CN101481450A - Light-sensitive self-initiated polyurethane acrylic ester oligomer and method for synthesizing the same - Google Patents
Light-sensitive self-initiated polyurethane acrylic ester oligomer and method for synthesizing the same Download PDFInfo
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- CN101481450A CN101481450A CNA2008100557240A CN200810055724A CN101481450A CN 101481450 A CN101481450 A CN 101481450A CN A2008100557240 A CNA2008100557240 A CN A2008100557240A CN 200810055724 A CN200810055724 A CN 200810055724A CN 101481450 A CN101481450 A CN 101481450A
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- acrylic ester
- polyurethane acrylic
- ester oligomer
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Abstract
The invention discloses a photosensitive self-initiation polyurethane acrylic ester oligomer and a method for synthesizing the same. The method comprises the following steps: first, reacting diisocyanate with a terminal hydroxy compound so as to obtain a compound with isocyanate as the terminal group; and then, reacting the hydroxyl-containing light initiator and acrylic acid hydroxy ester with the rest isocyanate to obtain the polyurethane acrylic ester oligomer that has a mixed terminal capped by propylene acyloxy and light initiator active group. When in use, the photosensitive self-initiation polyurethane acrylic ester oligomer can achieve the photosensitive self-initiation polymerization and curing proposal with the addition of no or little light initiator. Besides, the photosensitive self-initiation polyurethane acrylic ester oligomer also can be used as a macro molecular light initiator; and the photosensitive self-initiation polyurethane acrylic ester oligomer has excellent compatibility with other polyurethane acrylic ester oligomers.
Description
Technical field
The invention belongs to a kind of can be photosensitive from the polyurethane acrylic ester oligomer and the synthetic method thereof that cause.
Background technology
UV-curing technology is a kind of new technology of material industry.It has solvent-free, and is pollution-free, saves the energy, and multiple advantages such as economize on resources is an eco-friendly new technology.Since nearly half a century, this technology has obtained application more and more widely at industrial circles such as coating, printing ink, binding agents, demonstrates bright development prospect day by day.
In the ultraviolet light polymerization formula for a product, the most basic component has three kinds of components such as light-cured resin oligopolymer, monomer diluent and photoinitiator.Although these three kinds of components can exert an influence to every characteristic of material, the basic role of these three kinds of components still can be distinguished substantially, can not replace mutually.Light-cured resin is the most basic polymeric material, and it has determined system to solidify the fundamental characteristics of material afterwards; Monomer diluent mainly is to be used for diluting full-bodied light-cured resin, guarantee system had the rheological characteristics of suitable construction process requirement before solidifying, the effect of photoinitiator then is the free radical or the cation group that can produce sufficient amount under ultraviolet light irradiation at the utmost point in the short period of time, make system fast initiated polymerization solidify.
In technology in the past, three kinds of different componentss prepare respectively alone, just can mix at last according to a certain ratio when just having arrived the preparation the finished product.Up-to-date technical development is to toxic, transport property, the extractibility of photoinitiator system, and many-sided characteristics such as volatility, smell are all had higher requirement.For this reason, produced and some component wherein can have been merged, with the purpose of some performance of reaching improved system.
Summary of the invention
The present invention is by combining light-cured resin oligopolymer and photoinitiator, prepare a kind of oligopolymer that under ultraviolet light irradiation, can realize from initiated polymerization, this resin can not add or add less photoinitiator when the preparation the finished product, simplified Recipe, simultaneously because photosensitive group is combined among the oligomer molecule chain, formed a kind of effect of macromolecular photoinitiator, can effectively reduce the toxic of small molecules light trigger, transport property, extractibility, volatility and smell etc., simultaneously also guaranteed to have good consistency in the system between the various types of materials molecule, every product that can the processability excellence.
What the present invention relates to can be photosensitive from the polyurethane acrylic ester oligomer that causes, and its constitutional features can following formula (I) be represented:
R1 represents and removes two hydroxyls in two ends main chain part afterwards in the terminal hydroxy group compound of molecular weight between 400-2000 in the formula; R1 can be a polyethers, also can be polyester, or the block polymer of polyethers or polyester;
R2 represents the remainder that removes two isocyanate group in the diisocyanate cpd in the formula, and diisocyanate cpd commonly used has tolylene diisocyanate, diphenylmethanediisocyanate, isophorone diisocyanate, oneself two the support vulcabond.
R4 and R5 can represent one of following A, two kinds of structures of B at the same time or separately:
Structural formula A is:
Structural formula B is:
Wherein R3 represents one of two kinds of structures such as second two support bases or methyl second two support bases.
Wherein the molar fraction B/ (A+B) of structural formula B and A+B sum formation is between interval (0,100).
What the present invention relates to is can be photosensitive as follows from the preparation method of the polyurethane acrylic ester oligomer that causes: following umber is all in molal quantity.
