CN102416347A - Multi-ionic liquid catalyst and application thereof in synthesizing acrylate compounds - Google Patents
Multi-ionic liquid catalyst and application thereof in synthesizing acrylate compounds Download PDFInfo
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- CN102416347A CN102416347A CN2011102556808A CN201110255680A CN102416347A CN 102416347 A CN102416347 A CN 102416347A CN 2011102556808 A CN2011102556808 A CN 2011102556808A CN 201110255680 A CN201110255680 A CN 201110255680A CN 102416347 A CN102416347 A CN 102416347A
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Abstract
The invention discloses a multi-ionic liquid catalyst, comprising multiple central ions, wherein, cations are multiple quarternary ammonium ions, and anions are strong acid group anions. Compared with present ionic liquid with single central ion, the multi-ionic liquid catalyst has higher catalytic activity, and can be used for catalyzing the esterification of polyfunctional alcohols and polyfunctional acids at low temperatures. The invention further discloses a synthetic method of acrylate compounds, characterized in that: the multi-ionic liquid is used as the catalyst and the reaction medium, and high-efficient synthesis of various acrylate compounds can be realized at low temperatures. According to the invention, the advantages of high yield, easy separation of products, long service life of the catalyst, wide applicable scope, and the like are achieved.
Description
Technical field
The present invention relates to a kind of polybasic ion liquid catalyst and the application in acrylic ester compound is synthetic thereof.
Background technology
Ionic liquid is meant that mainly they have the incomparable special performance of a lot of molecular solvent by organic cation and inorganic or organic anion constitutes in room temperature or be bordering on the organic salt compound that is in a liquid state under the room temperature.Result of study shows that ionic liquid has good catalytic activity to esterification.This method not only can obtain higher conversion ratio and productive rate, and compares with conventional method, also has two remarkable advantages: 1, product (ester class) is insoluble to ionic liquid; In course of reaction, product and reaction system are separated automatically, help promoting molecular balance to carry out to positive reaction on the one hand; On the other hand; After reaction was accomplished, product can be separated from catalyst system and catalyzing through standing demix expediently, enhances productivity; 2, the ionic-liquid catalyst after the use can directly recycle under the situation of any processing; And maintenance advantages of high catalytic activity; Still can be after processed even if reduced through the ionic-liquid catalyst catalytic activity that repeatedly recycles; Recover its catalytic activity, further prolong the service life of catalyst.
The ionic liquid that is applied to the catalyzing esterification reaction the earliest is acid aluminium chloride ionic liquid, but owing in the esterification process water generates is arranged, the aluminium chloride ionic liquid can receive destruction to a certain degree unavoidably, causes shorten the service life of catalyst.Developed into afterwards through sulfonate ion, sulfate ion are replaced the chlorate ions, and obtained meeting the stable Bronsted acidic ion liquid of water, it shows certain activity when the multiple alcoholic acid esterification of catalysis reacts.Human 1-butyl such as Trissa-3-methylimidazole tosilate ionic-liquid catalyst; The esterification of having studied acetate and phenmethylol is synthetic; Reacted 2 hours, maximum conversion rate and product selectivity all reach 100%, and the product easy separation; The rear catalyst that dewaters is reused 4 times, and conversion ratio is still greater than 85%.In recent years; The application of ionic liquid in esterification that also there have been a large amount of patent reports in China, for example CN1405140 and CN101172253 have introduced the esterification by 1-methyl-3-hexyl imidazoles ionic liquid-catalyzed aliphatic or aromatic acid of tetrafluoride boron and straight chain alcohol respectively; CN1554638 discloses multiple anion and (has comprised CF
3SO
3 -, CF
3COO
-, HSO
3 -, CH
3COO
-Deng) the ion liquid synthetic method formed with the alkyl pyridine cationoid, and to the catalytic activity of small molecular alcohol acid esters reaction; CN1880295, CN101024612, CN101255111, CN101024613, CN101049573 etc. have also introduced the synthetic method of alkyl pyrrolidine ketone acidic ion liquid and the application in the catalytic esterification at ambient temperature thereof, all show excellent catalytic activity and reusability.
