CN103193675A - Method for preparing ethyl methacrylate isocyanate - Google Patents
Method for preparing ethyl methacrylate isocyanate Download PDFInfo
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- CN103193675A CN103193675A CN2013100997769A CN201310099776A CN103193675A CN 103193675 A CN103193675 A CN 103193675A CN 2013100997769 A CN2013100997769 A CN 2013100997769A CN 201310099776 A CN201310099776 A CN 201310099776A CN 103193675 A CN103193675 A CN 103193675A
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- trichloromethyl
- methacrylic acid
- carbonic ether
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- jia jibingxisuanyizhi
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Abstract
The invention discloses a method for preparing ethyl methacrylate isocyanate. According to the method, an inhibitor and a catalyst N,N-dimethylformamide are added into methacrylic acid as the raw material, a mixture solution of bis(trichloromethyl) carbonate A and an organic solvent A is dripped inside under the protection of nitrogen gas, and then ethanolamine hydrochloride is added to prepare a methacrylate aminoethyl hydrochloride solution; and an organic base is added to the methacrylate aminoethyl hydrochloride solution, and a mixture solution of bis(trichloromethyl) carbonate B and an organic solvent B is dripped inside, and the ethyl methacrylate isocyanate is obtained after reaction. Based on the method, the use of toxic and harmful phosgene and the production of side products are avoided; the method is beneficial for safety production, has the advantages that raw material is low in price and easily obtained; and the reaction conditions are modest, the reaction yield is high and so on, and effectively solves the problems of tedious operation, low yield, serious environmental pollution and the like in the existing methods.
Description
(1) technical field
The present invention relates to a kind of preparation method of Jia Jibingxisuanyizhi isocyanic ester.
(2) background technology
Jia Jibingxisuanyizhi isocyanic ester (MOI) contains isocyanate group and the polymerisable carbon-to-carbon double bond of high reaction activity, can be used for producing various functional polymer materials, as liquid photo-resist, film photo-resist and tackiness agent etc., be widely used in fields such as medical treatment, electronics, printing, building, automobile, household electrical appliances, glass.Japan is clear to declare with electrician company, and compare with traditional isocyanate-monomer, the MOI monomer is used for phototype setting higher rate.
The synthetic route of report Jia Jibingxisuanyizhi isocyanic ester mainly contains in the existing document:
1, phosgenation
Japanese Patent JP63010750 has reported that with the 2-oxazolidone be raw material, at first with hydrogenchloride generation ring-opening reaction, the gained compound again with methacrylic acid generation esterification, obtain the Jia Jibingxisuanyizhi isocyanic ester with phosgene reaction then, yield is 45%.
Japanese Patent JP02129163 discloses the use methacrylic chloride and the ethanolamine hydrochloric salt reaction generates methacrylic acid amino-ethyl ester hydrochloride, generates the Jia Jibingxisuanyizhi isocyanic ester with phosgene reaction then, and yield is 56%.
Phosgenation prepares isocyanic ester and has more deficiency, and for example: phosgene is severe toxicity, explosion hazard gases, all has potential safety hazard in preparation, storage, use, and is bigger to environmental hazard; Metering and inconvenient operation; The content height of hydrolyzable chlorine can influence quality product in the product.And the HCl that in reaction process, produces can with the two key generation addition reactions of methacryloyl, thereby cause reaction yield low.
The side reaction that addition reaction causes takes place for solving on the two keys of propenyl, Japan Showa Denko K. K has reported with the methacrylic acid to be raw material, make 3-chloro-2-methyl-prop acyl chlorides with phosgene reaction earlier, obtain 3-chloro-2 Methylpropionic acid (2-ethyl isocyanate base) ester with ethanolamine hydrochloric salt, phosgene reaction successively then, eliminate reaction finally by triethylamine catalysis and make Jia Jibingxisuanyizhi isocyanic ester (CN1934075), the final step yield is 70%.Yet this method has also been used hypertoxic phosgene, and intermediate need separate, and causes operating process more loaded down with trivial details, the unfavorable suitability for industrialized production of using.
