CN103342644B - A kind of preparation method of polyalcohol acrylate - Google Patents
A kind of preparation method of polyalcohol acrylate Download PDFInfo
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- CN103342644B CN103342644B CN201310312326.3A CN201310312326A CN103342644B CN 103342644 B CN103342644 B CN 103342644B CN 201310312326 A CN201310312326 A CN 201310312326A CN 103342644 B CN103342644 B CN 103342644B
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Abstract
The present invention relates to a kind of preparation method of polyalcohol acrylate, it is characterized in that: comprise the steps: major ingredient polyvalent alcohol and vinylformic acid to add in esterification container, add solid acid catalyst again, add stopper, react at certain temperature and vacuum degree condition, then elimination solid acid catalyst, distills residual vinylformic acid and water, namely obtains polyalcohol acrylate.Compared with prior art, the invention has the beneficial effects as follows: not containing volatile organic matter, product yield is high, is environment-friendly and green product, environmentally safe, improve product quality.
Description
Technical field
The present invention relates to compou nd synthesis field, particularly a kind of preparation method of polyalcohol acrylate, polyalcohol acrylate can be used for radiation curing reactive diluent.
Background technology
The synthetic method of esters of acrylic acid reactive thinner mainly contains direct esterification, ester-interchange method, chloride method and addition esterification process, the water generated in its building-up process, all removed by dewatering agent, conventional dewatering agent has benzene,toluene,xylene, hexanaphthene etc., utilizes the water produced with esterification form azeotropic liquid and take away.Alkane price, high volatility; Benzene boiling point is on the low side, and volatility is large, toxic; Toluene toxicity ratio benzene is lower slightly; Xylene boiling point is high; In industries such as coating, ink and tamanoris, use is limited to benzene-series solvent.
When ester-interchange method prepares multi-functional acrylate, lower member ester is used mostly to be methyl acrylate, due to its boiling point lower (70 DEG C), therefore esterification can only be carried out at a lower temperature, reaction times is extended, and Methanol product can form azeotrope with methyl acrylate again, and its boiling point is about 60 DEG C, reactant methyl acrylate can be taken away, thus reduce output and product yield.
In chloride method preparation process, there is a large amount of HCL and SO
2produce, absorb with alkali lye and water, its waste water easily pollutes environment.
In addition esterification process acrylic ester synthesizing process, require at high temperature under high pressure, alcohol and acetylene direct reaction, particularly acetylene has explosion hazard, and product yield is low.
Along with photocuring technology is constantly developed and fast development, radiation curing industry is constantly increasing acrylate product consumption, its Application Areas scope has covered the every aspect of social production, and main association industry comprises: building decoration, packages printing, household electrical appliance, microelectronics, automobile, instrument, sports goods etc.
Along with the continuous increase of environmental protection pressure, country adds sternly to volatile organic matter emission control, replaces solvent type acrylate will be inexorable trend with the acrylate not containing volatile organic matter.
Summary of the invention:
The object of this invention is to provide a kind of preparation method of polyalcohol acrylate, obtained polyalcohol acrylate has good physicochemical property, and not containing solvent in the inventive method preparation process, and preparation cost is low, and yield that is easy and simple to handle, product is high.
For achieving the above object, technical scheme provided by the invention is:
A kind of preparation method of polyalcohol acrylate, major ingredient polyvalent alcohol and vinylformic acid is comprised the steps: to add in esterification container, add solid acid catalyst again, add stopper, react at certain temperature and vacuum degree condition, then elimination solid acid catalyst, distills residual vinylformic acid and water, namely obtains polyalcohol acrylate.
Particularly, the preparation method of this polyalcohol acrylate, comprises the steps:
1), by major ingredient polyvalent alcohol and vinylformic acid put into esterification container, add solid acid catalyst, add stopper, stirring reaction, obtain reaction mass;
2), esterification reaction process carries out under vacuo, the pressure controlled in esterification container is 0.05 ~ 0.098Mpa, raise esterification reaction temperature, along with the carrying out of esterification process, constantly steam the water that reaction generates, until detect that the acid number in reaction soln is 30-50mgHOK/g, start to be cooled to normal temperature;
3), reactant after esterification is filtered to still kettle, filters solid acid catalyst, residual vinylformic acid is distilled under vacuum, vacuum degree control exists: 0.09-0.098Mpa, distillation temperature controls: 98-115 DEG C, until material acid number is 0.5-1mgKOH/g, starts to be cooled to normal temperature, namely obtain product.
Further, described polyvalent alcohol is TriMethylolPropane(TMP) or Dipentaerythritol or ditrimethylolpropane.
Preferably, in this preparation method, solvent is not added.
Preferably, described stopper is MEHQ or is a point thiazine.
Preferably, described solid acid catalyst is the polymer microsphere solid acid catalyst with sulfonic acid group.
