CN102050938A - Method for preparing ultraviolet photocuring polyurethane resin based on polybasic isocyanate and polybasic hydroxy polyacrylate - Google Patents
Method for preparing ultraviolet photocuring polyurethane resin based on polybasic isocyanate and polybasic hydroxy polyacrylate Download PDFInfo
- Publication number
- CN102050938A CN102050938A CN 201010577067 CN201010577067A CN102050938A CN 102050938 A CN102050938 A CN 102050938A CN 201010577067 CN201010577067 CN 201010577067 CN 201010577067 A CN201010577067 A CN 201010577067A CN 102050938 A CN102050938 A CN 102050938A
- Authority
- CN
- China
- Prior art keywords
- isocyanate
- weight parts
- preparation
- ultraviolet curing
- urethane resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to a method for preparing ultraviolet photocuring polyurethane resin based on polybasic isocyanate and polybasic hydroxy polyacrylate. The method comprises the following steps of: 1) adding monohydroxy acrylic ester, butanol and dibutyltin dilaurate into a constant-pressure dropping funnel; 2) regulating the temperature of an oil bath pot to be between 20 and 50 DEG C after dropping is finished in the step 1), reacting for 1 to 2 hours and stopping the reaction; 3) adding 20 to 30 weight parts of polyhydroxy acrylic resin and 0.5 to 1.5 weight parts of inhibitor 4-methoxy phenol into a reaction product obtained in the step 2); and 4) adding 5 to 15 weight parts of active monomer thinner according to the solid content to obtain a product. The method has the advantages of performing polyfunctional monomer premature crosslinking, introducing more double bonds, and improving the crosslinking and relative molecular weight of a paint film; and the product has high mechanical properties and greatly improved corrosion resistance.
Description
Technical field
The present invention relates to a kind of preparation method of ultraviolet curing urethane resin, relate in particular to a kind of preparation method of the ultraviolet curing urethane resin based on multicomponent isocyanate and multi-hydroxy polyacrylic ester.
Background technology
Along with the fast development of industry, environment protection and save energy more and more come into one's own, and fundamental change has all taken place for the developing direction of coatings industry and product structure." 4E " principle (Economy, Efficiency, Environment and Energy) that proposed in 1977 with EPA is a sign especially, coating develops towards resource-saving, province's energy, pollution-free direction, and occurred with series such as water-borne coatings, radiation curable coating, powder coating, high solid coating is " saving type " coating of representative thereupon.Wherein ultraviolet-curing paint with its excellent performance, becomes the focus of present research and application as a kind of emerging coating.
Ultraviolet light polymerization is meant under the effect of UV-light, liquid oligopolymer (comprising monomer) forms the process of solid product through crosslinking polymerization, having high-level efficiency, low consumed advantage, and have the incomparable advantage of many traditional coatings, is a kind of environmentally friendly technology.At present, UV-cured resin is with its unique technique advantage, demonstrate great vitality, technological transformation for conventional industries, also provide advanced technique means, be widely used for fields such as chemical industry, machinery, electronics, light industry, transportation, communication for the foundation of new high-tech industry (particularly electronics and information industry) and development.But conventional UV-cured resin physical strength is relatively poor, and not corrosion-resistant, therefore occurs easily scratching under outdoor life-time service condition, not rub resistance.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of the ultraviolet curing urethane resin based on multicomponent isocyanate and multi-hydroxy polyacrylic ester, shortcoming such as the ultraviolet curing urethane resin physical strength that overcomes prior art is low, and is not corrosion-resistant.
The present invention is achieved like this, and its characterization method step is:
1) adds the monohydroxy acrylate of 20 ~ 30 weight parts, the butanols of 15 ~ 20 weight parts and the catalyzer of 0.1 ~ 1 weight part in the constant pressure funnel, in 30 ~ 50 ℃ of temperature ranges, slowly splash in the multicomponent isocyanate that 30 ~ 50 weight parts are housed, dropwised in 0.5 ~ 1 hour;
2) after step 1) dropwises, adjust oil bath pan temperature to 20 ~ 50 ℃, react after 1 ~ 2 hour, every 1 hour with acetone-Di-n-Butyl Amine method mensuration isocyanate content, after question response reaches theoretical level of response, i.e. stopped reaction;
3) to step 2) reacted product adds the acrylic polyol resin and 0.5 ~ 1.5 weight part stopper of 20 ~ 30 weight parts, reacted 8 ~ 12 hours down at 40 ~ 50 ℃, measure isocyanate group mass contg, stopped reaction after content is less than 2% with acetone-Di-n-Butyl Amine method;
4) test procedure 3) reacted product, determine the solid content of product, add the reactive monomer thinner of 5 ~ 15 weight parts according to solid content, promptly get product.
