CN101735441A - Method for preparing ultraviolet curing polyester acrylic ester prepolymer - Google Patents
Method for preparing ultraviolet curing polyester acrylic ester prepolymer Download PDFInfo
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- CN101735441A CN101735441A CN 200910191824 CN200910191824A CN101735441A CN 101735441 A CN101735441 A CN 101735441A CN 200910191824 CN200910191824 CN 200910191824 CN 200910191824 A CN200910191824 A CN 200910191824A CN 101735441 A CN101735441 A CN 101735441A
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Abstract
The invention relates to a method for preparing an ultraviolet curing polyester acrylic ester prepolymer, which comprises the following steps of: firstly, adding the prepared adipic acid, 1,4-butylene glycol, pentaerythritol, dimethylolpropionic acid and a catalyst into a reaction vessel to perform reflux reaction for 1 to 3 hours when the temperature is raised to 125 to 140 DEG C, and then distributing water to obtain a mixture; and secondly, cooling to 100 to 110 DEG C, adding hydroquinone and acroleic acid into the mixture to perform reflux reaction for 1 to 3 hours when the temperature is raised to 130 to 145 DEG C, distributing the water again till no water is distilled off, and cooling the discharge to obtain the ultraviolet curing polyester acrylic ester prepolymer. The method has the advantages of having high yield and simple postprocessing, greatly reducing by-products, effectively reducing the cost, and saving resources. The obtained ultraviolet curing polyester acrylic ester prepolymer has excellent photoreaction activity and extremely good intermiscibility, and can be subjected to copolymerization with other alkene monomers; and when being used in UV curing paint, the coating layer has good adhesion, hardness and luster. The method for preparing the ultraviolet curing polyester acrylic ester prepolymer has the characteristics of excellent film-forming property, low viscosity and economy.
Description
Technical field
The present invention relates to the preparation method that ultraviolet-curing paint prepares one of most important material-ultraviolet curing polyester acrylic ester prepolymer, belong to chemical material technical field.
Background technology
Ultraviolet light polymerization (UV curing) is meant under action of ultraviolet light, and photoactive substance generation chemical reaction in the system produces biologically active fragment, the polymerization of reactive monomer or oligopolymer, crosslinked in the initiator system, thus make system become solid-state coating by liquid coating moment.From German Bayer AG in 1967 develop first-generation UV coating material solidified since, the UV curing technology worldwide obtains develop rapidly, and applies in electronics, printing, building, decoration, medicine, machinery, chemical industry and automobile and other industries rapidly.Ultraviolet photocureable material has kept 8%～10% rapid growth from seventies abroad since the commercialization always.
The UV solidify material belongs to the novel material category of national industrial policies encourage growth, has the unrivaled advantage of traditional material, meets " environmental protection " theory, and is suitable for large-scale promotion, carries out large-scale production.Not only have ink film tenacity height, anti-soil, resistance to wear and advantage such as good solubility-resistence as the UV curing inks, and has a good thixotropy of UV, the processing of effects such as frost flower, refractive power, frosted, wrinkle can be carried out under certain condition, thereby the high precision printing and the special printing of high screen density can be carried out; The tens of height to up to a hundred meters of per minute solidify travelling speed in addition, have satisfied the production requirement of modernized big insutry; Curing inks also has 100% highly filled, save energy, safety that more valuable is, not having quality such as organic volatile deposits yields when producing and solidify, complied with current social enviroment protection and energy-conservation requirement, is the ideal green environment-friendly ink.In a word, UV printing ink meet " 5E " (Energy saving, Ecology, Economics, Ease of application, Excellencefinish) principle has good application and development prospect.
