于世涛;《精细化工》;20021231;第19卷(第4期);238-240 * |
| 谷亚昕.H4SiW12O40催化合成衣康酸二甲酯.《化工时刊》.2008,第22卷(第1期),35-36. |
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