CN103613545A - Method for preparing ethylidene-urea ethyl acrylate - Google Patents
Method for preparing ethylidene-urea ethyl acrylate Download PDFInfo
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- CN103613545A CN103613545A CN201310610634.4A CN201310610634A CN103613545A CN 103613545 A CN103613545 A CN 103613545A CN 201310610634 A CN201310610634 A CN 201310610634A CN 103613545 A CN103613545 A CN 103613545A
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- vinylformic acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D233/28—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D233/30—Oxygen or sulfur atoms
- C07D233/32—One oxygen atom
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Abstract
The invention discloses a method for preparing ethylidene-urea ethyl acrylate, relating to the technical field of synthesis of compounds containing ethylidene-urea heterocycles. According to the method, ethylidene-urea ethyl acrylate is prepared through heating acrylic acid and N-hydroxyethyl ethylene urea in the presence of a catalyst, a polymerization inhibitor and a water carrying agent and carrying out condensation reaction, wherein the water carrying agent is an azeotropic water carrying medium, and generated water is continuously separated from a reaction system through refluxing carrying water, the water carrying agent and a moisture layer. The method is of one-step reaction and has high yield, the byproduct is water, and no any harmful and toxic substance is generated and discharged, so that the method is a very environmental-friendly organic synthesis method.
Description
Technical field
The present invention relates to the synthesis technical field containing the compound of ethylene-urea heterocycle.
Background technology
It is changeable that polyacrylate resin (comprising pure third, phenylpropyl alcohol, vinegar third, the silicon third gradegrade C) has developed into performance at present, and purposes is the widest, one of macromolecule resin system of consumption maximum.Vinylformic acid ethylidene-urea ethyl ester is kind of a special functional acrylate monomer, and chemical structural formula is:
Vinylformic acid ethylidene-urea ethyl ester and similar acrylate monomer copolymerization can be prepared and had features and high performance acrylic resin, to meet multiple application requiring.In its chemical structure of vinylformic acid ethylidene-urea ethyl ester, contain ethylidene-urea functional group, when preparing with other general acrylate monomer copolymerizations the polyacrylic ester that contains ethylidene-urea side group, copolyreaction formula is as follows:
This polyacrylic resin that contains ethylidene-urea side group (1) can increase substantially the sticking power of itself and multiple base material, (2) can at room temperature carry out irreversible absorption formaldehyde molecule, thereby preparation has interior exterior wall coatings and the automotive trim coating of absorbing formaldehyde function.The reaction principle of its irreversible absorption formaldehyde is as follows:
(3) include ethylidene-urea active lateral group polyacrylate resin can with multiple linking agent crosslinking curing, increase substantially the multiple performances such as resin mechanics, heat-resisting, resistant to chemical media, its cross-linking and curing reaction is exemplified below:
a.
b.
(4) polyacrylate resin that includes ethylidene-urea active lateral group progressively improves with ethylidene-urea content (N content), and the flame retardant properties of resin increases substantially.
In sum, vinylformic acid ethylidene-urea ethyl ester can be given conventional acrylic ester resin several functions, and its multiple performance is improved.
Application number is the preparation method that 201110037793.0 Chinese patent discloses (methyl) vinylformic acid ethylidene-urea alkyl ester monomer, with Hydroxyethyl acrylate, react with thionyl chloride and make vinylformic acid chloro ethyl ester, react with ethylidene-urea, sodium hydroxide and obtain vinylformic acid ethyl carbamide ethyl ester again, this reaction yield is high, and its weak point is byproduct of reaction SO
2with HCl gas be harmful and noxious substance, and be two-step reaction.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of preparation method of vinylformic acid ethylidene-urea ethyl ester, and the method is single step reaction, and yield is high, and by product is water, without any harmful poisonous material, generates discharge, is the methodology of organic synthesis of very environmental protection.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of preparation method of vinylformic acid ethylidene-urea ethyl ester, condensation reaction is carried out in the heating under catalyzer, stopper and band aqua exist of vinylformic acid and N – hydroxyethyl ethylene urea, prepares vinylformic acid ethylidene-urea ethyl ester; Described band aqua is azeotropic band water medium, by backflow, is with water, band aqua and water stratification, constantly from reaction system, isolates the water of generation, and reaction formula is:
Preferably, the mol ratio of vinylformic acid and N – hydroxyethyl ethylene urea is 1:1-4:1.
