CN101735343A - Aqueous macromolecular photoinitiator and preparation method thereof - Google Patents
Aqueous macromolecular photoinitiator and preparation method thereof Download PDFInfo
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- CN101735343A CN101735343A CN200910200534A CN200910200534A CN101735343A CN 101735343 A CN101735343 A CN 101735343A CN 200910200534 A CN200910200534 A CN 200910200534A CN 200910200534 A CN200910200534 A CN 200910200534A CN 101735343 A CN101735343 A CN 101735343A
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- macromolecular photoinitiator
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- aqueous macromolecular
- triethylamine
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Abstract
The invention relates to an aqueous macromolecular photoinitiator and a preparation method thereof. The general formula of the aqueous macromolecular photoinitiator is (i). The aqueous macromolecular photoinitiator prepared by the method has the photoinitiating efficiency equivalent to a corresponding micro-molecular photoinitiator and has better compatibility with an aqueous light-cured resin; carboxylate ions and sulfosalt ions exist in a molecular chain simultaneously, so the resin has better water solubility than an aqueous macromolecular photoinitiator only containing carboxylate ions; and in addition, the price of an introduced chain extender (4-aminobenzenesulfonic acid) used for sulfonic acid group is lower than that of a conventional aqueous functional monomer (dihydromethylpropionic acid), so that the cost of products is reduced and the industrial production is facilitated. At the same time, in the method, the chain is extended by using the functional monomer with photoinitiating function, so the content of photoinitiating radicals in the resin per gram is improved and the aqueous macromolecular photoinitiator has better photoinitiating efficiency than the aqueous macromolecular photoinitiator taking end radicals as the photoinitiating radicals.
Description
Technical field
The present invention relates to a kind of aqueous macromolecular photoinitiator and synthetic method thereof.
Background technology
One of direction of 21 century coating development is an environment-friendly type coating, and it comprises high-solid level and solventless coatings, water-borne coatings, powder coating and radiation curable coating etc.Waterborne radiation curable coating is a kind of inheriting and having developed on the basis of traditional photocuring technology advantage, utilizes a kind of novel environment friendly coating of water as dispersion medium.
In the aqueous photo-curing system, light trigger is and one of important component, and at present, traditional oiliness small molecules light trigger is widely used in the aqueous photo-curing system, but its many drawback affects the final performance of aqueous photo-curing system equally.Compare with oil soluble small molecules light trigger, aqueous macromolecular photoinitiator rolls into one the advantage of water-based system and photocuring technology, have free from extraneous odour, do not move, with advantages such as resin compatible is good.Have at present report with maleic anhydride and with light trigger 1-[4-(2-hydroxyl hydroxyethyl)-phenyl]-reaction of 2-hydroxy-2-methyl-1-propane, prepare and have certain hydrophilic polymerisable small molecules light trigger, then it is carried out the epoxy acrylic resin that has light-initiated function that radical polymerization prepares water outlet; Small molecules oil soluble light trigger is also arranged as function monomer, adopt toluene diisocyanate, polytetrahydrofuran dibasic alcohol, dimethylol propionic acid, Hydroxyethyl acrylate and Irgacure 2959 (1-[4-(2-hydroxy ethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane) to synthesize the UV solidfication water polyurethane acrylic resin that is connected to light-initiated base.Utilize dimethylol propionic acid to introduce the carboxylic acid group, obtain wetting ability with salify in the warp then at the resin side chain; But Shang Weijian is with small molecules light trigger 2-hydroxyl-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-phenmethyl]-phenyl }-2-methyl-propane is function monomer, is equipped with the relevant report of aqueous macromolecular photoinitiator with the chain extension legal system.In addition, usually adopting with the carboxyl in the aqueous polyurethane is hydrophilic radical, add the alkali neutralization, make the resin possess hydrophilic property, but Shang Weijian introduces the carboxylic acid group in resin after, method with chain extension is introduced sulfonic group again, adds the alkali neutralization, thereby prepares a kind of relevant report of aqueous macromolecular photoinitiator of dual anion type.