Prepolymer claims oligopolymer or oligopolymer again, is meant the low-molecular(weight)polymer that contains unsaturated functional group, is most important component in the UV printing ink, and its performance plays a decisive role to the character of solidification process and cured film.On structure, oligopolymer all is the low-molecular-weight resin that contains the C=C unsaturated double-bond, and molecular-weight average mostly is an acrylic resin between hundreds of is to several thousand.The most frequently used oligopolymer has epoxy acrylate, urethane acrylate, polyester acrylate and alkaline soluble acrylic resin etc. in the UV curing inks.Polyester acrylate is as a human subject resin that often uses in the UV ink formulations (the hyperbranched ultraviolet curing polyester acrylic ester oligopolymer of product is to be mainly used in high-grade printing industry such as one of the flexographic ink of tobacco and wine packing and light-curable ink important source material of blending oil and oil polish), removing provides toughness preferably, outside the physical and mechanical propertiess such as tensile strength, can also improve the wetting fruit of base-material, strengthen the bonding strength of pigments system plastics, metal seal face to pigment.The CN2000 series polyester acrylate of U.S. Sartomer is primarily aimed at the exploitation of UV curing inks.They have suitable oleophylic-hydrophilic balance, are applicable to the modulation of UV litho printing ink.The also alternative part reactive thinner of the polyester acrylate that viscosity is lower, the flowing property of increase printing ink.Yet domestic construction application to this resinoid mainly depends on import, and import price is generally 200～400 yuan every kilogram and does not wait, and the higher price and the monopolization of gordian technique have seriously hindered the UV curing technology and promoted in the big area of China.
For the UV cured resin, its viscosity has very big influence to performance, flow time and the cost etc. of coating.Usually the viscosity of resin increases along with the increase of oligomer molecular weight, and therefore traditional UV cured resin often needs to add a large amount of activity diluting monomers and controls viscosity, with obtain can practical application prescription.So not only the performance to cured film has very big influence, and has also increased the cost of coating products.
Summary of the invention
At the prior art above shortcomings, the preparation method who the purpose of this invention is to provide a kind of main raw material-ultraviolet curing polyester acrylic ester prepolymer of ultraviolet-curing paint, the ultraviolet-curing paint that contains the polyester acrylic ester prepolymer of present method preparation has the characteristics of excellent property and good economy performance, and the polyester acrylic ester prepolymer that present method obtains fully can the import substitution product.
Technical scheme of the present invention is achieved in that
The preparation method of ultraviolet curing polyester acrylic ester prepolymer, it may further comprise the steps:
(1) gets the raw materials ready-get the raw materials ready: hexanodioic acid: 1 by following component and mol ratio, 4-butyleneglycol: tetramethylolmethane: dimethylol propionic acid: vinylformic acid=0.9～1.1: 0.4～0.6: 0.4～0.65: 0.7～0.8: 0.6～2.0, the catalyzer tosic acid is a hexanodioic acid, 1,0.01～0.5% of 4-butyleneglycol, tetramethylolmethane and four kinds of component total masses of dimethylol propionic acid, hydroquinone of polymerization retarder is 0.0001～0.1% of a total reactant total mass;
(2) synthesis of polyhydroxy polyester: with the hexanodioic acid of getting ready, 1,4-butyleneglycol, tetramethylolmethane, dimethylol propionic acid and catalyzer add reaction vessel, heat under the nitrogen protection condition, and each component that makes adding that heats while stirring is fully dissolved; Back flow reaction when being warming up to 125～140 ℃, return time 1～3h divides water then;
(3) polyol polyester esterification: when the question response container is cooled to 100～110 ℃ of left and right sides, add hydroquinone of polymerization retarder and vinylformic acid, heat up then, reflux when being warming up to 130～145 ℃, return time 1～3h, divide water again, distillate until anhydrous, cooling discharging promptly gets ultraviolet curing polyester acrylic ester prepolymer.
Further, the proportioning that above-mentioned raw materials is relatively optimized is: hexanodioic acid: 1,4-butyleneglycol: tetramethylolmethane: dimethylol propionic acid: acrylic acid mass ratio is 0.99: 0.51: 0.54: 0.60: 1.00, the catalyzer tosic acid is a hexanodioic acid, 1,0.1% of 4-butyleneglycol, tetramethylolmethane and four kinds of component total masses of dimethylol propionic acid, hydroquinone of polymerization retarder is 0.02% of a total reactant total mass.