Catalyzer is that weight ratio is 1 to 1 Tai-Ace S 150 and the mixture of aluminum chloride, and catalyst levels is the 1%-10% of reaction system gross weight.
Stopper is thiodiphenylamine, para benzoquinone, Methylene blue, Resorcinol or MEHQ, and stopper consumption is the 0.1%-5% of vinylformic acid weight.
Band aqua is hexanaphthene, benzene or toluene, is vinylformic acid and N – hydroxyethyl ethylene urea grams sum 0.5-4.0 times with aqua milliliter used number.
Temperature of reaction is 75～110 ℃.
In the present invention, reaction system gross weight refers to vinylformic acid used in reaction, N – hydroxyethyl ethylene urea, catalyzer, stopper and with the gross weight of aqua.Catalyzer is: the Tai-Ace S 150 that weight ratio is 1 to 1 and the mixture of aluminum chloride, catalyzer add the generation that can promote vinylformic acid ethylidene-urea ethyl ester, improve reaction yield.Adding of stopper can be avoided vinyl monomer generation polymerization side reactions, improved the yield of vinylformic acid ethylidene-urea ethyl ester.Band aqua is azeotropic band water medium, by backflow, is with water, band aqua and water stratification, constantly from reaction system, isolates the water of generation, prevents the generation of reversed reaction.Cheap with aqua hexanaphthene, benzene, toluene, and boiling point is low, makes temperature of reaction at 75～110 ℃, and temperature of reaction is easy to control.
The beneficial effect that adopts technique scheme to produce is:
(1) the present invention is single step reaction, and production efficiency is high, and raw material cheap, be easy to get;
(2) by product of the present invention is water, without any harmful poisonous material, generates discharge, is the methodology of organic synthesis of very environmental protection;
(3) the present invention adopts catalyzer: the Tai-Ace S 150 that weight ratio is 1 to 1 and the mixture of aluminum chloride, and make the yield of vinylformic acid ethylidene-urea ethyl ester can reach 90%, and because catalyzer is solid catalyst, very easily separated with reaction system.
Embodiment
Embodiment 1
72g vinylformic acid (1mol), 65g N-hydroxyethyl ethylene urea (0.5mol), 8g catalyzer (Tai-Ace S 150 that weight ratio is 1 to 1 and the mixture of aluminum chloride), 200ml hexanaphthene, 0.2g thiodiphenylamine (stopper) are incorporated with in the reaction three-necked bottle of reflux exchanger and water-and-oil separator successively.Be heated with stirring to 80 ℃, the hexanaphthene band water that comes to life and reflux.80 ℃ of insulation reaction 6hr, no longer increase to aquifer yield in water-and-oil separator.From water trap, emit the water of generation, continuing 80 ℃ of insulation 1.5hr steams and reclaims the about 180ml of major part (approximately 90%) hexanaphthene and next under reduced pressure steam unnecessary vinylformic acid, stop heating, reaction system is cooled to 30～40 ℃, add 200ml dehydrated alcohol and sodium carbonate 10g, stirring reaction product 45min, to remove catalyzer and residual vinylformic acid.Filter, decompression steams ethanol and obtains vinylformic acid ethylidene-urea ethyl ester 82g, yield 89%, product Chun Du≤95%.
Embodiment 2
46g vinylformic acid (0.64mol), 65g N-hydroxyethyl ethylene urea (0.5mol), 10g catalyzer (Tai-Ace S 150 that weight ratio is 1 to 1 and the mixture of aluminum chloride), 60ml hexanaphthene, 0.1g thiodiphenylamine (stopper) are incorporated with in the reaction three-necked bottle of reflux exchanger and water-and-oil separator successively, be heated with stirring to 83 ℃ of left and right, the hexanaphthene backflow that comes to life, continuous separated water outlet, reaction 8hr no longer increases to aquifer yield in water-and-oil separator, temperature of reaction rises to 90 ℃ of left and right, continues to steam and reclaims major part (approximately 70%) hexanaphthene.With the same aftertreatment of embodiment 1, obtain vinylformic acid ethylidene-urea ethyl ester 81g, yield 88%, product Chun Du≤92%.