Acrylic ester compound is a photocuring diluent commonly used in the photocureable coating; Major product comprises trihydroxy propane triacrylate, ethylene glycol dimethacrylate, butanediol dimethylacrylate, hexanediol dimethacrylate, methacrylic acid benzyl ester etc.; Along with the continuous expansion in photocureable coating market, the consumption of acrylic ester compound is also in continuous expansion.At present, acrylic ester compound mainly is to obtain through the high temperature dehydration reaction under the effect of strong acid catalyst through acrylic or methacrylic acid and polyalcohol.Because acrylic ester compound contains unsaturated double-bond, easy polymerization reaction take place causes unstable product quality under the hot conditions; In addition, employed strongly acidic catalyst has stronger corrosivity to consersion unit, causes cost of equipment maintenance high; Moreover this reacts required reaction temperature higher (120 ℃～200 ℃) and needs through azeotropic water removing, causes the energy consumption height, easily environment is brought negative effect.
Therefore, adopt the synthetic of ionic liquid-catalyzed acrylic ester compound, reduce reaction temperature, have important practical significance.The ionic-liquid catalyst of at present having reported has advantages of high catalytic activity and repeat performance for the monobasic alcoholic acid esterification; Can be used for the synthetic of single functionality acrylic ester compound; Like acrylic acid benzyl ester and methacrylic acid benzyl ester; Yet its catalyzing esterification activity to polyfunctional acrylic ester compounds (referring to contain the acrylic ester compound of two or more unsaturated double-bonds) is not high, and product yield is low.
For this reason, the present invention aims to provide a kind of ionic-liquid catalyst efficiently and at acrylic ester compound, and the especially application of polyfunctional acrylic ester compounds in synthetic is to overcome the deficiency of prior art.
Summary of the invention
The object of the present invention is to provide a kind of polybasic ion liquid catalyst, it contains a plurality of ions center, and the ionic liquid of comparing existing single ionic center has higher catalytic activity, can be under lower temperature catalysis polyfunctionality alcohol, sour esterification.
Another object of the present invention is to provide a kind of synthetic method of acrylic ester compound; This method is catalyst and reaction media with above-mentioned polybasic ion liquid; Can under lower temperature conditions, realize the efficient synthetic of multiple acrylic ester compound, have that productive rate height, product are easy to separate, catalyst long service life and an advantage such as applied widely.
The objective of the invention is to realize through following technical scheme:
A kind of polybasic ion liquid catalyst; It contains two or more ions center; Its cation is polynary quaternary ammonium ion; Comprise tetramethylethylenediamine cation, tetramethyl butane diamine cation, 4-methyl hexamethylene diamine cation, triethylenediamine cation, hexa cation etc., preferably the hexa cation; Its anion is the strong acid radical ion; Comprise alkyl sulfonate ion (for example methanesulfonate ions, ethylsulfonic acid radical ion, propyl sulfonic acid radical ion, butyl sulfonic acid radical ion etc.), acetate ion, hydrogen sulfate ion, phosphate anion or nitrate ion etc., preferably alkyl sulfonate ion.
The preparation method of said polybasic ion liquid catalyst is: with polynary tertiary amine and strong acid is raw material, forms in 2～6 hours at 30 ℃～60 ℃ following stirring reactions.Wherein, the mol ratio between the nitrogen-atoms in said strong acid and the said polynary tertiary amine is 1: 0.8～12, preferably 1: 0.95～1.05.Described polynary tertiary amine comprises tetramethylethylenediamine, tetramethyl butane diamine, 4-methyl hexamethylene diamine, triethylenediamine, hexa etc.; Described strong acid comprises alkyl sulfonic acid, acetate, sulfuric acid, phosphoric acid or nitric acid etc., preferably alkyl sulfonic acid.
A kind of synthetic method of acrylic ester compound; Is raw material with acrylic or methacrylic acid with polyalcohol; With described polybasic ion liquid is that catalyst and reaction media carry out esterification; Reaction temperature is 20 ℃～100 ℃, and preferably 50 ℃～80 ℃, the reaction time is 1～7 hour; The mol ratio of the carboxyl in hydroxyl in the said polyalcohol and the said acrylic or methacrylic acid is 1: 1～1.2, and the addition of said ionic-liquid catalyst is 10%～30% of the sour gross weight of polyalcohol and acrylic or methacrylic.After finishing, reaction left standstill 10～30 minutes; The system AUTOMATIC ZONING; Esterification products floats on the upper strata because of its density is less; The solution that polybasic ion liquid catalyst and water byproduct form promptly obtains the esterification crude product because of density is sunken to lower floor greatly after upper materials is separated, and lower floor's material can directly be used for next catalytic cycle.