Described multicomponent isocyanate is a kind of in tolylene diisocyanate, isophorone diisocyanate, diphenylmethanediisocyanate, triphenylmethane triisocyanate, vulcabond low-grade polymer (trimerization/pentamer) and biuret, poly methylene poly phenyl poly isocyanate, the hexamethylene diisocyanate trimer.
Described monohydroxy acrylate is a kind in (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, (methyl) vinylformic acid hydroxy butyl ester and the pentaerythritol triacrylate.
A kind of in the organo-metallic salt catalyzer such as tertiary amine catalysts such as described catalyzer is triethylamine, diethylene diamine, the N-methylmorpholine and two lauric acid butyl tin, stannous octoate and organo-bismuth.
Described stopper is branch subtype stoppers such as MEHQ, Resorcinol, para benzoquinone, phenothiazine, beta-phenyl naphthylamines, p-ten.-butylcatechol, perhaps a kind of in the inorganics such as cuprous chloride, iron trichloride.
Described polyhydroxy polycarboxylic acrylate resin is that the following material of solution polymerization makes: the esterification monomer of one or more (methyl) vinylformic acid and C1-C6 alkyl alcohol, at least a kind of (methyl) acrylic ester monomer that contains hydroxyl.
Described reactive monomer thinner is a kind of in Viscoat 295, ethoxylated trimethylolpropane triacrylate, propylene glycol diacrylate, isobornyl acrylate, tri (propylene glycol) diacrylate, the 1,6 hexanediol diacrylate.
Advantage of the present invention is: ultraviolet curing urethane resin provided by the invention mainly is based on multicomponent isocyanate and multi-hydroxy polyacrylic ester, and adopt the monomer end-blocking of monohydroxy esters of acrylic acid, so not only can the polyfunctionality monomer crosslinked too early, can introduce simultaneously more two key, improve the crosslinked and relative molecular weight of paint film; Product has excellent mechanical property, and corrosion resistance nature obtained strengthening greatly, and its every performance all is better than common ultraviolet curing acrylic urethane; Characteristics such as in addition, this resin has also that synthesis technique is simple, raw materials cost is low and the shelf lives is long.
Embodiment
Embodiment 1
The acetone that adopts-Di-n-Butyl Amine method during the isocyanate group mass contg in the present embodiment explanation test reaction.
Concrete testing method is as follows:
1) preparation 0.1mol/L HCl standardized solution.
2) preparation 0.1mol/L Di-n-Butyl Amine-acetone standardized solution.
3) with HCl standard solution titration Di-n-Butyl Amine reference liquid 10 ml, use HCl reference liquid volume V
1Ml.
4) in the Erlenmeyer flask of 150ml, add W
1The sample of g reactant (when transformation efficiency is higher the amount of taking by weighing can a little louder) adds acetone solution, adds a small amount of indicator tetrabromophenol sulfonphthalein at last.
5) add Di-n-Butyl Amine reference liquid 10 ml and stir, insulation is 15 minutes about 25 ℃.
6) use the HCl standard solution titration, color is used HCl reference liquid volume V by blue yellowing
2Ml.
The calculating of isocyanate groups molality:
W
1-weighing reactant quality; W
Always-reactant total mass;
W
B-adding B constituent mass; (C
NCO)
0Isocyanate groups molality in the-B component.
By monitoring, determine the degree that reaction is carried out, and determine that for final the reaction times provides theoretical foundation isocyanate group mass contg in the reaction process.
Embodiment 2
Present embodiment illustrates the preparation method of ultraviolet curing urethane resin provided by the invention.