2, N, N-carbonyl dimidazoles method
EP2377847 discloses a kind of N of utilization, the method of N-carbonyl dimidazoles synthesize methyl acrylic acetoacetic ester isocyanic ester, this method comprises: with tosic acid monohydrate, methacrylic acid, thanomin hybrid reaction, make methacrylic acid amino-ethyl ester tosilate through salify, esterification, again with N, the reaction of N-carbonyl dimidazoles generates methacrylic acid-2-[(imidazoles-1-carbonyl)-amino]-ethyl ester, add the tosic acid monohydrate then, behind the reflux dewatering, make the Jia Jibingxisuanyizhi isocyanic ester finally by thermolysis, yield is 48%.The deficiency of this method is raw material N, and N-carbonyl dimidazoles price is higher, and N, and the N-carbonyl dimidazoles is still and adopts phosgene synthetic, and reaction yield is lower, long reaction time, and operating process is more loaded down with trivial details, causes industrialization cost height.
3, carbamate thermal decomposition method
JP05186415 has reported and has used the 2-[(methoxycarbonyl) amino] Jia Jibingxisuanyizhi is raw material, is B at atomic ratio
1P
1Si
5Under the catalyst action of (except Sauerstoffatom), make the Jia Jibingxisuanyizhi isocyanic ester in 350 ℃ of following thermolysiss, yield is 78%.This method raw material is not easy to obtain, the temperature of reaction height, and energy consumption is big, to the requirement harshness of equipment, and product easily polymerization at high temperature.
(3) summary of the invention
The object of the invention provides a kind of synthetic method of Jia Jibingxisuanyizhi isocyanic ester, and this method reaction yield height, production cost is low, reaction conditions is gentle, simple and safe operation, environmental friendliness.
The technical solution used in the present invention is:
The invention provides a kind of preparation method of Jia Jibingxisuanyizhi isocyanic ester, described method is:
(1) with the methacrylic acid is raw material, add stopper and catalyzer, under 30～120 ℃, drip the mixing solutionss of two (trichloromethyl) carbonic ether A and organic solvent A under the nitrogen protection, insulation reaction was down to room temperature after 1～10 hour, drop into ethanolamine hydrochloric salt under the nitrogen protection, in 30～120 ℃ of stirring reactions 2～10 hours, make and contain methacrylic acid amino ethyl ester hydrochloride solution; Described stopper is one or more the combination in Resorcinol, cuprous chloride, thiodiphenylamine, MEHQ or the 2,6 di tert butyl 4 methyl phenol, is preferably thiodiphenylamine or Resorcinol; Described catalyzer is N, dinethylformamide; The amount of substance ratio that feeds intake of described methacrylic acid and stopper, catalyzer, two (trichloromethyl) carbonic ether A, ethanolamine hydrochloric salt is 1.0:0.001～0.1:0.001～0.01:0.3～1.0:0.8～1.2; Described organic solvent A quality consumption is 2～20 times of two (trichloromethyl) carbonic ether quality;
(2) in the methacrylic acid amino ethyl ester hydrochloride solution of step (1) gained, add organic bases under the nitrogen protection, slowly drip the mixing solutions of being formed by two (trichloromethyl) carbonic ether B and organic solvent B down at 40～150 ℃ then, after the insulation reaction 3～10 hours, after the reaction solution aftertreatment got the organic layer drying, obtain the Jia Jibingxisuanyizhi isocyanic ester; The amount of substance ratio that adds methacrylic acid in described organic bases and the step (1) is 0.1～3:1; The amount of substance ratio that adds methacrylic acid in described two (trichloromethyl) carbonic ether B and the step (1) is 0.3～1.0:1; Described organic solvent B quality consumption is 1～20 times of two (trichloromethyl) carbonic ether quality.