Summary of the invention
One of purpose of the present invention provides a kind of aqueous macromolecular photoinitiator.
Two of purpose of the present invention is to provide the preparation method of this initiator.
For achieving the above object, the present invention adopts following technical scheme:
A kind of aqueous macromolecular photoinitiator is characterized in that this initiator is the compound with general formula (i):
Wherein, R
3Structural formula be:
The structural formula of R is:
A=1～10 wherein, b=1～20, c=1～10, d=1～10; The structural formula of I is:
R
1Be in the following structural formula any:
B is any in the following structural formula:
A is any in the following structural formula:
N=1～45 wherein;
A kind of method for preparing above-mentioned aqueous macromolecular photoinitiator is characterized in that this method may further comprise the steps:
A) under inert atmosphere, by mass percentage, 5%～15% small molecules light trigger and 20%～40% vulcabond were reacted 3～5 hours under 75～95 ℃ of temperature, add 4%～15% dimethylol propionic acid, reacted 1.5～2.5 hours under 75～85 ℃ of temperature, the dibasic alcohol of adding 30%～70%, be warming up to 80～95 ℃ of reactions 2～3 hours, the Hydroxyethyl acrylate or the Propylene glycol monoacrylate of adding 10%～20%, react under 70～80 ℃ of temperature to isocyanate group and reach theoretical value, be cooled to 45～55 ℃, add triethylamine, obtain the prepolymer that end group is an isocyanate group; The mass percent sum of described each raw material is 100%; The quality of the triethylamine that is added calculates according to the following equation:
W
1＝W
2÷M
2×M
1
W wherein
1For adding triethylamine quality, W
2For adding dimethylol propionic acid quality, M
1Be triethylamine molecular weight, M
2Be the dimethylol propionic acid molecular weight, described mass unit is gram;
B) by mass percentage, with 2%～5% chainextender 4-aniline sulfonic acid and 50%～80% deionized water, be warming up to 65～75 ℃, add the resulting prepolymer of 20%～50% step a, react to the isocyanate group completely dissolve, be cooled to 45～55 ℃, regulate pH=8, promptly obtain solid content and be the dispersion liquid of 20%～40% aqueous macromolecular photoinitiator with triethylamine; The mass percent sum of described each raw material is 100%.
Above-mentioned small molecules light trigger is 2-hydroxyl-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-phenmethyl]-phenyl }-2-methyl-propane.
Above-mentioned dibasic alcohol is a neopentyl glycol, 1, ammediol, polypropylene glycol, ethylene glycol or polyoxyethylene glycol.
Above-mentioned vulcabond is tolylene diisocyanate, isophorone diisocyanate or hexamethylene diisocyanate.
The method of calculation of the theoretical value that described isocyanate group reaches are: hydroxyl mole number in theoretical value=total isocyanate group mole number-reactant, available Di-n-Butyl Amine method is measured the isocyanate group mole number and is calculated.
A kind of aqueous macromolecular photoinitiator of the present invention is dual anion type water-based polymkeric substance, and its dianion is meant carboxylate ion and sulfonate ion; Wherein carboxylate ion is by dimethylol propionic acid and isocyanic ester radical reaction, introduces carboxyl, uses in the triethylamine then and gained; Sulfonate ion is by chainextender 4-aniline sulfonic acid and isocyanic ester radical reaction, introduces sulfonic group, uses in the triethylamine then and gained.