Thermometer is being housed, agitator, dropping funnel, in the reaction flask of condenser and nitrogen inlet, add 1 part of terminal hydroxy group compound, and can add the solvent of some amount according to circumstances, be warming up to preset temperature then, the omnidistance nitrogen that feeds in the reaction process, drip the diisocyanate cpd of 2 umber amounts and the catalyzer of respective numbers, stop behind the reaction certain hour, system is reduced to room temperature, reactor is sealed with black material, add light trigger UV2959 again, be warming up to another preset temperature, reaction certain hour, the stopper of continuation dropwise addition of acrylic acid hydroxy ester and some amount, continue the reaction certain hour, sampling, is reacted and is finished till the absorption peak of this group disappears with the content of the isocyanate group in the infrared spectrometer test reaction liquid.Vacuum pumps solvent, and reaction solution is reduced to room temperature, and reaction finishes.Total consumption of UV2959 that adds in the reaction and crylic acid hydroxy ester should be 1 umber amount, and arbitrary component is all non-vanishing.
Above-mentioned chemical reaction can represent with following reaction formula, wherein:
(a) be diisocyanate cpd;
(b) be the terminal hydroxy group compound;
(c) be isocyanate terminated compound after vulcabond and the addition of terminal hydroxy group compound;
(d) be light trigger UV2959;
(e) be crylic acid hydroxy ester;
Look different the compounds that generate following three kinds (f), (g), (h) different structure of light trigger UV2959 and crylic acid hydroxy ester compound proportioning in the reaction:
(f) this is with the end capped polyurethane acrylic ester oligomer of acryloxy, and the polyurethane acrylic ester oligomer that this and general photo-curing material use is as good as, and the acryloxy of its middle-end position provides the chemical structure that can realize ultraviolet light polymerization;
(g) on a termination of molecular chain light trigger UV2959, the other end has connected the acryloyl-oxy group, this promptly is a kind of structure that realizes the resin oligopolymer of photocuring, can be considered a kind of structure of macromolecular photoinitiator again; This also is one of resulting structure involved in the present invention.
(h) all connected light trigger UV2959 group at the two ends of molecular chain, this can be considered a kind of macromolecular light trigger structure.Because this macromolecular main chain part is identical with the backbone structure of polyurethane acrylic ester oligomer, therefore the consistency with resin has obtained best assurance.This is two of the effective chemical structure that the present invention relates to.
In the building-up process of reality, (f), the performance that material showed and the effect of (g), (h) three kinds of structures have nothing in common with each other.Wherein (f) only has polymerizable functional but do not have from causing function, therefore can only use as common oligopolymer; (g) promptly having polymerizable functional and also have from causing function, is resulting structure real among the present invention, but because the initiation functional group content is too high, this class formation is unsuitable directly to be used separately, must piece together usefulness with the material of (f) structure; (h) do not have polymerizable functional and only have the initiation function, can only use as macromolecular photoinitiator.Therefore, according to reaction in the proportioning raw materials difference that drops into, can obtain the product of different performance and different purposes.
Embodiment
Following embodiment further specifies of the present invention.
Embodiment one:
Thermometer is being housed, agitator, dropping funnel, in the 3000ml reaction flask of condenser and nitrogen inlet, add the 400g poly(oxyethylene glycol) 400, be warming up to 80 ℃ then, the omnidistance nitrogen that feeds in the reaction process drips the mixture of the catalyzer dibutyl tin laurate of 348g tolylene diisocyanate and 0.5%, react after 2 hours temperature of charge to be risen to 90 ℃ and continue to react 2 hours, stopped reaction, system is reduced to room temperature, reactor is sealed with black material, be warming up to 70 ℃, drip light trigger UV2959 90g altogether, be dissolved among the 400g ethyl acetate, dropwise and continue reaction 1 hour, dropwise addition of acrylic acid hydroxyl ethyl ester 186g then, continue the reaction certain hour, the sampling content of the isocyanate group in the infrared spectrometer test reaction liquid, till the absorption peak of this group disappeared, vacuum extracted neat solvent, reaction solution is reduced to room temperature, and reaction finishes.
Embodiment two:
Embodiment one resulting material is mixed with tri (propylene glycol) diacrylate in the ratio of 1:1, and coating forms the liquid film of 0.1mm on sheet glass, uses high voltage mercury lamp irradiation, need not add light trigger and can make the liquid film polymerizing curable.
