CN1205343A - Synthetic process of photofixed polyester propenoic methyl carbamate - Google Patents
Synthetic process of photofixed polyester propenoic methyl carbamate Download PDFInfo
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- CN1205343A CN1205343A CN 97105247 CN97105247A CN1205343A CN 1205343 A CN1205343 A CN 1205343A CN 97105247 CN97105247 CN 97105247 CN 97105247 A CN97105247 A CN 97105247A CN 1205343 A CN1205343 A CN 1205343A
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Abstract
A process for synthesizing photosetting polyester acrylic aminoformate includes preparing polyester oligomer from binary alcohol, bibasic acid, acrylic acid, hexadiisocyanate, metatolyldiisocyanate and ethoxyl acrylate, regulating the viscosity of polyester with propantriol monoacetate and monoacrylate to obtain the polyester oligomer (A'), and addition of hexadiisocyanate (B') to obtain said photosetting matter with A'B'A' structure.
Description
The invention belongs to the synthetic method of photofixed polyester propenoic methyl carbamate.
Wen-Yenchiang in 1987 discloses at application superpolymer science magazine and has been entitled as " preparation and character that oligomer ester is closed in the photocuring insatiable hunger ", people such as comprehensive nineteen ninety Shen innovation disclose on coatings industry and have been entitled as " research of light-cured polyurethane acrylic coating ", its synthetic method is at first used dibasic alcohol and binary unsaturated acid synthesizing polyester oligopolymer (A), use 2 again, 4-phenyl diisocyanate and methacrylic acid hydroxyl ethyl ester reaction mol ratio are 1: 1, obtain 2-isocyanato-4-toluino formic acid vinylformic acid ethyl ester, its structure is as follows:
A added obtain unsaturated polyester methacrylic acid carbamate among the B, its molecular structure is BAB.
This method since between in building-up process, having adopted tolylene diisocyanate be raw material, so institute's synthetic polymkeric substance has color, the bright-coloured degree of color is affected when the preparation dyestuff like this, and the flow of solution and the less stable that are made into thinner.
The objective of the invention is to adopt dibasic alcohol, diprotic acid, vinylformic acid, hexamethylene diisocyanate, a toluenediisocyanate and Hydroxyethyl acrylate is raw material, the preparation polyester oligomer is a conditioning agent with glycerol monoacetate and mono-propionate, the oligopolymer (A ＇) that the viscosity of adjusting polyester obtains polyester adds hexamethylene diisocyanate (B ＇) then, generate photocuring polyester propenoic methyl carbamate, obtain the photocuring polyester propenoic methyl carbamate of A ＇ B ＇ A ＇ structure.
Reaction mechanism of the present invention is:
The structure that obtains product is A ＇ B ＇ A ＇
The present invention is the synthesizing polyester oligopolymer at first; adopt dibasic alcohol; be ethylene glycol; one condensed ethandiol; 1; the 2-propylene glycol; the glycerol mono-propionate; hexanodioic acid; vinylformic acid; its mol ratio is: dibasic alcohol: glycerol mono-propionate: hexanodioic acid: vinylformic acid=1: 0.1～0.2: 0.7～0.9: 0.2～0.4 adding accounts for the Catalyzed by p-Toluenesulfonic Acid agent that the raw material total amount is 1.2% (weight ratio); add benzene solvent again; its consumption and charging capacity weight ratio are 1.0: 1.5; under nitrogen protection; heating reflux reaction 8～10 hours; filter benzole soln; steam benzene and remove residual volatile matter under reduced pressure; obtain polyester oligomer, get 1 mole of adding of polyester oligomer (mol ratio) and account for total charging capacity 0.1% (weight ratio) dibutyl tin laurate, add then 0.5 mole 1; hexamethylene-diisocyanate; under nitrogen protection, 70～75 ℃ of reactions of temperature 3～4 hours obtain the polyester propenoic methyl carbamate resin.
Synthetic resin normal temperature of the present invention is viscous liquid, acid value 9, hydroxy radical content 2.5%, ultraviolet light polymerization speed＜0.4s down, fugitive constituent 1%, resin is good leveling property in thinner, the glossiness 44.3 of printing ink, package stability is more than 1 year, and water resisting property is good, excellent combination property.
Embodiment provided by the invention is as follows:
Embodiment 1:
With 1 mole of ethylene glycol, 0.1 mole of glycerol mono-propionate, 0.7 mole of hexanodioic acid, 0.4 mole in vinylformic acid; add respectively in the reaction flask, add agent of 2.5g Catalyzed by p-Toluenesulfonic Acid and 138.5g benzene solvent again, under nitrogen protection; reflux was reacted 10 hours, and dehydration rate reaches 98%.Filter benzole soln, steam benzene, remove residual volatile matter under reduced pressure, obtain polyester oligomer.Get 1 mole of polyester oligomer, add and to account for total charging capacity 0.1% (weight ratio) dibutyltin dilaurate catalyst, add then 0.5 mole 1; hexamethylene-diisocyanate; under nitrogen protection, the 70 ℃ of reactions 4 hours that heat up obtain the polyester propenoic methyl carbamate resin.