Polyalcohol of the present invention comprises ethylene glycol, hexylene glycol, trimethylolpropane, pentaerythrite, neopentyl glycol etc.
Polybasic ion liquid catalyst of the present invention contains a plurality of ions center, has higher catalytic activity than existing monobasic ionic-liquid catalyst.It is not only applicable to monohydric alcohol and monacid esterification, can synthesize acetate, acrylic acid ester of single functionality etc.; Also be applicable to simultaneously polyalcohol that the esterification difficulty is bigger and the esterification between the acrylic acid; Synthesize the polyfunctional acrylic ester compounds, for example ethylene glycol bisthioglycolate (methyl) acrylic acid ester, butanediol two (methyl) acrylic acid ester, hexylene glycol two (methyl) acrylic acid ester, trimethylolpropane tris (methyl) acrylic acid ester, pentaerythrite three (methyl) acrylic acid ester, pentaerythrite two (methyl) acrylic acid ester etc.
Polybasic ion liquid of the present invention can synthesize the efficient of catalysis polyfunctional acrylic ester compounds under the lower temperature conditions, and conversion ratio reaches more than 90%, need not add azeotropic solvent in the course of reaction and carry out processed; Energy consumption is low; And can prevent the polymerisation that unsaturated bond takes place under hot conditions, and the reaction finish after, product and catalyst system AUTOMATIC ZONING; Can obtain esterification products through simple separatory processing; Through the directly recycle of polybasic ion liquid catalyst of reclaiming, and can keep advantages of high catalytic activity, have long service life.
The specific embodiment
Embodiment 1～8 is the preparation method of polybasic ion liquid of the present invention, and embodiment 9～16 is the synthetic method of acrylic ester compound of the present invention.
Embodiment 1
Take by weighing N, N, N ', N '-tetramethylethylenediamine 116.21g; The volume of packing into is 500ml, has in the four neck round-bottomed flasks of condensation and agitating device, feeds nitrogen, is warming up to 40 ℃; After stirring 10min, take by weighing pyrovinic acid 192.2g, the constant pressure funnel of packing into is incubated 40 ℃; In four neck flasks, drip pyrovinic acid, dropwise in the 1h, heat release is obvious in the dropping process.Be warming up to 60 ℃ after dropwising, behind the insulation reaction 3h, promptly obtain ionic-liquid catalyst N, N, N ', N '-tetramethylethylenediamine dimethyl methyl hydrochlorate, its productive rate is 98%, stable to empty G&W, density is 1.208g/cm
3, fusing point is 28 ℃.
Embodiment 2
Take by weighing N, N, N ', N '-tetramethylethylenediamine 116.21g; The volume of packing into is 500ml, has in the four neck round-bottomed flasks of condensation and agitating device, feeds nitrogen, is warming up to 40 ℃; After stirring 10min, take by weighing propyl sulfonic acid 248.3g, the constant pressure funnel of packing into is incubated 40 ℃; In four neck flasks, drip propyl sulfonic acid, dropwise in the 1h, heat release is obvious in the dropping process.Be warming up to 60 ℃ after dropwising, behind the insulation reaction 3h, promptly obtain ionic-liquid catalyst N, N, N ', N '-tetramethylethylenediamine dipropyl sulfonate, its productive rate is 98%, stable to empty G&W, density is 1.179g/cm
3, fusing point is 19.7 ℃.
Embodiment 3
Take by weighing N, N, N ', N '-4-methyl hexamethylene diamine 172.3g; The volume of packing into is 500ml, has in the four neck round-bottomed flasks of condensation and agitating device, feeds nitrogen, is warming up to 40 ℃; After stirring 10min, take by weighing pyrovinic acid 192.2g, the constant pressure funnel of packing into is incubated 40 ℃; In four neck flasks, drip pyrovinic acid, dropwise in the 1h, heat release is obvious in the dropping process.Be warming up to 60 ℃ after dropwising, behind the insulation reaction 3h, promptly obtain ionic-liquid catalyst N, N, N ', N '-4-methyl hexamethylene diamine dimethyl methyl hydrochlorate, its productive rate is 97%, stable to empty G&W, density is 1.221g/cm
3, fusing point is 20 ℃.
