CN103524344B - A kind of preparation method of ethoxylation (2) 1,6 hexanediol diacrylate - Google Patents
A kind of preparation method of ethoxylation (2) 1,6 hexanediol diacrylate Download PDFInfo
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- CN103524344B CN103524344B CN201310472470.3A CN201310472470A CN103524344B CN 103524344 B CN103524344 B CN 103524344B CN 201310472470 A CN201310472470 A CN 201310472470A CN 103524344 B CN103524344 B CN 103524344B
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- ethoxylation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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Abstract
The present invention relates to a kind of ethoxylation (2) 1, the preparation method of 6-hexanediyl ester, comprise the steps: major ingredient ethoxylation (2) 1,6-hexylene glycol and vinylformic acid to add in esterification container, then add solid acid catalyst, add stopper, react at certain temperature and vacuum degree condition, then elimination solid acid catalyst, distill residual vinylformic acid and water, namely ethoxylation (2) 1,6 hexanediol diacrylate is 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.
Description
Technical field
The present invention relates to compou nd synthesis field, particularly the preparation method of a kind of ethoxylation (2) 1,6 hexanediol diacrylate, ethoxylation (2) 1,6 hexanediol diacrylate 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 ethoxylation (2) 1, the preparation method of 6-hexanediyl ester, obtained ethoxylation (2) 1,6-hexanediyl ester has good physicochemical property, not containing solvent in the inventive method preparation process, and preparation cost is low, 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 ethoxylation (2) 1, the preparation method of 6-hexanediyl ester, comprise the steps: major ingredient ethoxylation (2) 1,6-hexylene glycol and vinylformic acid to add in esterification container, then add solid acid catalyst, add stopper, react at certain temperature and vacuum degree condition, then elimination solid acid catalyst, distill residual vinylformic acid and water, namely ethoxylation (2) 1,6 hexanediol diacrylate is obtained.
Particularly, the preparation method of this ethoxylation (2) 1,6 hexanediol diacrylate, comprises the steps:
1), by major ingredient ethoxylation (2) 1,6-hexylene glycol 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 0.03 ~ 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 25-35mgHOK/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.
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.
Ethoxylation (2) 1, the 6-hexylene glycol 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 ethoxylation (2) 1,6 hexanediol diacrylate, comprises the steps:
1), by ethoxylation (2) 1,6-hexylene glycol 97g, vinylformic acid 57.6g, 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, yield is 95%, namely obtains product, packaging.
Embodiment 2:
A kind of preparation method of ethoxylation (2) 1,6 hexanediol diacrylate, comprises the steps:
1), by ethoxylation (2) 1,6-hexylene glycol 97g, vinylformic acid 57.6g, 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 0.075Mpa, the temperature to 110 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 3.5 hours, detect that the acid number of reaction soln is 35mgKOH/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 105 DEG C, vacuum tightness 0.095Mpa and water, control acid number when 0.76mgKOH/g, can stop distillation, be down to room temperature, yield is 94%, namely obtains product, packaging.
Embodiment 3:
A kind of preparation method of ethoxylation (2) 1,6 hexanediol diacrylate, comprises the steps:
1), by ethoxylation (2) 1,6-hexylene glycol 97g, vinylformic acid 57.6g, 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 35mgKOH/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, yield is 93.8%, namely obtains product, packaging.
Embodiment 4
In embodiment 1-3, 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 (2)
1. a preparation method for ethoxylation (2) 1,6 hexanediol diacrylate, is characterized in that: step is:
1), by major ingredient ethoxylation (2) 1,6-hexylene glycol 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 0.03 ~ 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 25-35mgKOH/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;
Described solid acid catalyst is the polymer microsphere solid acid catalyst with sulfonic acid group.
2. preparation method according to claim 1, is characterized in that: described stopper is MEHQ or is thiodiphenylamine.
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| CN105566113B (en) * | 2015-04-16 | 2017-10-31 | 湖南省金海科技有限公司 | A kind of clean preparation method of bifunctionality acrylate reactive diluent |
| CN106699553A (en) * | 2015-11-13 | 2017-05-24 | 惠州市长润发涂料有限公司 | Preparation method of 1,6-hexanediol diacrylate |
| CN113215825B (en) * | 2021-04-29 | 2023-04-07 | 江苏利田科技有限公司 | Fabric crease-resistant UV finishing agent and preparation method thereof |
Citations (4)
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|---|---|---|---|---|
| CN1683315A (en) * | 2005-03-02 | 2005-10-19 | 张本田 | Process for producing trihydroxy methyl propane triacrylate |
| CN101462959A (en) * | 2007-12-18 | 2009-06-24 | 天津市化学试剂研究所 | Method for preparing ethoxylated 1,6-hexanediyl ester |
| CN101838376A (en) * | 2010-05-11 | 2010-09-22 | 张春华 | Derived and branched multifunctional (methyl) acrylic ester composition containing citric acid |
| CN102311455A (en) * | 2011-05-19 | 2012-01-11 | 张春华 | Radiation-curable polyfunctional (meth)acrylic ester combination containing phosphonic group and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8772532B2 (en) * | 2011-08-03 | 2014-07-08 | Cognis Ip Management Gmbh | Process for preparing (meth)acrylic esters of polyols |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1683315A (en) * | 2005-03-02 | 2005-10-19 | 张本田 | Process for producing trihydroxy methyl propane triacrylate |
| CN101462959A (en) * | 2007-12-18 | 2009-06-24 | 天津市化学试剂研究所 | Method for preparing ethoxylated 1,6-hexanediyl ester |
| CN101838376A (en) * | 2010-05-11 | 2010-09-22 | 张春华 | Derived and branched multifunctional (methyl) acrylic ester composition containing citric acid |
| CN102311455A (en) * | 2011-05-19 | 2012-01-11 | 张春华 | Radiation-curable polyfunctional (meth)acrylic ester combination containing phosphonic group and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| SO42- /TiO2/ La3+催化合成季戊四醇三丙烯酸酯;周海峰等;《日用化学工业》;20050228;第35卷(第1期);19-22 * |
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Inventor after: Huang Fengqi Inventor after: Jia Zhenlin Inventor after: Huang Jianwen Inventor after: He Qiqiang Inventor before: Huang Fengqi Inventor before: Huang Jianwen Inventor before: He Qiqiang |
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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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