CN103524344A - Preparation method of ethoxylation (2) 1, 6-hexanediol diacrylate - Google Patents
Preparation method of ethoxylation (2) 1, 6-hexanediol diacrylate Download PDFInfo
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- CN103524344A CN103524344A CN201310472470.3A CN201310472470A CN103524344A CN 103524344 A CN103524344 A CN 103524344A CN 201310472470 A CN201310472470 A CN 201310472470A CN 103524344 A CN103524344 A CN 103524344A
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- ethoxylation
- acid catalyst
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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 invention relates to a preparation method of ethoxylation (2) 1,6-hexanediol diacrylate. The method comprises the following steps: adding a main material ethoxylation (2) 1, 6-hexanediol and acrylic acid into an esterification reaction container; adding a solid acid catalyst; adding an inhibitor; reacting at a certain temperature and under vacuum conditions; then filtering out the solid acid catalyst; and distilling residual acrylic acid and water to obtain the ethoxylation (2) 1, 6-hexanediol diacrylate. Compared with the prior art, the invention has the following beneficial effects: no volatile organic compounds, high product yield, environment-friendly green product, no pollution to the environment and improved quality of the product.
Description
Technical field
The present invention relates to compou nd synthesis field, the preparation method of a kind of ethoxylation (2) 1,6 hexanediol diacrylate particularly, 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 generating in its building-up process, all by dewatering agent, remove, conventional dewatering agent has benzene,toluene,xylene, hexanaphthene etc., utilizes the water producing 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 is more lower slightly than benzene; Dimethylbenzene boiling point is high; In industries such as coating, ink and tamanoris, benzene-series solvent has been limited to use.
When ester-interchange method is prepared multi-functional acrylate, use lower member ester mostly to be methyl acrylate, due to its boiling point lower (70 ℃), therefore esterification can only be carried out at lower temperature, reaction times is extended, and product methyl alcohol can form azeotrope with methyl acrylate again, and its boiling point is 60 ℃ of left and right, reactant methyl acrylate can be taken away, thereby reduce output and product yield.
In chloride method preparation process, there are 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 under High Temperature High Pressure, alcohol and acetylene direct reaction, particularly acetylene has explosion hazard, and product yield is low.
Along with constantly exploitation and fast-developing of photocuring technology, radiation curing industry is constantly increasing acrylate product consumption, its Application Areas scope has covered the every aspect of social production, and main associated industry comprises: building decoration, packages printing, household electrical appliance, microelectronics, automobile, instrument, sports goods etc.
Along with the continuous increase of environmental protection pressure, to volatile organic matter, emission control adds sternly in country, and with the acrylate that does not contain volatile organic matter, replacing solvent type acrylate will be inexorable trend.
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, the ethoxylation (2) 1 making, 6-hexanediyl ester has good physicochemical property, in the inventive method preparation process, do not contain solvent, and preparation cost is low, yield 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 glycols and vinylformic acid to add in esterification container, then add solid acid catalyst, add stopper, under certain temperature and vacuum degree condition, react, then elimination solid acid catalyst, distills residual vinylformic acid and water, obtain ethoxylation (2) 1,6 hexanediol diacrylate.
Particularly, the preparation method of this ethoxylation (2) 1,6 hexanediol diacrylate, comprises the steps:
1), major ingredient ethoxylation (2) 1,6-hexylene glycols and vinylformic acid are put into esterification container, add solid acid catalyst, add stopper, stirring reaction, obtains reaction mass;
2), esterification reaction process carries out under vacuum, the pressure of controlling in esterification container is 0.03～0.098Mpa, rising esterification reaction temperature, carrying out along with esterification process, constantly steam the water that reaction generates, until the acid number detecting in reaction soln is 25-35mgHOK/g, start to be cooled to normal temperature;
3), reactant after esterification is filtered to still kettle, filter out solid acid catalyst, under vacuum, distill residual vinylformic acid, vacuum degree control exists: 0.09-0.098Mpa, distillation temperature is controlled at: 98-115 ℃, until material acid number is 0.5-1mgKOH/g, start to be cooled to normal temperature, obtain product.