Or, preferably, the preparation method of described solid acid catalyst, comprise the steps: in stink cupboard, get 50ml titanium tetrachloride in 500ml large beaker, add the weak ammonia of 12%, be hydrolyzed into solution alkaline, precipitation completely, leave standstill after 24 hours, suction filtration, clean chlorion, grind to form after infrared drying and be less than 100 object powder, obtain TiO
2.
0.035mol rare earth oxide is dissolved in the dilute sulphuric acid 1L of 1.85mol/L, then by TiO
2be soaked in wherein (10g/25ml) 14 hours, suction filtration is dried, and activates 3 hours, namely make rare-earth solid superacid, be solid acid catalyst in retort furnace at 500 DEG C.
Preferably, described rare earth oxide is La
2o
3.
The polyvalent alcohol of the inventive method and certain mol proportion and vinylformic acid, under the existence of solid acid catalyst, react at certain temperature and vacuum tightness.In reaction process, along with the carrying out of esterification process, constantly steam the water that reaction generates.After esterification terminates, filter out the solid acid catalyst in reaction system, then steam residual vinylformic acid and water, can product be obtained.
Compared with prior art, the invention has the beneficial effects as follows: not containing volatile organic matter, product yield is high, is environment-friendly and green product, environmentally safe, improve product quality.
Embodiment
Below in conjunction with specific embodiment, the present invention will be further described, but do not limit protection scope of the present invention.
Embodiment 1:
A kind of preparation method of Viscoat 295 (TMPTA), comprises the steps:
1), by TriMethylolPropane(TMP) 80g, vinylformic acid 142g, solid acid catalyst 4.5g, thiodiphenylamine 0.5g, be placed in 500ml there-necked flask, and open and stir, stirring reaction 2 hours, carries out esterification.
2), vacuum pump is opened, pressure in control reaction flask is at 0.05Mpa, the temperature to 120 DEG C promoted again in flask has backflow to produce, the water that reaction generates constantly is flowed out by water trap, reaction times is 5 hours, detect that the acid number of reaction soln is 30mgKOH/g, stop heating up, start to be cooled to normal temperature.
3), filter material, the vinylformic acid that distillation removing is residual under the condition of temperature 98 DEG C, vacuum tightness 0.09Mpa and water, control acid number when 0.92mgKOH/g, can stop distillation, be down to room temperature, look number is 80APHA, yield is 95%, namely obtains product, packaging.
Embodiment 2:
A kind of preparation method of Dipentaerythritol Pentaacrylate (DPHA), comprises the steps:
1), by Dipentaerythritol 80 grams, vinylformic acid 136g, solid acid catalyst 4.5g, MEHQ 0.5g, be placed in 500ml there-necked flask, and open and stir, stirring reaction 2 hours, carries out esterification.
2), open vacuum pump, the pressure in control reaction flask is at 0.075Mpa, then the temperature to 110 DEG C promoted in flask has backflow to produce, the water that reaction generates constantly is flowed out by water trap, reaction times is 3.5 hours, detects that the acid number of reaction soln is 40mgKOH/g, stops heating up.Start to be cooled to normal temperature.
3), filter material, the vinylformic acid that distillation removing is residual under the condition of temperature 105 DEG C, vacuum tightness 0.095Mpa and water, control acid number when 0.76mgKOH/g, can stop distillation, be down to room temperature, look number is 70APHA, yield is 94%, namely obtains product, packaging.
Embodiment 3:
A kind of preparation method of ditrimethylolpropane tetraacrylate (DiTMP4A), comprises the steps:
1), by ditrimethylolpropane 80 grams, vinylformic acid 111g, solid acid catalyst 4.5g, MEHQ 0.5g, be placed in 500ml there-necked flask, and open and stir, stirring reaction 2 hours, carries out esterification.
2), open vacuum pump, the pressure in control reaction flask is at 0.098Mpa, then the temperature to 98 DEG C promoted in flask has backflow to produce, the water that reaction generates constantly is flowed out by water trap, reaction times is 2 hours, detects that the acid number of reaction soln is 50mgKOH/g, stops heating up.Start to be cooled to normal temperature.
3), filter material, the vinylformic acid that distillation removing is residual under the condition of temperature 115 DEG C, vacuum tightness 0.098Mpa and water, control acid number when 0.58mgKOH/g, can stop distillation, be down to room temperature, look number is 50APHA, yield is 93.8%, namely obtains product, packaging.
Embodiment 4
In embodiment 1,2,3, the preparation method of solid acid catalyst, comprises the steps:
In stink cupboard, get 50ml titanium tetrachloride in 500ml large beaker, add the weak ammonia of 12%, be hydrolyzed into solution alkaline, precipitation completely, leaves standstill after 24 hours, suction filtration, cleans chlorion, grinds to form and be less than 100 object powder, obtain TiO after infrared drying
2.