Embodiment 2:
With 1 mole of glycol ether, 0.2 mole of glycerol mono-propionate; 0.9 mole of hexanodioic acid; 0.2 mole in vinylformic acid adds respectively in the reaction flask, adds agent of 3.4g Catalyzed by p-Toluenesulfonic Acid and 187g benzene solvent again; under nitrogen protection; heating reflux reaction 8 hours, dehydration rate reaches more than 98%, filters benzole soln; steam benzene, remove residual volatile matter under reduced pressure.Obtain the polyester oligomer; get 1 mole of polyester oligomer; add the dibutyltin dilaurate catalyst that accounts for total charging capacity 0.1% (weight ratio); slowly add then 0.5 mole 1; hexamethylene-diisocyanate, under nitrogen protection, temperature is controlled at 75 ℃; reacted 3 hours, and obtained the polyester propenoic methyl carbamate resin.
Embodiment 3:
With 0.5 mole of ethylene glycol, 0.5 mole of glycol ether, 0.14 mole of glycerol mono-propionate; 0.83 mole of hexanodioic acid, 0.3 mole in vinylformic acid adds in the reaction flask respectively; add the agent of 2.7g Catalyzed by p-Toluenesulfonic Acid; add the 150g benzene solvent again, under nitrogen protection, heating reflux reaction 9 hours; filter benzole soln; steam and remove benzene, remove residual volatile matter under reduced pressure, obtain polyester oligomer.Poly-1 mole of polyester oligomer adds the dibutyltin dilaurate catalyst of total charging capacity 0.1% (weight ratio), slowly add then 0.5 mole 1; hexamethylene-diisocyanate; under nitrogen protection, 70 ℃ of reactions of temperature 4 hours obtain the polyester propenoic methyl carbamate resin.
Claims (1)
1. the synthetic method of a photofixed polyester propenoic methyl carbamate; it is characterized in that at first synthesizing polyester oligopolymer; adopt dibasic alcohol; be ethylene glycol; one condensed ethandiol; 1; the 2-propylene glycol; the glycerol mono-propionate; hexanodioic acid; vinylformic acid; its mol ratio is: dibasic alcohol: glycerol mono-propionate: hexanodioic acid: vinylformic acid=1: 0.1～0.2: 0.7～0.9: 0.2～0.4 adding accounts for the Catalyzed by p-Toluenesulfonic Acid agent that the raw material total amount is 1.2% (weight ratio); add benzene solvent again; its consumption and charging capacity weight ratio are 1.0: 1.5; under nitrogen protection; heating reflux reaction 8～10 hours; filter benzole soln, steam benzene and remove residual volatile matter under reduced pressure, obtain polyester oligomer; get 1 mole of adding of polyester oligomer (mol ratio) and account for total charging capacity 0.1% (weight ratio) dibutyl tin laurate; the hexamethylene diisocyanate that adds 0.5 mole then is under nitrogen protection; 70～75 ℃ of reactions of temperature 3～4 hours obtain the polyester propenoic methyl carbamate resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97105247A CN1072686C (en) | 1997-07-10 | 1997-07-10 | Synthetic process of photofixed polyester propenoic methyl carbamate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97105247A CN1072686C (en) | 1997-07-10 | 1997-07-10 | Synthetic process of photofixed polyester propenoic methyl carbamate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1205343A true CN1205343A (en) | 1999-01-20 |
| CN1072686C CN1072686C (en) | 2001-10-10 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97105247A Expired - Fee Related CN1072686C (en) | 1997-07-10 | 1997-07-10 | Synthetic process of photofixed polyester propenoic methyl carbamate |
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| CN (1) | CN1072686C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102421823A (en) * | 2009-05-12 | 2012-04-18 | 巴斯夫欧洲公司 | Method for the continuous production of (meth)acrylic acid esters containing urethane groups |
| CN103881054A (en) * | 2012-12-20 | 2014-06-25 | 江南大学 | Preparation method of UV curable resin used for antifogging coating |
| CN104194589A (en) * | 2014-09-09 | 2014-12-10 | 苏州圣谱拉新材料科技有限公司 | Unsaturated polyester photocureable coating for ceramics |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2538812A1 (en) * | 1975-09-01 | 1977-03-03 | Wacker Chemitronic | METHOD OF DOPING SEMICONDUCTOR RODS |
| JPS5765714A (en) * | 1980-10-06 | 1982-04-21 | Nippon Synthetic Chem Ind Co Ltd:The | Photocurable resin composition |
| JPS58160313A (en) * | 1982-03-18 | 1983-09-22 | Harima Kasei Kogyo Kk | Photosetting resin |
| JPS6023411A (en) * | 1984-04-02 | 1985-02-06 | Nippon Paint Co Ltd | Preparation of photosensitive compound |
| JPS6381112A (en) * | 1986-09-24 | 1988-04-12 | Mitsubishi Petrochem Co Ltd | Photosetting aromatic gel composition |
-
1997
- 1997-07-10 CN CN97105247A patent/CN1072686C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102421823A (en) * | 2009-05-12 | 2012-04-18 | 巴斯夫欧洲公司 | Method for the continuous production of (meth)acrylic acid esters containing urethane groups |
| CN102421823B (en) * | 2009-05-12 | 2014-07-16 | 巴斯夫欧洲公司 | Method for the continuous production of (meth)acrylic acid esters containing urethane groups |
| CN103881054A (en) * | 2012-12-20 | 2014-06-25 | 江南大学 | Preparation method of UV curable resin used for antifogging coating |
| CN103881054B (en) * | 2012-12-20 | 2016-04-20 | 江南大学 | A kind of preparation method of anti-fog coating UV cured resin |
| CN104194589A (en) * | 2014-09-09 | 2014-12-10 | 苏州圣谱拉新材料科技有限公司 | Unsaturated polyester photocureable coating for ceramics |
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| Publication number | Publication date |
|---|---|
| CN1072686C (en) | 2001-10-10 |
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