Further, the temperature that drips the mixing solutions of two (trichloromethyl) carbonic ether A and organic solvent A in the described step (1) is 40～60 ℃, and the insulation reaction time is 3～5 hours.
Further, drop in the described step (1) behind the ethanolamine hydrochloric salt in 60～90 ℃ of stirring reactions 4～8 hours.
Further, the amount of substance ratio that feeds intake of methacrylic acid and stopper described in the described step (1), catalyzer, two (trichloromethyl) carbonic ether A, ethanolamine hydrochloric salt is 1.0:0.005～0.01:0.001～0.005:0.4～0.6:1.0.
Further, organic solvent A is methylene dichloride, trichloromethane, ethyl acetate, 1 in the described step (1), and one or more combination in 2-ethylene dichloride, benzene,toluene,xylene, chlorobenzene, the santochlor is preferably toluene or chlorobenzene.
Further, organic bases is triethylamine, Tri-n-Propylamine, tri-isopropyl amine, tri-n-butylamine, tri-isobutylamine, diisopropylethylamine, dimethylcyclohexylamine, pyridine, 4-dimethylamino pyridine, N-methyl beautiful jade, N-methyl piperidine, N in the described step (2), N dimethylamine base-4-pyridine, N, dinethylformamide, N, N-lupetidine, N, accelerine or N, the combination of one or more in the N-Diethyl Aniline, be preferably tri-n-butylamine or N, accelerine.
Further, the temperature that drips the mixing solutions of being made up of two (trichloromethyl) carbonic ether B and organic solvent B in the step (2) is 70～110 ℃, and the reaction times is 3～5h.
Further, the amount of substance ratio of adding methacrylic acid is 0.8～1.5:1 in organic bases described in the step (2) and the step (1); The amount of substance ratio that adds methacrylic acid in described two (trichloromethyl) carbonic ether B and the step (1) is 0.45～0.6:1.
Further, organic solvent B is methylene dichloride, trichloromethane, ethyl acetate, 1 in the described step (2), one or more combination in 2-ethylene dichloride, benzene,toluene,xylene, chlorobenzene, the santochlor, described organic solvent B is identical with organic solvent A, is preferably toluene or chlorobenzene.
Further, the reaction solution post-treating method is described in the described step (2): after reaction finishes, reaction solution is cooled to room temperature, filter, the washing of gained filtrate water, the organic layer drying of telling, concentrated solvent, 87～89 ℃/10mmHg of the underpressure distillation collection cut of reclaiming, drying obtains the Jia Jibingxisuanyizhi isocyanic ester.
Beneficial effect of the present invention is embodied in:
(1) adds organic bases in the reaction process, can effectively stop the formation of by product 3-chloro-2 Methylpropionic acid (2-ethyl isocyanate base) ester, and then improve reaction yield, reduced the content of remaining hydrolysis chlorine in the product simultaneously, improved quality product.
(2) reaction conditions gentleness, and respectively go on foot reaction intermediate and need not separation and purification, directly can be used for the next step, thereby simplified operation sequence.
(3) be raw material with methacrylic acid cheap and easy to get, substitute poisonous and hazardous phosgene, sulfur oxychloride, phosphorus oxychloride as chloride reagent with two (trichloromethyl) carbonic ether, the on-site preparation methacrylic chloride, rather than the β-chloro propionyl chloride of CN1934075 report, reduced environmental pollution, and avoided direct and used the methacrylic chloride expensive, that toxicity is big, pungency is strong to be raw material.
(4) the alternative phosgene of two (trichloromethyl) carbonic ethers of the friendly reagent of environment for use prepares the Jia Jibingxisuanyizhi isocyanic ester, has eliminated potential safety hazard from the source, has reaction conditions gentleness, easy and simple to handle, yield advantages of higher.
Organic solvent A of the present invention, organic solvent B are organic solvent, name for ease of distinguishing the used organic solvent difference of each step, and letter itself does not have implication.
