CN102557935A - Preparation method of 1, 2, 3-glycerin triacrylate - Google Patents
Preparation method of 1, 2, 3-glycerin triacrylate Download PDFInfo
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- CN102557935A CN102557935A CN2010106020655A CN201010602065A CN102557935A CN 102557935 A CN102557935 A CN 102557935A CN 2010106020655 A CN2010106020655 A CN 2010106020655A CN 201010602065 A CN201010602065 A CN 201010602065A CN 102557935 A CN102557935 A CN 102557935A
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Abstract
The invention discloses a preparation method of 1, 2, 3-glycerin triacrylate, which uses bio-based material (1, 2, 3-glycerin) as a raw material, overcomes the space reaction steric hindrance of three hydroxyl radicals of the molecule and esterifies the hydroxyl radicals of three carbon atoms completely. Esterification reaction is carried out on the 1, 2, 3-glycerin and crylic acid under the existence of a catalyst, a polymerization inhibitor and a water-carrying agent, and then the target product (1, 2, 3-glycerin triacrylate) provided by the invention is obtained. The preparation method has the advantages that since solid acid or heteropoly acid is used as the catalyst and environmentally-friendly alkane is used as the water-carrying agent, the operation is safe and simple, the corrosion to equipment is avoided and the pollution to the environment is reduced.
Description
Technical field
The present invention relates to a kind of 1,2, the preparation method of 3-USP Kosher triacrylate.Relate in particular to a kind of use bio-based material 1,2, the 3-USP Kosher overcomes the space reaction steric hindrance of three hydroxyls of this molecule as raw material, makes the preparation method of three whole esterifications of hydroxyl on the carbon atom.
Background technology
Synthetic polyalcohol acrylate series product are gone up in industry at present; Mainly use the vitriol oil to be catalyzer; Prepared through esterification by vinylformic acid and polyvalent alcohol, there is following defective in the product that this technology obtains: 1. poor product quality, colourity, acidity and viscosity are higher, and are prone to muddy; 2. reaction back waste water and by product processing are loaded down with trivial details, and be serious to environmental influence; 3. product complex process, equipment corrosion are serious.
With bio-based material 1,2, the 3-USP Kosher is a feedstock production 1,2 at present, and the preparation method of 3-USP Kosher triacrylate does not appear in the newspapers.1,2 of the present invention's preparation, 3-USP Kosher triacrylate is a kind of novel product, is important vinylformic acid trifunctional esters monomer, and its molecular weight is 254, and outward appearance is colourless or light yellow liquid.This material has double bond content height, volatility is low, toxicity is little, cross-linking density is high, curing speed is fast characteristics, has in various fields such as the modification of photo-cured coating, printing ink and polymkeric substance and linking agents and uses future widely.
Summary of the invention
It is a kind of 1,2 that the technical problem that the present invention solves has provided, the preparation method of 3-USP Kosher triacrylate; With bio-based material 1,2, the 3-USP Kosher is a raw material; Overcome the space reaction steric hindrance of three hydroxyls of this molecule; Make three whole esterifications of the hydroxyl on the carbon atom, it is loaded down with trivial details that technology of the present invention has overcome in the existing compound method post-processing operation, the shortcoming of equipment corrosion.
Technical scheme of the present invention:
Reaction formula of the present invention is following:
The preparation method is:
In molar ratio 1,2, the 3-USP Kosher: the ratio of vinylformic acid=1: 3-4 is with 1; 2,3-USP Kosher and vinylformic acid are in the presence of catalyzer, stopper, band aqua, under 95 ± 5 ℃; Reacted 6-8 hour, band aqua consumption is 1,2; The 1-1.5 of 3-USP Kosher and acrylic acid total mass times, catalyst levels is the 2%-4% of reaction system total mass, and the stopper consumption is the 1%-2% of reaction system total mass; Here the reaction system total mass is meant 1,2, the total mass of 3-USP Kosher, vinylformic acid and band aqua.Neutralization obtains 1,2,3-USP Kosher triacrylate through after the underpressure distillation to reaction solution again through alkali earlier.
Described catalyzer is any one in p-methyl benzenesulfonic acid, silicotungstic acid or the phospho-wolframic acid; Described stopper is the mixture of any one or two kinds of Resorcinol, MEHQ, and described band aqua can be that any one or the two kinds of materials in toluene, benzene, normal hexane, the hexanaphthene mix.