Compared with prior art, the inventive method has following outstanding substantive distinguishing features and advantage: the present invention prepares a kind of aqueous macromolecular photoinitiator, this resin has good water-solubility, good with the consistency of aqueous photo-curing resin, there is not migration, possess the suitable light-initiated efficient of the small molecules light trigger corresponding, can well be applied in the aqueous photo-curing system, meet contemporary requirements of green environmental protection with it.In addition, after the present invention utilizes dimethylol propionic acid to introduce the carboxylic acid group as the Water-borne modification function monomer in molecular chain, utilize the relatively low 4-aniline sulfonic acid of price in molecular chain, to introduce sulfonic group again, make to have two anionic hydrophilic group simultaneously in this resin as the Water-borne modification function monomer.Find after tested, reaching under the identical water miscible condition, the prepared end group of the present invention contains the dual anion type water-based polyurethane resin of light-initiated group, the single anion type resin that more only with the carboxylate ion is the Water-borne modification group is compared, the mole number of required Water-borne modification group still less in its every gram resin, i.e. the deliquescent while in the water that has improved this resin, reduced its production cost again.Simultaneously, in this aqueous macromolecular photoinitiator of preparation, selected for use function monomer to carry out chain extension with photoinitiation, so just can improve the content of light-initiated group in every gram resin, make that this aqueous macromolecular photoinitiator is that the aqueous macromolecular photoinitiator of light-initiated group has better light-initiated efficient than end group.
Concrete embodiment
Embodiment one: add 8.50g2-hydroxyl-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-phenmethyl in thermometer, reflux condensing tube, churned mechanically there-necked flask are housed]-phenyl }-2-methyl-propane, 23.31g isophorone diisocyanate and 20.00ml acetone are at logical N
2Under the condition, 80 ℃, reacted 3 hours; Add the 2.92g dimethylol propionic acid then, cool to 75 ℃ gradually, reacted 2 hours, add the 21.60g polypropylene glycol, 1.34g ethylene glycol is warmed up to 80 ℃ gradually, reacts to isocyanate group and reaches theoretical value, is cooled to 50 ℃, add the 2.20g triethylamine, neutralization, stand-by; At another adding 0.87g4-aniline sulfonic acid in thermometer, reflux condensing tube, the churned mechanically there-necked flask is housed, the 100g deionized water, be heated to 70 ℃, add prepolymer, react to the isocyanate group completely dissolve, add the triethylamine neutralization, regulate PH=8～9, boil off acetone, promptly get solid content and be the dispersion liquid of 38% aqueous macromolecular photoinitiator, its median size is 95.5nm, and light-initiated group content is 0.16mmol/g.
Embodiment two: add 8.50g2-hydroxyl-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-phenmethyl in thermometer, reflux condensing tube, churned mechanically there-necked flask are housed]-phenyl }-2-methyl-propane, 18.27g tolylene diisocyanate and 20.00ml acetone are at logical N
2Under the condition, 80 ℃, reacted 3 hours; Add the 3.75g dimethylol propionic acid then, cool to 75 ℃ gradually, reacted 2 hours, add the 18.50g polypropylene glycol, 1.92g neopentyl glycol is warmed up to 80 ℃ gradually, reacts to isocyanate group and reaches theoretical value, is cooled to 50 ℃, add the 2.83g triethylamine, neutralization, stand-by; At another adding 0.87g4-aniline sulfonic acid in thermometer, reflux condensing tube, the churned mechanically there-necked flask is housed, the 100g deionized water, be heated to 70 ℃, add prepolymer, react to the isocyanate group completely dissolve, add the triethylamine neutralization, regulate PH=8～9, boil off acetone, promptly get solid content and be the dispersion liquid of 35% aqueous macromolecular photoinitiator, its median size is 75.32nm, and light-initiated group content is 0.16mmol/g.