1) adds 30 parts by weight of acrylic hydroxyl ethyl esters, the butanols of 15 weight parts and the catalyzer dibutyl tin dilaurate of 0.1 weight part in the constant pressure funnel, under the certain temperature condition, slowly splash in the multicomponent isocyanate that 30 weight parts are housed, dropwised in 1 hour
2) after step 1) dropwises, adjust oil bath pan temperature to 45 ℃, react after 2 hours, every 1 hour with acetone-Di-n-Butyl Amine method mensuration isocyanate content, after question response reaches preset value, i.e. stopped reaction.
3) to step 2) reacted product adds the acrylic polyol resin and the 1 weight part stopper 4-methoxyl group phenol of 20 weight parts, 50 ℃ of reactions 8 ~ 12 hours down.Measure isocyanate group mass contg, stopped reaction after content is less than 2% with acetone-Di-n-Butyl Amine method.
4) test procedure 3) reacted product, determine the solid content of product, add the reactive monomer thinner of 10 weight parts according to solid content, promptly get product.
Embodiment 3
Present embodiment illustrates the preparation method of ultraviolet curing urethane resin provided by the invention.
1) adds 40 parts by weight of acrylic hydroxyl ethyl esters, the butanols of 10 weight parts and the catalyzer dibutyl tin dilaurate of 0.5 weight part in the constant pressure funnel, under the certain temperature condition, slowly splash in the multicomponent isocyanate that 40 weight parts are housed, dropwised in 1 hour
2) after step 1) dropwises, adjust oil bath pan temperature to 45 ℃, react after 2 hours, every 1 hour with acetone-Di-n-Butyl Amine method mensuration isocyanate content, after question response reaches preset value, i.e. stopped reaction.
3) to step 2) reacted product adds the acrylic polyol resin and the 1 weight part stopper 4-methoxyl group phenol of 30 weight parts, 50 ℃ of reactions 8 ~ 12 hours down.Measure isocyanate group mass contg, stopped reaction after content is less than 2% with acetone-Di-n-Butyl Amine method.
4) test procedure 2) reacted product, determine the solid content of product, add the reactive monomer thinner of 15 weight parts according to solid content, promptly get product.
Embodiment 4
Present embodiment illustrates the performance of ultraviolet curing urethane resin provided by the invention.
The resin that the foregoing description 2-3 is obtained carries out performance test, and it the results are shown in Table 1.
1) resin solid content
According to the solid content of gravimetric determination resin, a certain amount of sample of weighing is put into baking oven and is weighed half an hour 120 ℃ of oven dry.
2) resin viscosity
Adopt the viscosity of rotational viscosimeter test resin, probe temperature is 25 ℃.
3) adopt set time pencil hardness method to determine set time, measure the pencil hardness of paint film under different set times, when pencil hardness does not change, be the set time of paint film.
4) physical strength of paint film
Pencil hardness is according to the method test of GB/T6739-1996, and snappiness is according to the method test of GB/T1731-93, and sticking power is according to the method test of GB/T9286-1998.
Embodiment 5
The present embodiment explanation is that matrix resin prepares ultraviolet-curing paint with ultraviolet curing urethane resin provided by the invention.
With above-mentioned UV-light light-cured polyurethane resin is that matrix resin prepares ultraviolet-curing paint, and its preparation method comprises the steps:
1), stirs fully to dissolving fully with light trigger and mixing diluents; 2) add the aforementioned body resin, it is even to be warming up to 45 ℃ of mechanical stirring; 3) be cooled to room temperature, add color stuffing, use the high speed shear dispersion machine, rotating speed is 3000 rev/mins, stirs after 1 ~ 2 hour, promptly obtains product
Wherein thinner is a methyl acrylate, product; Color stuffing is titanium dioxide and lime carbonate, product.Light trigger is product.
Table 2 has provided the concrete composition of coating.
Embodiment 6
The performance of present embodiment explanation ultraviolet-curing paint.
Coating UD-1 ~ UD-5 that above-mentioned example 5 is obtained is sprayed on the pretreated tinplate according to GB 1727-1992, and film thickness is controlled between the 23-35 micron.The panel that spraying is finished is placed on the ventilation, treats solvent evaporates after half an hour, uses 600W ultraviolet light polymerization light irradiation, and irradiation distance is 30 centimetres, and irradiation time is no more than 50 seconds.The performance of test cured paint film, it the results are shown in Table 3.