Compared with prior art, beneficial effect of the present invention is mainly reflected in: the present invention avoids using the formation of poisonous and hazardous phosgene and by product, be conducive to safety in production and have problems such as raw material is cheap and easy to get, reaction conditions is gentle, the reaction yield advantages of higher, and complex operation, the yield that efficiently solves existing method existence is low, environmental pollution is serious.Therefore, the inventive method has bigger implementary value and society, economy, environmental benefit.
(4) embodiment
The present invention is described further below in conjunction with specific embodiment, but protection scope of the present invention is not limited in this:
Embodiment 1:
(1) add in the 1L four neck flasks methacrylic acid (17.22g, 0.20mol), thiodiphenylamine (0.20g, 1mmol) and DMF (0.146g 2mmol), is warming up to 60 ℃ of (t under the nitrogen protection
1), slowly splash into by two (trichloromethyl) carbonic ether A(29.68g, 0.10mol) and the solution formed of toluene (59.35g), drip and finish insulation reaction 4h(T
1), get the methacryloyl chlorine solution; Be down to room temperature, (19.51g 0.20mol), is warming up to 65 ℃ of (t to drop into ethanolamine hydrochloric salt under the nitrogen protection
2), stirring reaction 6h(T
2).
(2) in the reaction solution of step (1) gained, add tri-n-butylamine (37.07g under the nitrogen protection; 0.20mol); under 110 ℃ (t3), slowly splash into then by two (trichloromethyl) carbonic ether B(29.68g; 0.10mol) and the solution formed of toluene (148.37g); drip and finish, continue insulation reaction 3h(T
3), after after reaction finishes reaction solution being cooled to room temperature (25 ℃), filter the washing of gained filtrate water, the organic layer anhydrous sodium sulfate drying, after reclaiming solvent, the cut of 87～89 ℃/10mmHg, drying are collected in underpressure distillation, get Jia Jibingxisuanyizhi isocyanic ester 25.20g, amount with methacrylic acid is calculated, and yield is that 81.2%, GC purity is 99.6%.
Embodiment 2:
With methacrylic acid in embodiment 1 step (1): thiodiphenylamine: DMF: two (trichloromethyl) carbonic ether A: ethanolamine hydrochloric salt feed intake amount of substance than being 1.0:0.005:0.005:0.7:1.0; Organic bases described in the step (2) is tri-n-butylamine, adds the amount of substance of methacrylic acid in organic bases and the step (1) than being 2.0:1.0; Add the amount of substance of methacrylic acid in two (trichloromethyl) carbonic ether B described in the step (2) and the step (1) than being 1.0:1.0.Other operations get Jia Jibingxisuanyizhi isocyanic ester 23.64g with embodiment 1, calculate with the amount of methacrylic acid, and yield is that 76.2%, GC purity is 99.7%.
Embodiment 3:
With methacrylic acid in the step (1): thiodiphenylamine: DMF: two (trichloromethyl) carbonic ether A: ethanolamine hydrochloric salt feed intake amount of substance than being 1.0:0.001:0.001:0.3:0.8; Organic bases described in the step (2) is tri-n-butylamine, adds the amount of substance of methacrylic acid in organic bases and the step (1) than being 3.0:1.0; Add the amount of substance of methacrylic acid in two (trichloromethyl) carbonic ether B described in the step (2) and the step (1) than being 0.3:1.0.Other operations are with embodiment 1.Get product Jia Jibingxisuanyizhi isocyanic ester 15.48g, calculate with the amount of methacrylic acid, yield is that 49.9%, GC purity is 99.5%.
Embodiment 4:
Methacrylic acid in the step (1): thiodiphenylamine: DMF: two (trichloromethyl) carbonic ether A: the amount of substance ratio that feeds intake of ethanolamine hydrochloric salt is 1.0:0.005:0.001:0.45:1.0; Organic bases described in the step (2) is triethylamine, adds the amount of substance of methacrylic acid in organic bases and the step (1) than being 1.2:1.0; Add the amount of substance of methacrylic acid in two (trichloromethyl) carbonic ether B described in the step (2) and the step (1) than being 0.45:1.0.Temperature of reaction t
1=30 ℃, t
2=40 ℃, t
3=110 ℃; Reaction times T
1=10h, T
2=10h, T
3=3h.Other operations are with embodiment 1.Get product Jia Jibingxisuanyizhi isocyanic ester 23.36g, calculate with the amount of methacrylic acid, yield is that 75.3%, GC purity is 99.3%.