By 0.035molLa
2o
3be dissolved in the dilute sulphuric acid 1L of 1.85mol/L, then by TiO
2be soaked in wherein (10g/25ml) 14 hours, suction filtration is dried, and activates 3 hours, namely make rare-earth solid superacid, be solid acid catalyst in retort furnace at 500 DEG C.
Claims (1)
1. a preparation method for ditrimethylolpropane tetraacrylate, is characterized in that: step is:
1), by ditrimethylolpropane 80 grams, vinylformic acid 111g, solid acid catalyst 4.5g, MEHQ 0.5g, be placed in 500ml there-necked flask, and open and stir, stirring reaction 2 hours, carries out esterification;
2), vacuum pump is opened, pressure in control reaction flask is at 0.098Mpa, the temperature to 98 DEG C promoted again in flask has backflow to produce, the water that reaction generates constantly is flowed out by water trap, reaction times is 2 hours, detect that the acid number of reaction soln is 50mgKOH/g, stop heating up, start to be cooled to normal temperature;
3), filter material, the vinylformic acid that distillation removing is residual under the condition of temperature 115 DEG C, vacuum tightness 0.098Mpa and water, control acid number when 0.58mgKOH/g, can stop distillation, be down to room temperature, look number is 50APHA, yield is 93.8%, namely obtains product, packaging;
The preparation method of described solid acid catalyst, comprise the steps: in stink cupboard, get 50ml titanium tetrachloride in 500ml large beaker, add the weak ammonia of 12%, be hydrolyzed into solution alkaline, precipitation completely, leave standstill after 24 hours, suction filtration, clean chlorion, grind to form after infrared drying and be less than 100 object powder, obtain TiO
2; By 0.035molLa
2o
3be dissolved in the dilute sulphuric acid 1L of 1.85mol/L, then by TiO
2be soaked in wherein 14 hours, concentration 10g/25ml, suction filtration is dried, and activates 3 hours, namely make rare-earth solid superacid, be solid acid catalyst in retort furnace at 500 DEG C.
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| CN105820050B (en) * | 2016-04-18 | 2018-11-02 | 苏州吉人高新材料股份有限公司 | A kind of environment-friendly type lactate acrylate monomer and preparation method thereof |
| CN108003436B (en) * | 2017-12-22 | 2020-11-03 | 江苏美翔体育用品有限公司 | Preparation method of PE composite material |
| CN110156573A (en) * | 2019-07-01 | 2019-08-23 | 南通百川新材料有限公司 | Synthesis process of trimethylolpropane diallyl ether |
| CN111646901A (en) * | 2020-06-22 | 2020-09-11 | 南通百川新材料有限公司 | Preparation method of ditrimethylolpropane tetraacrylate |
| CN112194579A (en) * | 2020-10-10 | 2021-01-08 | 湖南创大玉兔化工有限公司 | Method capable of efficiently removing multi-acrylate impurities |
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| CN1585736A (en) * | 2001-11-15 | 2005-02-23 | 巴斯福股份公司 | Method for producing (meth)acrylic acid esters of polyhydric alcohols |
| CN1683315A (en) * | 2005-03-02 | 2005-10-19 | 张本田 | Process for producing trihydroxy methyl propane triacrylate |
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Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102146038A (en) * | 2010-11-24 | 2011-08-10 | 天津市天骄辐射固化材料有限公司 | Method for preparing ditrimethylolpropane tetraacrylate |
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| CN1585736A (en) * | 2001-11-15 | 2005-02-23 | 巴斯福股份公司 | Method for producing (meth)acrylic acid esters of polyhydric alcohols |
| CN1683315A (en) * | 2005-03-02 | 2005-10-19 | 张本田 | Process for producing trihydroxy methyl propane triacrylate |
| CN102146034A (en) * | 2010-11-24 | 2011-08-10 | 天津市天骄辐射固化材料有限公司 | Method for preparing dipentaerythritol pentaacrylate |
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| 林进等.稀土固体超强酸SO42-/TiO2/La3+催化合成丁酸异戊酯.《无机化学学报》.2000,第16卷(第5期),第829-832页. * |
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Inventor after: Feng Linsheng Inventor after: Huang Fengqi Inventor after: Jia Zhenlin Inventor after: Feng Wusheng Inventor before: Feng Linsheng Inventor before: Huang Fengqi Inventor before: Feng Wusheng |
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Effective date of registration: 20151013 Address after: 301510 Tianjin city Ninghe County zaojiacheng zaojiacheng Town Village West Century Tianxin Industrial Park Applicant after: Tianjin Tianjiao Radiation Curable Material Co., Ltd. Address before: Fifth 300132 Tianjin city Hongqiao District Road No. 8-8 Applicant before: Tianjin Tiaojiao Chemical Co., Ltd. |
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