Embodiment 3
140g vinylformic acid (1.94mol), 65g hydroxyethyl ethylene urea (0.5mol), 4g catalyzer (Tai-Ace S 150 that weight ratio is 1 to 1 and the mixture of aluminum chloride), 300ml hexanaphthene, 0.14g thiodiphenylamine (stopper) are added in the reaction three-necked bottle that reflux exchanger and water-and-oil separator are housed successively, be heated with stirring to 75 ℃, the hexanaphthene continuous separated water outlet that refluxes that comes to life, reaction 6hr temperature rises to 80 ℃ of left and right, no longer increase to aquifer yield in water-and-oil separator, continue to steam and reclaim major part (approximately 95%) hexanaphthene.With the same aftertreatment of embodiment 1, obtain vinylformic acid ethylidene-urea ethyl ester 82g, yield 89%, product Chun Du≤95%.
Embodiment 4
Band aqua hexanaphthene is changed into benzene, and other conditionally complete is identical with embodiment 1, reaction and aftertreatment equally, yield 90%, product Chun Du≤95%.
Embodiment 5
Band water ring hexane is changed into benzene, and other conditionally complete is identical with embodiment 2, reaction and aftertreatment equally, yield 90%, product Chun Du≤92%.
Embodiment 6
Band water ring hexane is changed into benzene, and other conditionally complete is identical with embodiment 3, reaction and aftertreatment equally, yield 90%, product Chun Du≤95%.
Embodiment 7
Change stopper 0.2g thiodiphenylamine into 2.3g MEHQ, other conditionally complete is identical with embodiment 1, reaction and aftertreatment equally, yield 90%, product Chun Du≤95%.
Embodiment 8
Change stopper 0.2g thiodiphenylamine into 10g MEHQ, other conditionally complete is identical with embodiment 1, reaction and aftertreatment equally, yield 90%, product Chun Du≤92%.
Embodiment 9
140g vinylformic acid (1.94mol), 65g hydroxyethyl ethylene urea (0.5mol), 10g catalyzer (Tai-Ace S 150 that weight ratio is 1 to 1 and the mixture of aluminum chloride), 300ml toluene, 7g MEHQ (stopper) are added in the reaction three-necked bottle that reflux exchanger and water-and-oil separator are housed successively, be heated with stirring to 95 ℃ of backflows that come to life, continuous separated water outlet.Reaction 6hr, temperature rises to 110 ℃ of left and right, no longer increases to aquifer yield in water-and-oil separator, continues to steam and reclaims most of toluene, with same processing of embodiment 1, obtains product 78g, yield 85%, product Chun Du≤92%.
Embodiment 10
Change 200ml hexanaphthene into 548ml hexanaphthene, other conditionally complete is identical with embodiment 1, reaction and aftertreatment equally, yield 90%, product Chun Du≤95%.
Embodiment 11
Change stopper 0.2g thiodiphenylamine into 3g para benzoquinone, other conditionally complete is identical with embodiment 1, reaction and aftertreatment equally, yield 88%, product Chun Du≤95%.
Embodiment 12
Change stopper 0.2g thiodiphenylamine into 2g Methylene blue, other conditionally complete is identical with embodiment 1, reaction and aftertreatment equally, yield 90%, product Chun Du≤95%.
Embodiment 13
Change stopper 0.2g thiodiphenylamine into 5g Resorcinol, other conditionally complete is identical with embodiment 1, reaction and aftertreatment equally, yield 90%, product Chun Du≤95%.
Embodiment 14
Change catalyzer (Tai-Ace S 150 that weight ratio is 1 to 1 and the mixture of aluminum chloride) 10g into 18g, other conditionally complete is identical with embodiment 2, reaction and aftertreatment equally, yield 90%, product Chun Du≤92%.
Embodiment 15
Change catalyzer (Tai-Ace S 150 that weight ratio is 1 to 1 and the mixture of aluminum chloride) 10g into 1.6g, other conditionally complete is identical with embodiment 2, reaction and aftertreatment equally, yield 88%, product Chun Du≤92%.