Embodiment three: add 8.50g2-hydroxyl-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-phenmethyl in thermometer, reflux condensing tube, churned mechanically there-necked flask are housed]-phenyl }-2-methyl-propane, 17.01g hexamethylene diisocyanate and 20.00ml acetone are at logical N
2Under the condition, 80 ℃, reacted 3 hours; Add the 3.11g dimethylol propionic acid then, cool to 75 ℃ gradually, reacted 2 hours, add the 20.90g polypropylene glycol, 1.59g1 ammediol is warmed up to 80 ℃ gradually, reacts to isocyanate group and reaches theoretical value, be cooled to 50 ℃, add the 2.34g triethylamine, neutralization, stand-by; At another adding 0.87g4-aniline sulfonic acid in thermometer, reflux condensing tube, the churned mechanically there-necked flask is housed, the 100g deionized water, be heated to 70 ℃, add prepolymer, react to the isocyanate group completely dissolve, add the triethylamine neutralization, regulate PH=8～9, boil off acetone, promptly get solid content and be the dispersion liquid of 35% aqueous macromolecular photoinitiator, its median size is 77.50nm, and light-initiated group content is 0.16mmol/g.
Embodiment four: add 10.20g2-hydroxyl-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-phenmethyl in thermometer, reflux condensing tube, churned mechanically there-necked flask are housed]-phenyl }-2-methyl-propane, 21.92g tolylene diisocyanate and 20.00ml acetone are at logical N
2Under the condition, 80 ℃, reacted 3 hours; Add the 4.50g dimethylol propionic acid then, cool to 75 ℃ gradually, reacted 2 hours, add the 22.20g polypropylene glycol, 2.30g neopentyl glycol is warmed up to 80 ℃ gradually, reacts to isocyanate group and reaches theoretical value, is cooled to 50 ℃, add the 3.40g triethylamine, neutralization, stand-by; At another adding 1.10g4-aniline sulfonic acid in thermometer, reflux condensing tube, the churned mechanically there-necked flask is housed, the 100g deionized water, be heated to 70 ℃, add prepolymer, react to the isocyanate group completely dissolve, add the triethylamine neutralization, regulate PH=8 ~ 9, boil off acetone, promptly get solid content and be the dispersion liquid of 40% aqueous macromolecular photoinitiator, its median size is 72.35nm, and light-initiated group content is 0.18mmol/g.
Claims (5)
1. aqueous macromolecular photoinitiator is characterized in that this initiator is the compound with general formula (i):
Wherein, R
3Structural formula be:
The structural formula of R is:
A=1～10 wherein, b=1～20, c=1～10, d=1～10; The structural formula of I is:
R
1Be in the following structural formula any:
B is any in the following structural formula:
A is any in the following structural formula:
N=1～45 wherein;
2. method for preparing aqueous macromolecular photoinitiator according to claim 1 is characterized in that this method may further comprise the steps:
A. under inert atmosphere, by mass percentage, 5%～15% small molecules light trigger and 20%～40% vulcabond were reacted 3～5 hours under 75～95 ℃ of temperature, add 4%～15% dimethylol propionic acid, reacted 1.5～2.5 hours under 75～85 ℃ of temperature, the dibasic alcohol of adding 30%～70%, be warming up to 80～95 ℃ of reactions 2～3 hours, the Hydroxyethyl acrylate or the Propylene glycol monoacrylate of adding 10%～20%, react under 70～80 ℃ of temperature to isocyanate group and reach theoretical value, be cooled to 45～55 ℃, add triethylamine, obtain the prepolymer that end group is an isocyanate group; The mass percent sum of described each raw material is 100%; The quality of the triethylamine that is added calculates according to the following equation:
W
1＝W
2÷M
2×M
1
W wherein
1For adding triethylamine quality, W
2For adding dimethylol propionic acid quality, M
1Be triethylamine molecular weight, M
2Be the dimethylol propionic acid molecular weight, described mass unit is gram;
B. by mass percentage, with 2%～5% chainextender 4-aniline sulfonic acid and 50%～80% deionized water, be warming up to 65～75 ℃, add the resulting prepolymer of 20%～50% step a, react to the isocyanate group completely dissolve, be cooled to 45～55 ℃, regulate pH=8, promptly obtain solid content and be the dispersion liquid of 20%～40% aqueous macromolecular photoinitiator with triethylamine; The mass percent sum of described each raw material is 100%.
3.