Embodiment 4
Take by weighing triethyl group diamines 112.17g, deionized water 60g, the volume of packing into is 500ml, has in the four neck round-bottomed flasks of condensation and agitating device; Feed nitrogen, be warming up to 50 ℃, behind the stirring 10min; Take by weighing pyrovinic acid 192.2g, the constant pressure funnel of packing into is incubated 50 ℃; In four neck flasks, drip pyrovinic acid, dropwise in the 1h, heat release is obvious in the dropping process.Be warming up to 60 ℃ after dropwising, behind the insulation reaction 3h, promptly obtain ionic-liquid catalyst triethyl group diamines dimethyl methyl hydrochlorate, its non-volatile component content is 83.1%, and productive rate is 98%, and stable to empty G&W, density is 1.283g/cm
3
Embodiment 5
Take by weighing hexa 140.20g, deionized water 100g, the volume of packing into is 1000ml, has in the four neck round-bottomed flasks of condensation and agitating device; Feed nitrogen, be warming up to 50 ℃, behind the stirring 10min; Take by weighing butyl sulfonic acid 552.7g, the constant pressure funnel of packing into is incubated 50 ℃; In four neck flasks, drip butyl sulfonic acid, dropwise in the 1h, heat release is obvious in the dropping process.Be warming up to 60 ℃ after dropwising, behind the insulation reaction 3h, promptly obtain ionic-liquid catalyst hexa tetrabutyl sulfonate, its non-volatile component content is 87.3%, and productive rate is 98%, and stable to empty G&W, density is 1.206g/cm
3
Embodiment 6
Take by weighing N, N, N ', N '-tetramethylethylenediamine 116.21g; The volume of packing into is 500ml, has in the four neck round-bottomed flasks of condensation and agitating device, feeds nitrogen, is warming up to 40 ℃; After stirring 10min, take by weighing the concentrated sulfuric acid (mass fraction is 98.3%) 199.4g, the constant pressure funnel of packing into is incubated 40 ℃; In four neck flasks, drip the concentrated sulfuric acid, dropwise in the 1h, heat release is obvious in the dropping process.Be warming up to 60 ℃ after dropwising, behind the insulation reaction 3h, promptly obtain ionic-liquid catalyst N, N, N ', N '-tetramethylethylenediamine dithionate, its productive rate are 97.1%, stable to empty G&W, density is 1.217g/cm
3, fusing point is 31 ℃.
Embodiment 7
Take by weighing N, N, N ', N '-tetramethylethylenediamine 116.21g; The volume of packing into is 500ml, has in the four neck round-bottomed flasks of condensation and agitating device, feeds nitrogen, is warming up to 40 ℃; After stirring 10min, take by weighing phosphoric acid (mass fraction is 80%) 245.3g, the constant pressure funnel of packing into is incubated 40 ℃; In four neck flasks, drip the concentrated sulfuric acid, dropwise in the 1h, heat release is obvious in the dropping process.Be warming up to 60 ℃ after dropwising, behind the insulation reaction 3h, rotary evaporation (60 ℃) dewaters, and promptly obtains ionic-liquid catalyst N, N, and N ', N '-tetramethylethylenediamine diphosphate, its productive rate are 92.4%, stable to empty G&W, density is 1.223g/cm
3, fusing point is 32 ℃.
Embodiment 8
Take by weighing N, N, N ', N '-tetramethylethylenediamine 116.21g; The volume of packing into is 500ml, has in the four neck round-bottomed flasks of condensation and agitating device, feeds nitrogen, is warming up to 60 ℃; After stirring 10min, take by weighing glacial acetic acid 120.2g, the constant pressure funnel of packing into is incubated 60 ℃; In four neck flasks, drip the concentrated sulfuric acid, dropwise in the 1h, heat release is obvious in the dropping process.Be warming up to 80 ℃ after dropwising, behind the insulation reaction 3h, promptly obtain ionic-liquid catalyst N, N, N ', N '-tetramethylethylenediamine two glacial acetic acid salt, its productive rate is 91.6%, stable to empty G&W, density is 1.201g/cm
3, fusing point is 29 ℃.
Embodiment 9
The ionic-liquid catalyst 120g that adds benzylalcohol 432.5g, methacrylic acid 361.6g (excessive 5%) successively in the 2000ml that condenser pipe and agitating device the are housed four neck round-bottomed flasks and make (this addition be benzylalcohol and methacrylic acid gross weight 15%) by embodiment 1; Stirring is warming up to 40 ℃; Leave standstill 10min behind the insulation reaction 5h; Make the reaction system AUTOMATIC ZONING, emit lower floor's catalyst and water, supernatant liquor is a methacrylic acid benzyl ester crude product; Its productive rate is 92%, and refraction index is n20/D1.513.