Claims (3)
1, a kind of can be photosensitive from the polyurethane acrylic ester oligomer and the synthetic method thereof that cause, it is characterized in that: described compound can photosensitive molecular structural formula be from the polyurethane acrylic ester oligomer that causes:
R1 represents and removes two hydroxyls in two ends main chain part afterwards in the terminal hydroxy group compound of molecular weight between 400-2000 in the formula; R1 can be a polyethers, also can be polyester, or the block polymer of polyethers or polyester;
R2 represents the remainder that removes two isocyanate group in the diisocyanate cpd in the formula, and diisocyanate cpd commonly used has tolylene diisocyanate, diphenylmethanediisocyanate, isophorone diisocyanate, oneself two the support vulcabond;
R4 and R5 can represent one of following A, two kinds of structures of B at the same time or separately:
Structural formula A is:
Structural formula B is:
Wherein R3 represents one of two kinds of structures such as second two support bases or methyl second two support bases.
2, a kind of can be photosensitive from the polyurethane acrylic ester oligomer and the synthetic method thereof that cause, it is characterized in that: among described oligopolymer, have the group B of photoinitiators function and can realize that the formed molar fraction of group A of photocuring function is: B/ (A+B) is between interval (0,100).
3, a kind of can be photosensitive from the polyurethane acrylic ester oligomer and the synthetic method thereof that cause, it is characterized in that synthetic method is as follows: at first hydroxyl telechelic polyester or end hydroxy polyether and diisocyanate cpd are reacted in the ratio of 1:2 mole, the reaction that one of them isocyanate group takes place in the assurance diisocyanate cpd also reacts completely, and then contain the crylic acid hydroxy ester of structural formula A in the adding molecule, Hydroxyethyl acrylate or Propylene glycol monoacrylate, with the light trigger UV2959 that contains structural formula B in the molecule, and both mole number sums should equal the mole number of terminal hydroxy group compound; Reaction finishes and promptly can obtain required compound; What the difference that adds ratio according to UV2959 can obtain different qualities can be photosensitive from the polyurethane acrylic ester oligomer that causes.
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| CN 200810055724 CN101481450B (en) | 2008-01-07 | 2008-01-07 | Light-sensitive self-initiated polyurethane acrylic ester oligomer and method for synthesizing the same |
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| CN 200810055724 CN101481450B (en) | 2008-01-07 | 2008-01-07 | Light-sensitive self-initiated polyurethane acrylic ester oligomer and method for synthesizing the same |
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| CN101481450A true CN101481450A (en) | 2009-07-15 |
| CN101481450B CN101481450B (en) | 2012-12-12 |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101811951A (en) * | 2010-05-07 | 2010-08-25 | 甘肃金盾化工有限责任公司 | Preparation method of 2-hydroxyl-1-{4-(2-hydroxyethyl) phenyl}-2-methyl-1-acetone |
| CN101914175A (en) * | 2010-08-05 | 2010-12-15 | 江南大学 | Method for preparing self-initiation ultraviolet-curing amphiphilic macromolecular resin |
| CN102432805A (en) * | 2011-08-31 | 2012-05-02 | 河南金誉包装科技股份有限公司 | Photo-curable polyurethane acrylate vinyl/propenyl ether heterozygous pre-polymer and preparation method thereof |
| CN102884098A (en) * | 2010-05-11 | 2013-01-16 | 汉高股份有限及两合公司 | Film-forming radiation-crosslinking adhesive |
| CN104530335A (en) * | 2014-09-19 | 2015-04-22 | 北京化工大学 | Preparation method of thermoplastic polyurethane-polystyrene block copolymer |
| CN105646830A (en) * | 2014-11-10 | 2016-06-08 | Tcl集团股份有限公司 | Photosensitive polyurethane, preparation method therefor and application of photosensitive polyurethane |
| CN106047136A (en) * | 2016-05-24 | 2016-10-26 | 恒昌涂料（惠阳）有限公司 | UV (Ultraviolet) coating material capable of being recoated and preparation method therefor |
| CN106752875A (en) * | 2017-01-06 | 2017-05-31 | 浙江新迪在龙涂料科技有限公司 | A kind of preparation of UV curing nanos transparent heat insulating dope |
| CN107337996A (en) * | 2017-07-21 | 2017-11-10 | 江苏宏泰高分子材料有限公司 | Solvent-free anti-corrosion of metal UV solidifications blacking of complete hiding and preparation method thereof |