1) pencil hardness
Measure according to GB/T6739-1996.
2) sticking power
Measure according to GB/T9286-1998, adopt stroke lattice device that paint film is carried out the cutting of lattice system of battle formations shape, make it penetrate into ground just, judge the rank of sticking power from stroke area that lattice zone ground comes off by paint film, its result is with 0～5 grade of expression, and 0 grade best, and 5 grades the poorest.
3) snappiness
Measure according to GB/T1731-93, with test panel 1-3 in second behind the crooked 180o of mandrel rod, represent the snappiness of paint film not cause the minimum mandrel rod diameter of paint film destructive (mm).
4) water tolerance
Undertaken by GB/T1733-1993, the water mark is dried with absorbent cotton or soft paper in water-fast back, places and treats that it was cooled under the standard conditions naturally in 30 minutes, detects in 1 hour.
Claims (7)
1. preparation method based on the ultraviolet curing urethane resin of multicomponent isocyanate and multi-hydroxy polyacrylic ester is characterized in that method steps is:
1) adds the monohydroxy acrylate of 20 ~ 30 weight parts, the butanols of 15 ~ 20 weight parts and the catalyzer of 0.1 ~ 1 weight part in the constant pressure funnel, in 30 ~ 50 ℃ of temperature ranges, slowly splash in the multicomponent isocyanate that 30 ~ 50 weight parts are housed, dropwised in 0.5 ~ 1 hour;
2) after step 1) dropwises, adjust oil bath pan temperature to 20 ~ 50 ℃, react after 1 ~ 2 hour, every 1 hour with acetone-Di-n-Butyl Amine method mensuration isocyanate content, after question response reaches theoretical level of response, i.e. stopped reaction;
3) to step 2) reacted product adds the acrylic polyol resin and 0.5 ~ 1.5 weight part stopper of 20 ~ 30 weight parts, reacted 8 ~ 12 hours down at 40 ~ 50 ℃, measure isocyanate group mass contg, stopped reaction after content is less than 2% with acetone-Di-n-Butyl Amine method;
4) test procedure 3) reacted product, determine the solid content of product, add the reactive monomer thinner of 5 ~ 15 weight parts according to solid content, promptly get product.
2. the preparation method of the ultraviolet curing urethane resin based on multicomponent isocyanate and multi-hydroxy polyacrylic ester according to claim 1 is characterized in that described multicomponent isocyanate is a kind of in tolylene diisocyanate, isophorone diisocyanate, diphenylmethanediisocyanate, triphenylmethane triisocyanate, vulcabond low-grade polymer (trimerization/pentamer) and biuret, poly methylene poly phenyl poly isocyanate, the hexamethylene diisocyanate trimer.
3. the preparation method of the ultraviolet curing urethane resin based on multicomponent isocyanate and multi-hydroxy polyacrylic ester according to claim 1 is characterized in that described monohydroxy acrylate is a kind in (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, (methyl) vinylformic acid hydroxy butyl ester and the pentaerythritol triacrylate.
4. the preparation method of the ultraviolet curing urethane resin based on multicomponent isocyanate and multi-hydroxy polyacrylic ester according to claim 1, it is characterized in that a kind of in tertiary amine catalysts such as described catalyzer is triethylamine, diethylene diamine, the N-methylmorpholine and the organo-metallic salt catalyzer such as two lauric acid butyl tin, stannous octoate and organo-bismuth.
5. the preparation method of the ultraviolet curing urethane resin based on multicomponent isocyanate and multi-hydroxy polyacrylic ester according to claim 1, it is characterized in that described stopper is branch subtype stoppers such as MEHQ, Resorcinol, para benzoquinone, phenothiazine, beta-phenyl naphthylamines, p-ten.-butylcatechol, perhaps a kind of in the inorganics such as cuprous chloride, iron trichloride.
6. the preparation method of the ultraviolet curing urethane resin based on multicomponent isocyanate and multi-hydroxy polyacrylic ester according to claim 1, it is characterized in that described polyhydroxy polycarboxylic acrylate resin is that the following material of solution polymerization makes: the esterification monomer of one or more (methyl) vinylformic acid and C1-C6 alkyl alcohol, at least a kind of (methyl) acrylic ester monomer that contains hydroxyl.