Preferably, in this preparation method, do not add solvent.
Preferably, described stopper is MEHQ or is a minute 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 12% weak ammonia, be hydrolyzed into solution and be alkalescence, precipitation completely, after standing 24 hours, suction filtration, cleans chlorion, after infrared drying, grind to form 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 in retort furnace, activates 3 hours at 500 ℃, makes rare-earth solid superacid, is solid acid catalyst.
Preferably, described rare earth oxide is La
2o
3.
The inventive method be ethoxylation (2) 1, the 6-hexylene glycols of certain mol proportion and vinylformic acid under the existence of solid acid catalyst, under certain temperature and vacuum tightness, react.In reaction process, along with the carrying out of esterification process, constantly steam the water that reaction generates.After esterification finishes, filter out the solid acid catalyst in reaction system, then steam residual vinylformic acid and water, can obtain product.
Compared with prior art, the invention has the beneficial effects as follows: do not contain volatile organic matter, product yield is high, is environment-friendly and green product, and environmentally safe improves 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 preparation method for 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, is placed in 500ml there-necked flask, open to stir, stirring reaction 2 hours, carries out esterification.
2), open vacuum pump, pressure in control reaction flask is at 0.05Mpa, the temperature to 120 ℃ promoting again in flask has the generation of backflow, the water that reaction is generated constantly flows out by water trap, reaction times is 5 hours, the acid number that reaction soln detected is 30mgKOH/g, stops heating up, and starts to be cooled to normal temperature.
3), filter material, under the condition of 98 ℃ of temperature, vacuum tightness 0.09Mpa, residual vinylformic acid and water are removed in distillation, control acid number when 0.92mgKOH/g, can stop distillation, are down to room temperature, yield is 95%, obtains product, packing.
Embodiment 2:
A preparation method for 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, is placed in 500ml there-necked flask, open to stir, stirring reaction 2 hours, carries out esterification.
2), open vacuum pump, pressure in control reaction flask is at 0.075Mpa, the temperature to 110 ℃ promoting again in flask has the generation of backflow, the water that reaction is generated constantly flows out by water trap, reaction times is 3.5 hours, the acid number that reaction soln detected is 35mgKOH/g, stops heating up, and starts to be cooled to normal temperature.
3), filter material, under the condition of 105 ℃ of temperature, vacuum tightness 0.095Mpa, residual vinylformic acid and water are removed in distillation, control acid number when 0.76mgKOH/g, can stop distillation, are down to room temperature, yield is 94%, obtains product, packing.
Embodiment 3:
A preparation method for 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, is placed in 500ml there-necked flask, open to stir, stirring reaction 2 hours, carries out esterification.
2), open vacuum pump, control pressure in reaction flask at 0.098Mpa, then promote temperature to 98 ℃ in flask and have to reflux and produce, the water that reaction is generated constantly flows out by water trap, reaction times is 2 hours, and the acid number that reaction soln detected is 35mgKOH/g, stops heating up.Start to be cooled to normal temperature.
3), filter material, under the condition of 115 ℃ of temperature, vacuum tightness 0.098Mpa, residual vinylformic acid and water are removed in distillation, control acid number when 0.58mgKOH/g, can stop distillation, are down to room temperature, yield is 93.8%, obtains product, packing.
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 12% weak ammonia, be hydrolyzed into solution and be alkalescence, completely, after standing 24 hours, suction filtration, cleans chlorion to precipitation, grinds to form and be less than 100 object powder after infrared drying, obtains TiO
2.
By 0.035mol La
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 in retort furnace, activates 3 hours at 500 ℃, makes rare-earth solid superacid, is solid acid catalyst.
Claims (7)
1. an ethoxylation (2) 1, the preparation method of 6-hexanediyl ester, it is characterized in that: comprise the steps: major ingredient ethoxylation (2) 1,6-hexylene glycols and vinylformic acid to add in esterification container, then add solid acid catalyst, add stopper, under certain temperature and vacuum degree condition, react, then elimination solid acid catalyst, distills residual vinylformic acid and water, obtain ethoxylation (2) 1,6 hexanediol diacrylate.