Advantage of the present invention and beneficial effect are:
The present invention relates to 1,2, the preparation method of 3-USP Kosher triacrylate is different from traditional preparation method; Do not add the vitriol oil; Adopting solid acid or heteropolyacid is catalyzer, and the alkane of environmental protection is band aqua, simple and safe operation; Alleviated pollution and equipment corrosion, reduced production cost environment.
Embodiment
The present invention makes further detailed description through following examples to the present invention, need to prove: following embodiment is illustrative, is not determinate, can not limit protection scope of the present invention with following embodiment.
A kind of synthetic 1,2, the method for 3-USP Kosher triacrylate, compound method is: in molar ratio 1; 2, the 3-USP Kosher: the ratio of vinylformic acid=1: 3-4 is 1,2, and 3-USP Kosher and vinylformic acid are in the presence of catalyzer, stopper, band aqua; Under 95 ± 5 ℃, reacted 6-8 hour, band aqua consumption is 1,2; The 1-1.5 of 3-USP Kosher and acrylic acid total mass times, catalyst levels is the 2%-4% of reaction system total mass, and the stopper consumption is the 1%-2% of reaction system total mass; Here the reaction system total mass is meant 1,2, the total mass of 3-USP Kosher, vinylformic acid and band aqua; Described catalyzer is any one in p-methyl benzenesulfonic acid, silicotungstic acid or the phospho-wolframic acid; Described stopper is the mixture of any one or two kinds of Resorcinol, MEHQ, and described band aqua is that any one or the two kinds of materials in toluene, benzene, normal hexane, the hexanaphthene mix.Wherein 1,2, the 3-USP Kosher: acrylic acid mol ratio can be 1: 3.2,1: 3.5 or 1: 4 equal proportion; Temperature of reaction can be 95 ℃, 100 ℃ or 105 ℃ etc., and the reaction times can be 6h, 7h, 8h etc.; Catalyst levels can be 2%, 2.5%, 3% etc.; The consumption of stopper can be 1%, 1.2%, 1.5% etc.
Embodiment 1
In the there-necked flask that reflux exchanger, water trap, TM, whisking appliance are housed, add 1,2,3-USP Kosher 0.2mol (18.4g), vinylformic acid 0.7mol (50.4g); The band aqua is toluene 80ml, and catalyzer is silicotungstic acid 2.6g, and stopper is Resorcinol 1g; Stir and be heated to 100 ℃, reacted 7 hours, when the reactionless generation water of band aqua is taken out of, be the terminal point of reaction; Neutralization obtains title product 1,2,3-USP Kosher triacrylate through after the underpressure distillation to reaction solution again through alkali earlier.
Embodiment 2
In the there-necked flask that reflux exchanger, water trap, TM, whisking appliance are housed, add 1,2,3-USP Kosher 0.2mol (18.4g), vinylformic acid 0.7mol (50.4g); The band aqua is toluene 80ml, and catalyzer is phospho-wolframic acid 3g, and stopper is Resorcinol 1.2g; Stir and be heated to 105 ℃, reacted 5 hours, when the reactionless generation water of band aqua is taken out of, be the terminal point of reaction; Neutralization obtains title product 1,2,3-USP Kosher triacrylate through after the underpressure distillation to reaction solution again through alkali earlier.
Embodiment 3
In the there-necked flask that reflux exchanger, water trap, TM, whisking appliance are housed, add 1,2,3-USP Kosher 0.2mol (18.4g); Vinylformic acid 0.8mol (57.6g) band aqua is hexanaphthene 100ml, and catalyzer is silicotungstic acid 3g, and stopper is Resorcinol 1.1g; Stir and be heated to 95 ℃, reacted 6 hours, when the reactionless generation water of band aqua is taken out of, be the terminal point of reaction; Neutralization obtains title product 1,2,3-USP Kosher triacrylate through after the underpressure distillation to reaction solution again through alkali earlier.