Embodiment 5:
Methacrylic acid in the step (1): thiodiphenylamine: DMF: two (trichloromethyl) carbonic ether A: the amount of substance ratio that feeds intake of ethanolamine hydrochloric salt is 1.0:0.01:0.001:0.45:1.2; Organic bases described in the step (2) is tri-n-butylamine, adds the amount of substance of methacrylic acid in organic bases and the step (1) than being 0.8:1.0; Add the amount of substance of methacrylic acid in two (trichloromethyl) carbonic ether B described in the step (2) and the step (1) than being 0.45:1.0.Temperature of reaction t
1=95 ℃, t
2=90 ℃, t
3=80 ℃; Reaction times T
1=2h, T
2=2h, T
3=5h.Other operations are with embodiment 1.Get product Jia Jibingxisuanyizhi isocyanic ester 22.56g, calculate with the amount of methacrylic acid, yield is that 72.7%, GC purity is 99.1%.
Embodiment 6:
Methacrylic acid in the step (1): Resorcinol: DMF: two (trichloromethyl) carbonic ether A: the amount of substance ratio that feeds intake of ethanolamine hydrochloric salt is 1.0:0.008:0.005:0.5:1.0; Organic bases described in the step (2) is N, and accelerine adds the amount of substance of methacrylic acid than being 0.5:1.0 in organic bases and the step (1); Add the amount of substance of methacrylic acid in two (trichloromethyl) carbonic ether B described in the step (2) and the step (1) than being 0.6:1.0.
Organic solvent is dimethylbenzene in step (1), (2), and step (1) dimethylbenzene consumption is 10 times of two (trichloromethyl) carbonic ether A, and step (2) dimethylbenzene consumption is 2 times of two (trichloromethyl) carbonic ether B quality.Temperature of reaction t
1=100 ℃, t
2=95 ℃, t
3=135 ℃; Reaction times T
1=2h, T
2=4h, T
3=2h.Other operations are with embodiment 1.Get product Jia Jibingxisuanyizhi isocyanic ester 22.71g, calculate with the amount of methacrylic acid, yield is that 73.2%, GC purity is 99.5%.
Embodiment 7:
Methacrylic acid in the step (1): Resorcinol: DMF: two (trichloromethyl) carbonic ether A: the amount of substance ratio that feeds intake of ethanolamine hydrochloric salt is 1.0:0.01:0.01:0.5:1.0; Organic bases described in the step (2) is N, and accelerine adds the amount of substance of methacrylic acid than being 1.5:1.0 in organic bases and the step (1); Add the amount of substance of methacrylic acid in two (trichloromethyl) carbonic ether B described in the step (2) and the step (1) than being 0.5:1.0.
Organic solvent is methylene dichloride in step (1), (2), and step (1) methylene dichloride consumption is 3 times of two (trichloromethyl) carbonic ether A quality, and step (2) methylene dichloride consumption is 5 times of two (trichloromethyl) carbonic ether B quality.Temperature of reaction t
1=40 ℃, t
2=40 ℃, t
3=40 ℃; Reaction times T
1=8h, T
2=10h, T
3=10h.
Other operations are with embodiment 1.Get product Jia Jibingxisuanyizhi isocyanic ester 22.09g, yield is to calculate with the amount of methacrylic acid, and 71.2%, GC purity is 99.4%.