The synthetic method of aqueous macromolecular photoinitiator according to claim 2 is characterized in that described small molecules light trigger is 2-hydroxyl-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-phenmethyl]-phenyl }-2-methyl-propane.
4.
The synthetic method of aqueous macromolecular photoinitiator according to claim 2 is characterized in that described dibasic alcohol is a neopentyl glycol, 1, ammediol, polypropylene glycol, ethylene glycol or polyoxyethylene glycol.
5.
The synthetic method of aqueous macromolecular photoinitiator according to claim 2 is characterized in that described vulcabond is tolylene diisocyanate, isophorone diisocyanate or hexamethylene diisocyanate.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101864006A (en) * | 2010-07-16 | 2010-10-20 | 北京化工大学常州先进材料研究院 | Thioxanthone photoinitiator containing cyclic acetal and preparation method thereof |
| WO2013026451A1 (en) | 2011-08-24 | 2013-02-28 | Coloplast A/S | Polymers comprising photoinitiator moieties and dye moieties |
| WO2016052055A1 (en) * | 2014-09-30 | 2016-04-07 | 富士フイルム株式会社 | Gel particles, photosensitive composition, ink composition, method for manufacturing aqueous dispersion of gel particles, and image forming method |
| CN106589272A (en) * | 2016-12-06 | 2017-04-26 | 张家港鹤立恒新材料科技有限公司 | Preparation method of amphiphilic block copolymer based on water-based macromolecular photoinitiator |
| CN107987252A (en) * | 2017-11-17 | 2018-05-04 | 深圳市嘉卓成科技发展有限公司 | A kind of preparation method and water-soluble photoinitiator of self-emulsifying aqueous photoinitiator |
| CN114656591A (en) * | 2020-12-23 | 2022-06-24 | 北京化工大学 | Water-soluble macromolecular photoinitiator and preparation method and application thereof |
-
2009
- 2009-12-22 CN CN200910200534A patent/CN101735343A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101864006A (en) * | 2010-07-16 | 2010-10-20 | 北京化工大学常州先进材料研究院 | Thioxanthone photoinitiator containing cyclic acetal and preparation method thereof |
| WO2013026451A1 (en) | 2011-08-24 | 2013-02-28 | Coloplast A/S | Polymers comprising photoinitiator moieties and dye moieties |
| WO2016052055A1 (en) * | 2014-09-30 | 2016-04-07 | 富士フイルム株式会社 | Gel particles, photosensitive composition, ink composition, method for manufacturing aqueous dispersion of gel particles, and image forming method |
| CN107075070A (en) * | 2014-09-30 | 2017-08-18 | 富士胶片株式会社 | Gel particles, photosensitive composite, ink composite, the manufacture method of the water dispersion of gel particles and image forming method |
| CN107075070B (en) * | 2014-09-30 | 2019-12-03 | 富士胶片株式会社 | Gel particles, photosensitive composite, printing ink composition, gel particles water dispersion manufacturing method and image forming method |
| CN106589272A (en) * | 2016-12-06 | 2017-04-26 | 张家港鹤立恒新材料科技有限公司 | Preparation method of amphiphilic block copolymer based on water-based macromolecular photoinitiator |
| CN106589272B (en) * | 2016-12-06 | 2019-05-17 | 张家港鹤立恒新材料科技有限公司 | The preparation method of amphipathic nature block polymer based on aqueous macromolecular photoinitiator |
| CN107987252A (en) * | 2017-11-17 | 2018-05-04 | 深圳市嘉卓成科技发展有限公司 | A kind of preparation method and water-soluble photoinitiator of self-emulsifying aqueous photoinitiator |
| CN114656591A (en) * | 2020-12-23 | 2022-06-24 | 北京化工大学 | Water-soluble macromolecular photoinitiator and preparation method and application thereof |
| CN114656591B (en) * | 2020-12-23 | 2023-06-13 | 北京化工大学 | Water-soluble macromolecular photoinitiator and preparation method and application thereof |
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Open date: 20100616 |