| CN107698735A (en) * | 2017-10-31 | 2018-02-16 | 广东丽格科技股份有限公司 | A kind of low-viscosity polyester resin and its preparation method and application |
| 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 |
| CN110483730A (en) * | 2019-08-26 | 2019-11-22 | 江西迈亚科技有限公司 | A kind of polyurethane acrylic ester oligomer and the preparation method and application thereof method |
| CN110698974A (en) * | 2019-09-25 | 2020-01-17 | 依工特种材料（苏州）有限公司 | Low-odor UV-curing three-proofing paint composition |
| CN113667394A (en) * | 2021-08-16 | 2021-11-19 | 广东希贵光固化材料有限公司 | Temporary protective coating for UV (ultraviolet) light stripping and application thereof |
| CN114230747A (en) * | 2021-12-20 | 2022-03-25 | 江苏三木化工股份有限公司 | Preparation method of high-solid low-viscosity self-initiated epoxy acrylate oligomer |
| CN115595111A (en) * | 2022-10-28 | 2023-01-13 | 东莞市德聚胶接技术有限公司（Cn） | Oil-acid-resistant UV-moisture dual-curing adhesive |
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2008
- 2008-01-07 CN CN 200810055724 patent/CN101481450B/en not_active Expired - Fee Related
Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101811951A (en) * | 2010-05-07 | 2010-08-25 | 甘肃金盾化工有限责任公司 | Preparation method of 2-hydroxyl-1-{4-(2-hydroxyethyl) phenyl}-2-methyl-1-acetone |
| CN102884098A (en) * | 2010-05-11 | 2013-01-16 | 汉高股份有限及两合公司 | Film-forming radiation-crosslinking adhesive |
| CN102884098B (en) * | 2010-05-11 | 2015-02-25 | 汉高股份有限及两合公司 | Film-forming radiation-crosslinking adhesive |
| CN101914175A (en) * | 2010-08-05 | 2010-12-15 | 江南大学 | Method for preparing self-initiation ultraviolet-curing amphiphilic macromolecular resin |
| CN102432805A (en) * | 2011-08-31 | 2012-05-02 | 河南金誉包装科技股份有限公司 | Photo-curable polyurethane acrylate vinyl/propenyl ether heterozygous pre-polymer and preparation method thereof |
| CN102432805B (en) * | 2011-08-31 | 2013-03-27 | 河南金誉包装科技股份有限公司 | Photo-curable polyurethane acrylate vinyl/propenyl ether heterozygous pre-polymer and preparation method thereof |
| CN104530335B (en) * | 2014-09-19 | 2017-10-10 | 北京化工大学 | A kind of preparation method of thermoplastic polyurethane polystyrene block copolymer |
| CN104530335A (en) * | 2014-09-19 | 2015-04-22 | 北京化工大学 | Preparation method of thermoplastic polyurethane-polystyrene block copolymer |
| CN105646830B (en) * | 2014-11-10 | 2018-10-26 | Tcl集团股份有限公司 | A kind of light sensitive polyurethane and its preparation method and application |
| CN105646830A (en) * | 2014-11-10 | 2016-06-08 | Tcl集团股份有限公司 | Photosensitive polyurethane, preparation method therefor and application of photosensitive polyurethane |
| CN106047136A (en) * | 2016-05-24 | 2016-10-26 | 恒昌涂料（惠阳）有限公司 | UV (Ultraviolet) coating material capable of being recoated and preparation method therefor |
| CN106047136B (en) * | 2016-05-24 | 2018-02-16 | 恒昌涂料（惠阳）有限公司 | One kind can recoat UV coating and preparation method thereof |
| CN106752875A (en) * | 2017-01-06 | 2017-05-31 | 浙江新迪在龙涂料科技有限公司 | A kind of preparation of UV curing nanos transparent heat insulating dope |
| CN107337996A (en) * | 2017-07-21 | 2017-11-10 | 江苏宏泰高分子材料有限公司 | Solvent-free anti-corrosion of metal UV solidifications blacking of complete hiding and preparation method thereof |
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| 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 |
| CN110483730A (en) * | 2019-08-26 | 2019-11-22 | 江西迈亚科技有限公司 | A kind of polyurethane acrylic ester oligomer and the preparation method and application thereof method |
| CN110483730B (en) * | 2019-08-26 | 2021-05-11 | 江西迈亚科技有限公司 | Polyurethane acrylate oligomer and preparation method and application method thereof |
| CN110698974A (en) * | 2019-09-25 | 2020-01-17 | 依工特种材料（苏州）有限公司 | Low-odor UV-curing three-proofing paint composition |
| CN113667394A (en) * | 2021-08-16 | 2021-11-19 | 广东希贵光固化材料有限公司 | Temporary protective coating for UV (ultraviolet) light stripping and application thereof |
| CN114230747A (en) * | 2021-12-20 | 2022-03-25 | 江苏三木化工股份有限公司 | Preparation method of high-solid low-viscosity self-initiated epoxy acrylate oligomer |
| CN114230747B (en) * | 2021-12-20 | 2024-02-02 | 江苏三木化工股份有限公司 | Preparation method of high-solid low-viscosity self-initiated epoxy acrylate oligomer |
| CN115595111A (en) * | 2022-10-28 | 2023-01-13 | 东莞市德聚胶接技术有限公司（Cn） | Oil-acid-resistant UV-moisture dual-curing adhesive |
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| CN101481450B (en) | 2012-12-12 |
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