A temperature-time relationship of relatively optimizing in the aforesaid method is: when (2) goes on foot the synthesis of polyhydroxy polyester, begin back flow reaction when being warming up to 125 ℃, return time 2.5h; When (3) goes on foot the polyol polyester esterification, begin back flow reaction when being warming up to 140 ℃, return time 2h.
The present invention is with hexanodioic acid, 1,4-butyleneglycol, tetramethylolmethane, dimethylol propionic acid and vinylformic acid etc. are raw material, adopt " two step method " first synthesis of super branched polyol polyester, add the synthetic UV curing polyester acrylic ester prepolymer of vinylformic acid (or methacrylic acid) esterification end-blocking again, productive rate height not only, aftertreatment is simple, and has reduced by product widely, reduced cost effectively, economized on resources.Because this resin contains the high functionality of a plurality of acryloyl active reactive groups, makes it have good light reaction, during with co-blended such as other reactive monomer, can obtain extremely good intermiscibility, and can with other vinyl monomer generation copolyreaction.Be applied to UV coating material solidified in, coating shows good sticking power, hardness and gloss, (as CN2203) compares with the import analogous products, the present invention has film forming properties preferably, lower viscosity and both economical characteristics.
Owing to have excellent curing performance and UV solidify material compatibility, polyester acrylic ester prepolymer of the present invention is not only at the UV ink printing, and in photocuring fields such as wear-resistant paint, pressure sensitive adhesive, printing ink laminate adhesive very high actual application value and wide market arranged also.And be used for UV light-curable ink Printing industry with the CN2203 of polyester acrylic ester prepolymer import substitution of the present invention, then have important practical significance.
Embodiment
The invention will be further described below in conjunction with embodiment.
The preparation method of ultraviolet curing polyester acrylic ester prepolymer of the present invention, it may further comprise the steps:
(1) gets the raw materials ready-get the raw materials ready: hexanodioic acid: 1 by following component and mol ratio, 4-butyleneglycol: tetramethylolmethane: dimethylol propionic acid: vinylformic acid=0.9～1.1: 0.4～0.6: 0.4～0.65: 0.7～0.8: 0.6～2.0, the catalyzer tosic acid is a hexanodioic acid, 1,0.01～0.5% of 4-butyleneglycol, tetramethylolmethane and four kinds of component total masses of dimethylol propionic acid, hydroquinone of polymerization retarder is 0.0001～0.1% of a total reactant total mass;
(2) synthesis of polyhydroxy polyester: with the hexanodioic acid of getting ready, 1,4-butyleneglycol, tetramethylolmethane, dimethylol propionic acid and catalyzer add reaction vessel, heat under the nitrogen protection condition, and each component that makes adding that heats while stirring is fully dissolved; Back flow reaction when being warming up to 125～140 ℃, return time 1～3h divides water (vacuum hydro-extraction) then, can obtain average functionality and be 8～14 polyol polyester;
(3) polyol polyester esterification: when the question response container is cooled to 100～110 ℃ of left and right sides, add hydroquinone of polymerization retarder and vinylformic acid, heat up then, reflux when being warming up to 130～145 ℃, return time 1～3h, divide water (vacuum hydro-extraction) again, distillate until anhydrous, cooling discharging promptly gets ultraviolet curing polyester acrylic ester prepolymer.The number of the activity double key group of ultraviolet curing polyester acrylic ester prepolymer can change to determine according to acrylic acid consumption.