Embodiment 10
The ionic-liquid catalyst 146g that adds ethylene glycol 248.2g, methacrylic acid 723.2g (excessive 5%) successively in the 2000ml that condenser pipe and agitating device the are housed four neck round-bottomed flasks and make (this addition be ethylene glycol and methacrylic acid gross weight 15%) by embodiment 1; Stirring is warming up to 50 ℃; Leave standstill 10min behind the insulation reaction 5h; Make the reaction system AUTOMATIC ZONING, emit lower floor's catalyst and water, supernatant liquor is the ethylene glycol dimethacrylate crude product; Its productive rate is 91.3%, and refraction index is n20/D1.456.
Embodiment 11
The ionic-liquid catalyst 146g that adds ethylene glycol 248.2g, methacrylic acid 723.2g (excessive 5%) successively in the 2000ml that condenser pipe and agitating device the are housed four neck round-bottomed flasks and make (this addition be ethylene glycol and methacrylic acid gross weight 15%) by embodiment 6; Stirring is warming up to 50 ℃; Leave standstill 10min behind the insulation reaction 5h; Make the reaction system AUTOMATIC ZONING, emit lower floor's catalyst and water, supernatant liquor is the ethylene glycol dimethacrylate crude product; Its productive rate is 88.4%, and refraction index is n20/D1.456.
Embodiment 12
The ionic-liquid catalyst 146g that adds ethylene glycol 248.2g, methacrylic acid 723.2g (excessive 5%) successively in the 2000ml that condenser pipe and agitating device the are housed four neck round-bottomed flasks and make (this addition be ethylene glycol and methacrylic acid gross weight 15%) by embodiment 7; Stirring is warming up to 60 ℃; Leave standstill 10min behind the insulation reaction 5h; Make the reaction system AUTOMATIC ZONING, emit lower floor's catalyst and water, supernatant liquor is the ethylene glycol dimethacrylate crude product; Its productive rate is 68.4%, and refraction index is n20/D1.456.
Embodiment 13
The ionic-liquid catalyst 146g that adds ethylene glycol 248.2g, methacrylic acid 723.2g (excessive 5%) successively in the 2000ml that condenser pipe and agitating device the are housed four neck round-bottomed flasks and make (this addition be ethylene glycol and methacrylic acid gross weight 15%) by embodiment 8; Stirring is warming up to 80 ℃; Leave standstill 10min behind the insulation reaction 5h; Make the reaction system layering obvious, emit lower floor's catalyst and water, supernatant liquor is the ethylene glycol dimethacrylate crude product; Its productive rate is 43.4%, and refraction index is n20/D1.456.
Embodiment 14
The ionic-liquid catalyst 180g that adds hexylene glycol 472.6g, methacrylic acid 723.2g (excessive 5%) successively in the 2000ml that condenser pipe and agitating device the are housed four neck round-bottomed flasks and make (this addition be hexylene glycol and methacrylic acid gross weight 15%) by embodiment 1; Stirring is warming up to 50 ℃; Leave standstill 10min behind the insulation reaction 5h; Make the reaction system AUTOMATIC ZONING, emit lower floor's catalyst and water, supernatant liquor is the hexanediol dimethacrylate crude product; Its productive rate is 92.6%, and refraction index is n20/D 1.458.
Embodiment 15
In the 2000ml that condenser pipe and agitating device are housed four neck round-bottomed flasks, add trimethylolpropane 536.6g, acrylic acid 907.9g (excessive 5%) successively; Ionic-liquid catalyst 217g that makes by embodiment 1 (this addition be trimethylolpropane and acrylic acid gross weight 15%) and polymerization inhibitor p methoxy phenol 0.5g; Stirring is warming up to 70 ℃, leaves standstill 10min behind the insulation reaction 6h, makes the reaction system AUTOMATIC ZONING; Emit lower floor's catalyst and water; Supernatant liquor is the trimethylolpropane triacrylate crude product, and its productive rate is 87.6%, and refraction index is n20/D 1.475.