Embodiment 8:
Methacrylic acid in the step (1): 2,6 di tert butyl 4 methyl phenol: DMF: two (trichloromethyl) carbonic ether A: the amount of substance ratio that feeds intake of ethanolamine hydrochloric salt is 1.0:0.004:0.005:0.55:1.0; Organic bases described in the step (2) is N, and accelerine adds the amount of substance of methacrylic acid than being 0.9:1.0 in organic bases and the step (1); Add the amount of substance of methacrylic acid in two (trichloromethyl) carbonic ether B described in the step (2) and the step (1) than being 0.45:1.0.
Organic solvent is 1 in step (1), (2), the 2-ethylene dichloride, wherein step (1) 1,2-ethylene dichloride consumption is 2 times of two (trichloromethyl) carbonic ether A quality, step (2) 1,2-ethylene dichloride consumptions are 6 times of two (trichloromethyl) carbonic ether quality B.Temperature of reaction t
1=65 ℃, t
2=70 ℃, t
3=85 ℃; Reaction times T
1=4h, T
2=5h, T
3=5h.
Other operations are with embodiment 1.Get product Jia Jibingxisuanyizhi isocyanic ester 24.42g, calculate with the amount of methacrylic acid, yield is that 78.7%, GC purity is 99.8%.
Embodiment 9:
Methacrylic acid in the step (1): thiodiphenylamine: DMF: two (trichloromethyl) carbonic ether A: the amount of substance ratio that feeds intake of ethanolamine hydrochloric salt is 1.0:0.02:0.001:0.45:1.0; Organic bases described in the step (2) is N, and accelerine adds the amount of substance of methacrylic acid than being 1.0:1.0 in organic bases and the step (1); Add the amount of substance of methacrylic acid in two (trichloromethyl) carbonic ether B described in the step (2) and the step (1) than being 0.5:1.0.Organic solvent is chlorobenzene in the step (1), (2), and wherein step (1) chlorobenzene consumption be 2 times of two (trichloromethyl) carbonic ether A quality, and step (2) chlorobenzene consumption is 10 times of pair (trichloromethyl) carbonic ether B quality.Temperature of reaction t
1=50 ℃, t
2=75 ℃, t
3=85 ℃; Reaction times T
1=5h, T
2=5h, T
3=5h.
Other operations are with embodiment 1.Get product Jia Jibingxisuanyizhi isocyanic ester 23.37g, calculate with the amount of methacrylic acid, yield is that 75.3%, GC purity is 99.2%.
Embodiment 10:
Methacrylic acid in the step (1): MEHQ: DMF: two (trichloromethyl) carbonic ether A: the amount of substance ratio that feeds intake of ethanolamine hydrochloric salt is 1.0:0.0015:0.001:1.0:1.0; Organic bases described in the step (2) is diisopropyl ethyl amine, adds the amount of substance of methacrylic acid in organic bases and the step (1) than being 0.10:1.0; Add the amount of substance of methacrylic acid in two (trichloromethyl) carbonic ether B described in the step (2) and the step (1) than being 0.45:1.0.
Organic solvent is chlorobenzene in the step (1), (2), and wherein step (1) chlorobenzene consumption be 3 times of two (trichloromethyl) carbonic ether A quality, and step (2) chlorobenzene consumption is 3 times of pair (trichloromethyl) carbonic ether B quality.Temperature of reaction t
1=75 ℃, t
2=90 ℃, t
3=132 ℃; Reaction times T
1=3h, T
2=4h, T
3=2h.
Other operations are with embodiment 1.Get product Jia Jibingxisuanyizhi isocyanic ester 21.88g, calculate with the amount of methacrylic acid, yield is that 70.4%, GC purity is 99.0%.
Embodiment 11:
Methacrylic acid in the step (1): Resorcinol: DMF: two (trichloromethyl) carbonic ether A: the amount of substance ratio that feeds intake of ethanolamine hydrochloric salt is 1.0:0.1:0.001:0.4:1.0; Organic bases described in the step (2) is N, and accelerine adds the amount of substance of methacrylic acid than being 1.1:1.0 in organic bases and the step (1); Add the amount of substance of methacrylic acid in two (trichloromethyl) carbonic ether B described in the step (2) and the step (1) than being 0.60:1.0.