Wherein, can introduce activity double key with the acid of methacrylic acid instead of propylene in the polyol polyester esterification of (3) step, the number of activity double key (functionality) can be realized by change methacrylic acid, acrylic acid consumption.And the hexanodioic acid in present method can be used diacid or dicarboxylic anhydride replacements such as Succinic Acid, certain herbaceous plants with big flowers diacid, terephthalic acid, suitable divinyl acid anhydrides; 1, polyfunctional group alcohols such as the 4-butyleneglycol can spent glycol, glycerol, hexylene glycol, glycerine replace.Catalyzer can also be other organic catalyst except above-mentioned tosic acid, as: Phenylsulfonic acid, dodecyl sodium sulfonate; Also can be organic catalyst, as: H
2SO
4, H
3PO
4Stopper can also be inorganic stopper except Resorcinol, as: CuCl, FeCl
3Also can be other organic stopper, as: tert-butyl catechol, organic copper salt, quaternary amine etc.
The composition principle of present method: earlier with hexanodioic acid, tetramethylolmethane, 1,4-butyleneglycol, reaction generate polyol polyester, add vinylformic acid again and carry out blocking modification.Tetramethylolmethane is a tetravalent alcohol that contains primary hydroxyl, it is higher to make raw material gained hardness of paint film with it, and snappiness is lower, use fatty long-chain hexanodioic acid with the adjustment snappiness, but the average functionality of tetramethylolmethane and hexanodioic acid have the danger of gel greater than two in the side chain, so in this reaction, with 1, the 4-butyleneglycol is adjusted the average functionality of product, thereby reaches the problem of controlling polymers molecular weight.After reaction generates many hydroxyls polyester; add vinylformic acid and carry out blocking modification; be the residual hydroxyl reaction in vinylformic acid and the polyester, to reach the purpose of introducing the acryloyl active group, the number of the activity double key group of introducing can change to determine according to acrylic acid consumption.
Under the condition that catalyzer exists, diacid and glycol back flow reaction synthetic mesophase product--polyol polyester add vinylformic acid again and carry out esterification, adopt Resorcinol to make stopper to prevent product polyester acrylic ester prepolymer generation gelation.
The viscosity of polyester acrylate increases along with the increase of molecular weight.According to Mark-Houwink nonlinear equation [η]=KM
α η(in the formula: [η] is limiting viscosity; K, α are constant in certain temperature and molecular weight ranges; M polymkeric substance molecular-weight average; η is a polymer viscosity), polymer property viscosity is only determined by the molecular weight M of sample as can be known.In addition, add the dimethylol propionic acid (DMPA) of three-functionality-degree, make prepolymer produce branching and enhancing wetting ability, make viscosity increase.
Further, the proportioning that above-mentioned raw materials is relatively optimized is: hexanodioic acid: 1,4-butyleneglycol: tetramethylolmethane: dimethylol propionic acid: acrylic acid mass ratio is 0.99: 0.51: 0.54: 0.60: 1.00, the catalyzer tosic acid is that the second step reactant total mass (is a hexanodioic acid, 1,4-butyleneglycol, tetramethylolmethane and four kinds of component total masses of dimethylol propionic acid) 0.1%, hydroquinone of polymerization retarder is 0.02% of a total reactant total mass.
Regulate the hydroxyl carboxylic than may command prepolymer sticking power, improve cured coating film cohesiveness; Obtain the high and good prepolymer of cured coating film cohesiveness of viscosity, hydroxyl should be suitably excessive.Experiment shows that the hydroxyl carboxylic is than between 1.1-1.3 in the reactant formula system, and particularly when hydroxyl carboxylic ratio was 1.15, synthetic polyester acrylate over-all properties was more satisfactory.
A temperature-time relationship of relatively optimizing in the aforesaid method is: when (2) goes on foot the synthesis of polyhydroxy polyester, begin back flow reaction when being warming up to 125 ℃, return time 2.5h; When (3) goes on foot the polyol polyester esterification, begin back flow reaction when being warming up to 140 ℃, return time 2h.
The device of laboratory synthesizing polyester acrylic ester prepolymer comprises that mainly four-hole round-bottomed flask (500mL) is a reactor, adds electric mixer, and electric mantle heating and temperature control are by thermometer (0～200 ℃) observing response temperature.For preventing the oxidized variable color of resin, reaction needed is carried out under the nitrogen protection atmosphere.Reaction is under refluxad carried out, and adopts prolong to reflux; Prolong is used for the alcohol that refluxes in reaction early stage, and the reaction later stage adds water trap and carries out branch water; The condensation mouth of pipe is adorned a bypass vacuum pump, uses the vacuum forced dehydration in the reaction later stage.