2. preparation method according to claim 1, is characterized in that: the preparation method of this ethoxylation (2) 1,6 hexanediol diacrylate, comprises the steps:
1), major ingredient ethoxylation (2) 1,6-hexylene glycols and vinylformic acid are put into esterification container, add solid acid catalyst, add stopper, stirring reaction, obtains reaction mass;
2), esterification reaction process carries out under vacuum, the pressure of controlling in esterification container is 0.03～0.098Mpa, rising esterification reaction temperature, carrying out along with esterification process, constantly steam the water that reaction generates, until the acid number detecting in reaction soln is 25-35mgHOK/g, start to be cooled to normal temperature;
3), reactant after esterification is filtered to still kettle, filter out solid acid catalyst, under vacuum, distill residual vinylformic acid, vacuum degree control exists: 0.09-0.098Mpa, distillation temperature is controlled at: 98-115 ℃, until material acid number is 0.5-1mgKOH/g, start to be cooled to normal temperature, obtain product.
3. preparation method according to claim 1, is characterized in that: in this preparation method, do not add solvent.
4. according to the preparation method described in claim 1-3 any one, it is characterized in that: described stopper is MEHQ or is a minute thiazine.
5. according to the preparation method described in claim 1-4 any one, it is characterized in that: described solid acid catalyst is the polymer microsphere solid acid catalyst with sulfonic acid group.
6. according to the preparation method described in claim 1-4 any one, it is characterized in that: the preparation method of described solid acid catalyst, comprise the steps: in stink cupboard, get 50ml titanium tetrachloride in 500ml large beaker, add 12% weak ammonia, be hydrolyzed into solution and be alkalescence, precipitation is complete, after standing 24 hours, suction filtration, clean chlorion, after infrared drying, grind to form 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 in retort furnace, activates 3 hours at 500 ℃, makes rare-earth solid superacid, is solid acid catalyst.
7. according to the preparation method described in claim 6 any one, it is characterized in that: described rare earth oxide is La
2o
3.
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| CN201310472470.3A CN103524344B (en) | 2013-10-11 | 2013-10-11 | A kind of preparation method of ethoxylation (2) 1,6 hexanediol diacrylate |
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| CN201310472470.3A CN103524344B (en) | 2013-10-11 | 2013-10-11 | A kind of preparation method of ethoxylation (2) 1,6 hexanediol diacrylate |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105566113A (en) * | 2015-04-16 | 2016-05-11 | 湖南省金海科技有限公司 | Clean production method of bifunctional acrylic ester 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 |
| CN113215825A (en) * | 2021-04-29 | 2021-08-06 | 江苏利田科技股份有限公司 | Fabric crease-resistant UV finishing agent and preparation method thereof |
Citations (5)
| 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 |
| US20130035504A1 (en) * | 2011-08-03 | 2013-02-07 | Cognis Ip Management Gmbh | Process For Preparing (Meth)Acrylic Esters Of Polyols |
-
2013
- 2013-10-11 CN CN201310472470.3A patent/CN103524344B/en active Active
Patent Citations (5)
| 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 |
| US20130035504A1 (en) * | 2011-08-03 | 2013-02-07 | Cognis Ip Management Gmbh | Process For Preparing (Meth)Acrylic Esters Of Polyols |
Non-Patent Citations (1)
| Title |
|---|
| 周海峰等: "SO42- /TiO2/ La3+催化合成季戊四醇三丙烯酸酯", 《日用化学工业》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105566113A (en) * | 2015-04-16 | 2016-05-11 | 湖南省金海科技有限公司 | Clean production method of bifunctional acrylic ester reactive diluent |
| 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 |
| CN113215825A (en) * | 2021-04-29 | 2021-08-06 | 江苏利田科技股份有限公司 | Fabric crease-resistant UV finishing agent and preparation method thereof |
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| CN103524344B (en) | 2015-11-18 |
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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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