Claims (6)
1. a preparation method for vinylformic acid ethylidene-urea ethyl ester, is characterized in that: condensation reaction is carried out in the heating under catalyzer, stopper and band aqua exist of vinylformic acid and N – hydroxyethyl ethylene urea, prepares vinylformic acid ethylidene-urea ethyl ester; Described band aqua is azeotropic band water medium, by backflow, is with water, band aqua and water stratification, constantly from reaction system, isolates the water of generation, and reaction formula is:
2. the preparation method of vinylformic acid ethylidene-urea ethyl ester according to claim 1, is characterized in that the mol ratio of described vinylformic acid and N – hydroxyethyl ethylene urea is 1:1-4:1.
3. the preparation method of vinylformic acid ethylidene-urea ethyl ester according to claim 1, is characterized in that described catalyzer is that weight ratio is 1 to 1 Tai-Ace S 150 and the mixture of aluminum chloride, and described catalyst levels is the 1%-10% of reaction system gross weight.
4. the preparation method of vinylformic acid ethylidene-urea ethyl ester according to claim 1, is characterized in that described stopper is thiodiphenylamine, para benzoquinone, Methylene blue, Resorcinol or MEHQ, and described stopper consumption is the 0.1%-5% of vinylformic acid weight.
5. the preparation method of vinylformic acid ethylidene-urea ethyl ester according to claim 1, is characterized in that described band aqua is hexanaphthene, benzene or toluene, is vinylformic acid and N – hydroxyethyl ethylene urea grams sum 0.5-4.0 times with aqua milliliter used number.
6. the preparation method of vinylformic acid ethylidene-urea ethyl ester according to claim 1, is characterized in that described temperature of reaction is 75～110 ℃.
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Citations (6)
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|---|---|---|---|---|
| US2828224A (en) * | 1955-03-21 | 1958-03-25 | Rohm & Haas | Method of coating leather with polymers containing ureido groups and the resulting article |
| US5567826A (en) * | 1992-05-23 | 1996-10-22 | Roehm Gmbh Chemische Fabrik | Process for the production of terminally nitrogen heterocycle substituted (meth)acrylate by the use of a mixture of an alkali metal and alkaline earth metal catalyst |
| CN1179419A (en) * | 1996-09-16 | 1998-04-22 | 埃勒夫阿托化学有限公司 | Process for manufacture of alkylimidazolidone (methyl) acrylates |
| CN101088990A (en) * | 2006-06-13 | 2007-12-19 | 罗门哈斯公司 | Transesterification process for production of (meth)acrylate ester monomers |
| CN102167682A (en) * | 2011-02-14 | 2011-08-31 | 广东银洋树脂有限公司 | (Meth)acrylic ethidene urethyl ester monomer and preparation method thereof |
| CN102260128A (en) * | 2010-05-25 | 2011-11-30 | 南京凯时通新材料有限公司 | Process for preparing acrylate monomer and derivative thereof by using transesterification method |
-
2013
- 2013-11-27 CN CN201310610634.4A patent/CN103613545B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2828224A (en) * | 1955-03-21 | 1958-03-25 | Rohm & Haas | Method of coating leather with polymers containing ureido groups and the resulting article |
| US5567826A (en) * | 1992-05-23 | 1996-10-22 | Roehm Gmbh Chemische Fabrik | Process for the production of terminally nitrogen heterocycle substituted (meth)acrylate by the use of a mixture of an alkali metal and alkaline earth metal catalyst |
| CN1179419A (en) * | 1996-09-16 | 1998-04-22 | 埃勒夫阿托化学有限公司 | Process for manufacture of alkylimidazolidone (methyl) acrylates |
| CN101088990A (en) * | 2006-06-13 | 2007-12-19 | 罗门哈斯公司 | Transesterification process for production of (meth)acrylate ester monomers |
| CN102260128A (en) * | 2010-05-25 | 2011-11-30 | 南京凯时通新材料有限公司 | Process for preparing acrylate monomer and derivative thereof by using transesterification method |
| CN102167682A (en) * | 2011-02-14 | 2011-08-31 | 广东银洋树脂有限公司 | (Meth)acrylic ethidene urethyl ester monomer and preparation method thereof |
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Address after: 061000 Cangzhou city of Hebei Province, the Canal Zone Zhang Chuang-tzu Industrial Park Patentee after: Cangzhou Kangzhuang Chemical Co., Ltd. Address before: 061000 Cangzhou city of Hebei Province, the canal zone Yihe international A block 405 Patentee before: CANGZHOU KANGZHUANG CHEMICAL CO., LTD. |