Claims (6)
1. the preparation method of ultraviolet curing polyester acrylic ester prepolymer, it is characterized in that: it may further comprise the steps:
(1) gets the raw materials ready-get the raw materials ready: hexanodioic acid: 1 by following component and mol ratio, 4-butyleneglycol: tetramethylolmethane: dimethylol propionic acid: vinylformic acid=0.9～1.1: 0.4～0.6: 0.4～0.65: 0.7～0.8: 0.6～2.0, the catalyzer tosic acid is a hexanodioic acid, 1,0.01～0.5% of 4-butyleneglycol, tetramethylolmethane and four kinds of component total masses of dimethylol propionic acid, hydroquinone of polymerization retarder is 0.0001～0.1% of a total reactant total mass;
(2) synthesis of polyhydroxy polyester: with the hexanodioic acid of getting ready, 1,4-butyleneglycol, tetramethylolmethane, dimethylol propionic acid and catalyzer add reaction vessel, heat under the nitrogen protection condition, and each component that makes adding that heats while stirring is fully dissolved; Back flow reaction when being warming up to 125～140 ℃, return time 1～3h divides water then;
(3) polyol polyester esterification: when the question response container is cooled to 100～110 ℃ of left and right sides, add hydroquinone of polymerization retarder and vinylformic acid, heat up then, reflux when being warming up to 130～145 ℃, return time 1～3h, divide water again, distillate until anhydrous, cooling discharging promptly gets ultraviolet curing polyester acrylic ester prepolymer.
2. the preparation method of ultraviolet curing polyester acrylic ester prepolymer according to claim 1, it is characterized in that: described hexanodioic acid: 1,4-butyleneglycol: tetramethylolmethane: dimethylol propionic acid: acrylic acid mass ratio is 0.99: 0.51: 0.54: 0.60: 1.00, the catalyzer tosic acid is a hexanodioic acid, 1,0.1% of 4-butyleneglycol, tetramethylolmethane and four kinds of component total masses of dimethylol propionic acid, hydroquinone of polymerization retarder is 0.02% of a total reactant total mass.
3. the preparation method of ultraviolet curing polyester acrylic ester prepolymer according to claim 1 and 2 is characterized in that: when (2) goes on foot the synthesis of polyhydroxy polyester, begin back flow reaction when being warming up to 125 ℃, return time 2.5h; When (3) goes on foot the polyol polyester esterification, begin back flow reaction when being warming up to 140 ℃, return time 2h.
4. the preparation method of ultraviolet curing polyester acrylic ester prepolymer according to claim 3 is characterized in that: can introduce activity double key with the acid of methacrylic acid instead of propylene in the polyol polyester esterification of (3) step.
5. according to the preparation method of claim 1 or 2 or 4 described ultraviolet curing polyester acrylic ester prepolymers, it is characterized in that: described hexanodioic acid can use Succinic Acid, certain herbaceous plants with big flowers diacid, terephthalic acid or suitable divinyl acid anhydrides to replace; 1, polyfunctional group alcohols such as the 4-butyleneglycol can spent glycol, glycerol, hexylene glycol, glycerine replace.
6. the preparation method of ultraviolet curing polyester acrylic ester prepolymer according to claim 5 is characterized in that: the hydroxyl carboxylic is than between 1.1-1.3 in the reactant formula system.