Organic solvent is chlorobenzene in the step (1), (2), and wherein step (1) chlorobenzene consumption be 5 times of two (trichloromethyl) carbonic ether A quality, and step (2) chlorobenzene consumption is 4 times of pair (trichloromethyl) carbonic ether B quality.Temperature of reaction t
1=120 ℃, t
2=100 ℃, t
3=85 ℃; Reaction times T
1=1h, T
2=3h, T
3=5h.
Other operations are with embodiment 1.Get product Jia Jibingxisuanyizhi isocyanic ester 21.90g, calculate with the amount of methacrylic acid, yield is that 70.6%, GC purity is 99.0%.
Embodiment 12:
Methacrylic acid in the step (1): thiodiphenylamine: DMF: two (trichloromethyl) carbonic ether A: the amount of substance ratio that feeds intake of ethanolamine hydrochloric salt is 1.0:0.01:0.01:0.55:1.0; Organic bases described in the step (2) is tri-n-butylamine, adds the amount of substance of methacrylic acid in organic bases and the step (1) than being 1.5:1.0; Add the amount of substance of methacrylic acid in two (trichloromethyl) carbonic ether B described in the step (2) and the step (1) than being 0.45:1.0.
Organic solvent is ethyl acetate in the step (1), (2), and wherein step (1) ethyl acetate consumption be 4 times of two (trichloromethyl) carbonic ether A quality, and step (2) ethyl acetate consumption is 4 times of pair (trichloromethyl) carbonic ether B quality.Temperature of reaction t
1=82 ℃, t
2=82 ℃, t
3=82 ℃; Reaction times T
1=3h, T
2=5h, T
3=5h.
Other operations are with embodiment 1.Get product Jia Jibingxisuanyizhi isocyanic ester 22.62g, calculate with the amount of methacrylic acid, yield is that 72.9%, GC purity is 99.3%.
Claims (10)
1. the preparation method of a Jia Jibingxisuanyizhi isocyanic ester is characterized in that described method is:
(1) with the methacrylic acid is raw material, add stopper and catalyzer, under 30～120 ℃, drip the mixing solutionss of two (trichloromethyl) carbonic ether A and organic solvent A under the nitrogen protection, insulation reaction was down to room temperature after 1～10 hour, drop into ethanolamine hydrochloric salt under the nitrogen protection, in 30～120 ℃ of stirring reactions 2～10 hours, make and contain methacrylic acid amino ethyl ester hydrochloride solution; Described stopper is one or more the combination in Resorcinol, cuprous chloride, thiodiphenylamine, MEHQ or the 2,6 di tert butyl 4 methyl phenol; Described catalyzer is N, dinethylformamide; The amount of substance ratio that feeds intake of described methacrylic acid and stopper, catalyzer, two (trichloromethyl) carbonic ether A, ethanolamine hydrochloric salt is 1.0:0.001～0.1:0.001～0.01:0.3～1.0:0.8～1.2; Described organic solvent A quality consumption is 2～20 times of two (trichloromethyl) carbonic ether quality;
(2) in the methacrylic acid amino ethyl ester hydrochloride solution of step (1) gained, add organic bases under the nitrogen protection, slowly drip the mixing solutions of being formed by two (trichloromethyl) carbonic ether B and organic solvent B down at 40～150 ℃ then, after the insulation reaction 3～10 hours, after the reaction solution aftertreatment got the organic layer drying, obtain the Jia Jibingxisuanyizhi isocyanic ester; The amount of substance ratio that adds methacrylic acid in described organic bases and the step (1) is 0.1～3:1; The amount of substance ratio that adds methacrylic acid in described two (trichloromethyl) carbonic ether B and the step (1) is 0.3～1.0:1; Described organic solvent B quality consumption is 1～20 times of two (trichloromethyl) carbonic ether quality.