Embodiment 4
In the there-necked flask that reflux exchanger, water trap, TM, whisking appliance are housed, add 1,2,3-USP Kosher 0.2mol (18.4g); Vinylformic acid 0.8mol (57.6g), the band aqua is hexanaphthene 100ml, catalyzer is phospho-wolframic acid 3g; Stopper is MEHQ 1.3g, stirs and is heated to 95 ℃, reacts 8 hours; Terminal point for reacting when the reactionless generation water of band aqua is taken out of; Neutralization obtains title product 1,2,3-USP Kosher triacrylate through after the underpressure distillation to reaction solution again through alkali earlier.
Claims (6)
1. one kind 2, the preparation method of 3-USP Kosher triacrylate is characterized in that: with bio-based material 1,2; The 3-USP Kosher is a raw material, in molar ratio 1,2, and the 3-USP Kosher: the ratio of vinylformic acid=1: 3-4 is with 1; 2,3-USP Kosher and vinylformic acid under 95 ± 5 ℃, reacted 6-8 hour in the presence of catalyzer, stopper, band aqua; Band aqua consumption is 1,2, and the 1-1.5 of 3-USP Kosher and acrylic acid total mass times, catalyst levels is the 2%-4% of reaction system total mass; The stopper consumption is the 1%-2% of reaction system total mass, and the reaction system total mass is meant 1,2 here, the total mass of 3-USP Kosher, vinylformic acid and band aqua.Neutralization obtains 1,2,3-USP Kosher triacrylate through after the underpressure distillation to reaction solution again through alkali earlier.
2. according to claim 11,2, the preparation method of 3-USP Kosher triacrylate is characterized in that, described catalyzer is any one in p-methyl benzenesulfonic acid, silicotungstic acid or the phospho-wolframic acid.
3. according to claim 11,2, the preparation method of 3-USP Kosher triacrylate is characterized in that, described stopper is that any one or two kinds of materials of Resorcinol, MEHQ mix.
4. according to claim 11,2, the preparation method of 3-USP Kosher triacrylate is characterized in that, described band aqua is that any one or the two kinds of materials in toluene, benzene, normal hexane, the hexanaphthene mix.
5. according to claim 11,2, the preparation method of 3-USP Kosher triacrylate is characterized in that, described temperature of reaction is 95 ± 5 ℃.
6. according to claim 11,2, the preparation method of 3-USP Kosher triacrylate is characterized in that, the reaction times is 6-8 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010106020655A CN102557935A (en) | 2010-12-23 | 2010-12-23 | Preparation method of 1, 2, 3-glycerin triacrylate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010106020655A CN102557935A (en) | 2010-12-23 | 2010-12-23 | Preparation method of 1, 2, 3-glycerin triacrylate |
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| CN102557935A true CN102557935A (en) | 2012-07-11 |
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| CN2010106020655A Pending CN102557935A (en) | 2010-12-23 | 2010-12-23 | Preparation method of 1, 2, 3-glycerin triacrylate |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103160378A (en) * | 2013-01-31 | 2013-06-19 | 北京化工大学常州先进材料研究院 | Plant oil-based acrylic ester capable of photopolymerization and preparation method thereof |
| CN106187774A (en) * | 2016-07-18 | 2016-12-07 | 安庆飞凯高分子材料有限公司 | A kind of preparation method of 1,3 glycerol diacrylates |
-
2010
- 2010-12-23 CN CN2010106020655A patent/CN102557935A/en active Pending
Non-Patent Citations (4)
| Title |
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| 刘宏魏等: "聚甘油的酯化反应和产物破乳性能的研究", 《石油炼制与化工》 * |
| 张敬畅等: "丙烯酸酯化反应中固体酸催化剂的应用", 《北京化工大学学报》 * |
| 郑燕升等: "硅钨酸催化合成三羟甲基丙烷三丙烯酸酯研究", 《广西工学院学报》 * |
| 马荣华: "杂多酸催化合成三醋酸甘油酯", 《高师理科学刊》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103160378A (en) * | 2013-01-31 | 2013-06-19 | 北京化工大学常州先进材料研究院 | Plant oil-based acrylic ester capable of photopolymerization and preparation method thereof |
| CN106187774A (en) * | 2016-07-18 | 2016-12-07 | 安庆飞凯高分子材料有限公司 | A kind of preparation method of 1,3 glycerol diacrylates |
| CN106187774B (en) * | 2016-07-18 | 2019-04-16 | 安庆飞凯新材料有限公司 | A kind of preparation method of 1,3- glycerine diacrylate |
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Application publication date: 20120711 |