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Cited By (9)
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| CN102134311A (en) * | 2011-01-04 | 2011-07-27 | 南京工业大学 | Preparation method of terpene polyester acrylate |
| CN102532966A (en) * | 2010-12-28 | 2012-07-04 | 汪宏伟 | Preparation method of ultraviolet-curing UV (ultraviolet) oil |
| CN107418297A (en) * | 2017-05-26 | 2017-12-01 | 南京巨鲨显示科技有限公司 | A kind of anti-dizzy dye pressuresteam sterilization instruction ink of UV photocurings and preparation method thereof |
| CN107880258A (en) * | 2017-10-16 | 2018-04-06 | 广州五行材料科技有限公司 | Low viscosity modified polyester acrylate ester and preparation method thereof |
| CN110272536A (en) * | 2019-06-25 | 2019-09-24 | 湖北宜化集团有限责任公司 | A kind of synthetic method solidifying end-vinyl waterborne polyester for UV-LED |
| CN110272537A (en) * | 2019-06-25 | 2019-09-24 | 三峡大学 | A kind of synthetic method solidifying the modified end-vinyl waterborne polyester of aldehyde resin for UV-LED |
| CN111320958A (en) * | 2020-03-03 | 2020-06-23 | 常州华科聚合物股份有限公司 | UV/thermal dual-curing adhesive for solar photovoltaic back panel and preparation method thereof |
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| CN112226149A (en) * | 2020-10-23 | 2021-01-15 | 无锡博加电子新材料有限公司 | Strong acid-resistant alkali-soluble UV (ultraviolet) curing resin and application thereof in glass etching |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102532966A (en) * | 2010-12-28 | 2012-07-04 | 汪宏伟 | Preparation method of ultraviolet-curing UV (ultraviolet) oil |
| CN102134311A (en) * | 2011-01-04 | 2011-07-27 | 南京工业大学 | Preparation method of terpene polyester acrylate |
| CN102134311B (en) * | 2011-01-04 | 2013-02-06 | 南京工业大学 | Preparation method of terpene polyester acrylate |
| CN107418297A (en) * | 2017-05-26 | 2017-12-01 | 南京巨鲨显示科技有限公司 | A kind of anti-dizzy dye pressuresteam sterilization instruction ink of UV photocurings and preparation method thereof |
| CN107880258A (en) * | 2017-10-16 | 2018-04-06 | 广州五行材料科技有限公司 | Low viscosity modified polyester acrylate ester and preparation method thereof |
| CN110272537A (en) * | 2019-06-25 | 2019-09-24 | 三峡大学 | A kind of synthetic method solidifying the modified end-vinyl waterborne polyester of aldehyde resin for UV-LED |
| CN110272536A (en) * | 2019-06-25 | 2019-09-24 | 湖北宜化集团有限责任公司 | A kind of synthetic method solidifying end-vinyl waterborne polyester for UV-LED |
| CN110272537B (en) * | 2019-06-25 | 2021-06-18 | 三峡大学 | Synthetic method of UV-LED curing aldehyde resin modified vinyl-terminated waterborne polyester |
| CN110272536B (en) * | 2019-06-25 | 2021-08-13 | 湖北宜化集团有限责任公司 | Synthetic method for UV-LED (ultraviolet-light emitting diode) cured vinyl-terminated waterborne polyester |
| CN111320958A (en) * | 2020-03-03 | 2020-06-23 | 常州华科聚合物股份有限公司 | UV/thermal dual-curing adhesive for solar photovoltaic back panel and preparation method thereof |
| CN111320958B (en) * | 2020-03-03 | 2022-03-29 | 常州华科聚合物股份有限公司 | UV/thermal dual-curing adhesive for solar photovoltaic back panel and preparation method thereof |
| CN111334234A (en) * | 2020-03-12 | 2020-06-26 | 常州华科聚合物股份有限公司 | Special adhesive for solar photovoltaic back panel based on dual curing and preparation method thereof |
| CN112226149A (en) * | 2020-10-23 | 2021-01-15 | 无锡博加电子新材料有限公司 | Strong acid-resistant alkali-soluble UV (ultraviolet) curing resin and application thereof in glass etching |
| CN112226149B (en) * | 2020-10-23 | 2022-03-04 | 无锡博加电子新材料有限公司 | Strong acid-resistant alkali-soluble UV (ultraviolet) curing resin and application thereof in glass etching |
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