CN101481450B - 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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- CN101481450B CN101481450B CN 200810055724 CN200810055724A CN101481450B CN 101481450 B CN101481450 B CN 101481450B CN 200810055724 CN200810055724 CN 200810055724 CN 200810055724 A CN200810055724 A CN 200810055724A CN 101481450 B CN101481450 B CN 101481450B
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- polyurethane acrylic
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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 mixture and the preparation method 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, stickers, 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 each item 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 materials, 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 radical or the cation group that under ultraviolet light irradiation, can produce sufficient amount 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 all had higher requirement to many-sided characteristics such as the toxic of photoinitiator system, transport property, extractibility, volatility, smells.For this reason, produced and can some component wherein have been merged, with the purpose of some performance of reaching improved system.
Summary of the invention:
The present invention is through 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 during the finished product or adds photoinitiator less in preparation, has simplified Recipe, simultaneously because photosensitive group is combined among the oligomer molecule chain; Formed a kind of effect of macromolecular photoinitiator; Can effectively reduce toxic, transport property, extractibility, volatility and the smell etc. of small molecules light trigger, also guarantee to have good consistency in the system between the various types of materials molecule simultaneously, can the excellent each item product of processability.
What the present invention relates to can be photosensitive from the polyurethane acrylic ester oligomer mixture that causes, and its constitutional features is by shown in the formula I:
R in the formula
1Represent the main chain part of removing in the block polymer of end hydroxy polyether, polyester or polyethers and the polyester of molecular weight between 400-2000 after two hydroxyls in two ends.
R in the formula
2Represent tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI), isophorone diisocyanate (IPDI); Hexamethylene diisocyanate (HDI), the xylyl vulcabond; Dicyclohexyl methane diisocyanate, 3,3 '-dimethyl diphenyl base-4; 4 '-vulcabond, 1, the 5-naphthalene diisocyanate removes the remainder of two NCOs.
R
4And R
5Can 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:
R wherein
3Represent one of ethylene group or two kinds of structures of methyl ethylene base.
Wherein the x 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 following from the preparation method of the polyurethane acrylic ester oligomer that causes.Following umber is all in molal quantity.
TM is being housed, whisking appliance, tap funnel is in the reaction flask of condensing surface 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 drum is sealed with black material, add light trigger UV2959 again, be warming up to another preset temperature; The reaction certain hour, the stopper of continuation dropwise addition of acrylic acid ester OH and some amount continues the reaction certain hour; Sampling is with the content of the NCO in the IR test reaction liquid, and till the absorption peak of this group disappeared, reaction finished.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 2 umber amounts, 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 that drops into different, can obtain the product of different performance and different purposes.
Concrete implementation method
Following embodiment further specifies of the present invention, rather than limits scope of the present invention.
Embodiment one:
TM is being housed, whisking appliance, tap funnel is in the 3000ml reaction flask of condensing surface and nitrogen inlet; Add the 400g PEG 400, be warming up to 80 ℃ then, the omnidistance nitrogen that feeds in the reaction process; Drip the mixture of 348g tolylene diisocyanate (TDI) and 0.5% catalyzer dibutyl tin laurate, react and after 2 hours temperature of charge is risen to 90 ℃ of continuation and reacted stopped reaction 2 hours; System is reduced to room temperature, reactor drum is sealed with black material, be warming up to 70 ℃; Drip light trigger UV2959 90g (being dissolved among the 400g ETHYLE ACETATE) altogether, dropwise and continue reaction 1 hour, dropwise addition of acrylic acid hydroxyl ethyl ester 186g then; Continue the reaction certain hour, sampling is with the content of the NCO in the IR test reaction liquid, till the absorption peak of this group disappears; Vacuum extracts neat solvent, and reaction solution is reduced to room temperature, and reaction finishes.
Embodiment two:
With ratio and the tri (propylene glycol) diacrylate of embodiment one resulting material in 1: 1
(DPGDA) mix, 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 (1)
- One kind can be photosensitive from the compound method of the polyurethane acrylic ester oligomer that causes, it is characterized in that: TM is being housed, whisking appliance, tap funnel; In the 3000ml reaction flask of condensing surface and nitrogen inlet, add the 400g PEG 400, be warming up to 80 ℃ then, the omnidistance nitrogen that feeds in the reaction process; Drip the mixture of the catalyzer dibutyl tin laurate of 348g tolylene diisocyanate and 0.5%, react and after 2 hours temperature of charge is risen to 90 ℃ and continue to react 2 hours, stopped reaction is reduced to room temperature with system; Reactor drum is sealed with black material, be warming up to 70 ℃, drip light trigger UV2959 90g altogether; Be dissolved among the 400g ETHYLE ACETATE, dropwise and continue reaction 1 hour, dropwise addition of acrylic acid hydroxyl ethyl ester 186g then; Continue reaction, sampling is with the content of the NCO in the IR test reaction liquid, till the absorption peak of this group disappears; Vacuum extracts neat solvent, and reaction solution is reduced to room temperature, and reaction finishes; To react and finish the resulting material in back and mix with tri (propylene glycol) diacrylate, on sheet glass, be coated with the liquid film of formation 0.1mm, use high voltage mercury lamp irradiation, and need not add light trigger and can make the liquid film polymerizing curable in 1: 1 ratio.
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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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| DE102010028870A1 (en) * | 2010-05-11 | 2011-11-17 | Henkel Ag & Co. Kgaa | 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 |
| 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 |
| 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 |
| 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 |
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| 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 |
| CN107987252B (en) * | 2017-11-17 | 2020-09-01 | 深圳市嘉卓成科技发展有限公司 | Preparation method of self-emulsifying water-based photoinitiator and water-based photoinitiator |
| 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 |
| CN113667394B (en) * | 2021-08-16 | 2023-06-23 | 广东希贵光固化材料有限公司 | UV illumination demolding temporary protective coating and application thereof |
| 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 |
| CN115595111B (en) * | 2022-10-28 | 2023-07-04 | 东莞市德聚胶接技术有限公司 | Oil acid resistant UV-moisture dual-curing adhesive |
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