Embodiment 16
In the 2000ml that condenser pipe and agitating device are housed four neck round-bottomed flasks, add pentaerythrite 544.6g, acrylic acid 907.9g (excessive 5%) successively; Ionic-liquid catalyst 218g that is made by embodiment 5 (this addition be pentaerythrite and acrylic acid gross weight 15%) and polymerization inhibitor p methoxy phenol 1.0g stir and are warming up to 80 ℃, leave standstill 10min behind the insulation reaction 8h; Make the reaction system AUTOMATIC ZONING; Emit lower floor's catalyst and water, supernatant liquor is the pentaerythritol triacrylate crude product, and its productive rate is 88.4%; The content of pentaerythritol triacrylate is 78%, and refraction index is n20/D1.482.
Check experiment
The triethylene tetramine formates is ion liquid synthetic: in being furnished with the round-bottomed flask of magnetic agitation, add the triethylene tetramine of 14.7ml, add the 50ml absolute ethyl alcohol then; Stir 30min under the ice-water bath condition; Dropwise add 85% formic acid solution 17.8ml then while stirring, white precipitate occurs, continue to drip formic acid solution 2ml; Carry out suction filtration after reacting about 10min, the solid matter that leaches is triethylene tetramine formates ionic liquid.
Add trimethylolpropane 536.6g, acrylic acid 907.9g (excessive 5%), ionic-liquid catalyst triethylene tetramine formates 217g (this addition be trimethylolpropane and acrylic acid gross weight 15%) and polymerization inhibitor p methoxy phenol 1.0g in the 2000ml that condenser pipe and agitating device the are housed four neck round-bottomed flasks successively; Stirring is warming up to 70 ℃; Leave standstill 10min behind the insulation reaction 6h, reaction system does not have the AUTOMATIC ZONING phenomenon.
Experiment shows, is failed synthesizing of efficient catalytic polyfunctional acrylic ester compounds by the ionic-liquid catalyst that polynary primary amine/secondary amine and weak acid reaction generate.
Claims (10)
1. polybasic ion liquid catalyst, it is characterized in that: contain two or more ions center, its cation is polynary quaternary ammonium ion, and its anion is the strong acid radical ion.
2. polybasic ion liquid catalyst according to claim 1 is characterized in that: described polynary quaternary ammonium ion comprises tetramethylethylenediamine cation, tetramethyl butane diamine cation, 4-methyl hexamethylene diamine cation, triethylenediamine cation and hexa cation.
3. polybasic ion liquid catalyst according to claim 1 is characterized in that: described strong acid radical ion comprises alkyl sulfonate ion, acetate ion, hydrogen sulfate ion, phosphate anion and nitrate ion.
4. the preparation method of the said polybasic ion liquid catalyst of claim 1, it is characterized in that: with polynary tertiary amine and strong acid was raw material, 30 ℃～60 ℃ following stirring reactions 2～6 hours; Wherein, the mol ratio between the nitrogen-atoms in said strong acid and the said polynary tertiary amine is 1: 0.8～1.2.
5. preparation method according to claim 4; It is characterized in that: described polynary tertiary amine comprises tetramethylethylenediamine, tetramethyl butane diamine, 4-methyl hexamethylene diamine, triethylenediamine and hexa, and described strong acid comprises alkyl sulfonic acid, acetate, sulfuric acid, phosphoric acid and nitric acid.
6. the synthetic method of an acrylic ester compound; It is characterized in that: is raw material with acrylic or methacrylic acid with polyalcohol; With the described polybasic ion liquid of claim 1 is that catalyst and reaction media carry out esterification; Reaction temperature is 20 ℃～100 ℃, and the reaction time is 1～7 hour.
7. synthetic method according to claim 6 is characterized in that: the mol ratio of the carboxyl in hydroxyl in the said polyalcohol and the said acrylic or methacrylic acid is 1: 1～1.2.
8. synthetic method according to claim 6 is characterized in that: the addition of said ionic-liquid catalyst is 10%～30% of the sour gross weight of said polyalcohol and said acrylic or methacrylic.
9. synthetic method according to claim 6 is characterized in that: described polyalcohol comprises ethylene glycol, hexylene glycol, trimethylolpropane, pentaerythrite and neopentyl glycol.
10. synthetic method according to claim 6 is characterized in that: left standstill 10～30 minutes after reaction finishes, make the system AUTOMATIC ZONING, upper materials is separated obtained the esterification crude product.
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| CN102416347B (en) | 2013-11-20 |
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