2. the preparation method of Jia Jibingxisuanyizhi isocyanic ester according to claim 1, it is characterized in that the middle temperature that drips the mixing solutions of two (trichloromethyl) carbonic ether A and organic solvent A of described step (1) is 40～60 ℃, the insulation reaction time is 3～5 hours.
3. the preparation method of Jia Jibingxisuanyizhi isocyanic ester according to claim 1 is characterized in that dropping in the described step (1) behind the ethanolamine hydrochloric salt in 60～90 ℃ of stirring reactions 4～8 hours.
4. the preparation method of Jia Jibingxisuanyizhi isocyanic ester according to claim 1, what it is characterized in that methacrylic acid described in the described step (1) and stopper, catalyzer, two (trichloromethyl) carbonic ether A, ethanolamine hydrochloric salt feeds intake amount of substance than being 1.0:0.005～0.01:0.001～0.005:0.4～0.6:1.0.
5. the preparation method of Jia Jibingxisuanyizhi isocyanic ester according to claim 1, it is characterized in that organic solvent A is methylene dichloride, trichloromethane, ethyl acetate, 1 in the described step (1), one or more combination in 2-ethylene dichloride, benzene,toluene,xylene, chlorobenzene, the santochlor.
6. the preparation method of Jia Jibingxisuanyizhi isocyanic ester according to claim 1, it is characterized in that organic bases is triethylamine, Tri-n-Propylamine, tri-isopropyl amine, tri-n-butylamine, tri-isobutylamine, diisopropylethylamine, dimethylcyclohexylamine, pyridine, 4-dimethylamino pyridine, N-methyl beautiful jade, N-methyl piperidine, N in the described step (2), N dimethylamine base-4-pyridine, N, dinethylformamide, N, N-lupetidine, N, accelerine or N, the combination of one or more in the N-Diethyl Aniline.
7. the preparation method of Jia Jibingxisuanyizhi isocyanic ester according to claim 1, it is characterized in that the middle temperature that drips the mixing solutions of being made up of two (trichloromethyl) carbonic ether B and organic solvent B of described step (2) is 70～110 ℃, the reaction times is 3～5h.
8. the preparation method of Jia Jibingxisuanyizhi isocyanic ester according to claim 1, it is characterized in that organic solvent B is methylene dichloride, trichloromethane, ethyl acetate, 1 in the described step (2), one or more combination in 2-ethylene dichloride, benzene,toluene,xylene, chlorobenzene, the santochlor.
9. the preparation method of Jia Jibingxisuanyizhi isocyanic ester according to claim 1, the amount of substance ratio that it is characterized in that adding in organic bases described in the described step (2) and the step (1) methacrylic acid is 0.8～1.5:1; The amount of substance ratio that adds methacrylic acid in described two (trichloromethyl) carbonic ether B and the step (1) is 0.45～0.6:1.
10. the preparation method of Jia Jibingxisuanyizhi isocyanic ester according to claim 1, it is characterized in that the reaction solution post-treating method is described in the described step (2): after reaction finishes, reaction solution is cooled to room temperature, filter, the washing of gained filtrate water, the organic layer drying of telling, concentrated solvent, 87～89 ℃/10mmHg of the underpressure distillation collection cut of reclaiming, drying obtains the Jia Jibingxisuanyizhi isocyanic ester.
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| CN104086458A (en) * | 2014-07-09 | 2014-10-08 | 张家港瀚康化工有限公司 | Preparation method for isocyanate ethyl methacrylate |
| CN105330807A (en) * | 2015-11-25 | 2016-02-17 | 山东一诺威新材料有限公司 | Synthetic method of styrene-maleic anhydride modified resin for liquid photoresist |
| CN114929668A (en) * | 2020-01-06 | 2022-08-19 | 昭和电工株式会社 | (meth) acrylate compound having isocyanate group and method for producing same |
| CN116023301A (en) * | 2022-12-21 | 2023-04-28 | 浦拉司科技（上海）有限责任公司 | Synthetic method of isocyanate ethyl acrylate |
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