7. the preparation method of the ultraviolet curing urethane resin based on multicomponent isocyanate and multi-hydroxy polyacrylic ester according to claim 1, it is characterized in that described reactive monomer thinner is a kind of in Viscoat 295, ethoxylated trimethylolpropane triacrylate, propylene glycol diacrylate, isobornyl acrylate, tri (propylene glycol) diacrylate, the 1,6 hexanediol diacrylate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105770673A CN102050938B (en) | 2010-12-07 | 2010-12-07 | Method for preparing ultraviolet photocuring polyurethane resin based on polybasic isocyanate and polybasic hydroxy polyacrylate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105770673A CN102050938B (en) | 2010-12-07 | 2010-12-07 | Method for preparing ultraviolet photocuring polyurethane resin based on polybasic isocyanate and polybasic hydroxy polyacrylate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102050938A true CN102050938A (en) | 2011-05-11 |
| CN102050938B CN102050938B (en) | 2012-08-08 |
Family
ID=43955779
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010105770673A Expired - Fee Related CN102050938B (en) | 2010-12-07 | 2010-12-07 | Method for preparing ultraviolet photocuring polyurethane resin based on polybasic isocyanate and polybasic hydroxy polyacrylate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102050938B (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391470A (en) * | 2011-09-07 | 2012-03-28 | 南昌航空大学 | Preparation method for ionic liquid terminated polyurethane acrylate |
| CN102604035A (en) * | 2012-03-13 | 2012-07-25 | 广东深展实业有限公司 | Ultraviolet cured two-degree-of-functionality polyurethane acrylic ester base coating resin for vacuum coating |
| CN102659995A (en) * | 2012-04-24 | 2012-09-12 | 南昌航空大学 | Preparation method of ultraviolet-curable water-borne fluorinated paint with low surface energy |
| CN103387654A (en) * | 2012-05-08 | 2013-11-13 | 营口巨成教学科技开发有限公司 | Novel compound photo-curing material, and production method and application field thereof |
| CN104530789A (en) * | 2015-01-19 | 2015-04-22 | 广东希贵光固化材料有限公司 | Cationic photocureable coating for transfer printing film |
| CN105199077A (en) * | 2015-10-23 | 2015-12-30 | 青岛展辰新材料有限公司 | Preparation method of high-functionality wear-resistant cold light source cured polyurethane acrylate |
| CN105218783A (en) * | 2014-06-17 | 2016-01-06 | 江南大学 | The preparation method of the water-borne UV-curing star-shaped prepolymers of a kind of high reactivity |
| CN107667131A (en) * | 2015-04-03 | 2018-02-06 | 铁锈子弹有限责任公司 | VOC free is painted |
| CN110054755A (en) * | 2019-04-24 | 2019-07-26 | 广东东田转印新材料有限公司 | It is a kind of can the UV resin of surface drying, preparation method and applications |
| CN110869404A (en) * | 2017-07-10 | 2020-03-06 | 喜利得股份公司 | Method for producing urethane resin composition containing TEMPOL with improved storage stability |
| CN110903459A (en) * | 2019-11-25 | 2020-03-24 | 重庆沥智路桥工程有限公司 | Hydroxyl-terminated polyurethane methacrylic resin, preparation method and application thereof |
| CN112266457A (en) * | 2020-11-06 | 2021-01-26 | 广州市嵩达新材料科技有限公司 | Photocuring hydrophilic polyurea nano particle and preparation method and application thereof |
| CN109843963B (en) * | 2016-10-14 | 2022-05-13 | 旭化成株式会社 | Isocyanate composition, method for producing isocyanate polymer, and isocyanate polymer |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040171785A1 (en) * | 2003-02-26 | 2004-09-02 | Christoph Gurtler | Polyurethane coating systems |
| CN1712423A (en) * | 2004-06-25 | 2005-12-28 | 拜尔材料科学有限责任公司 | Polyurethane dispersions with high acid content |
| EP1609808A2 (en) * | 2004-06-25 | 2005-12-28 | Bayer MaterialScience LLC | Polyurethane dispersion prepared from a high acid functional polyester |
| CN1840559A (en) * | 2005-03-31 | 2006-10-04 | 拜尔材料科学有限公司 | Low surface energy polyisocyanates and their use in one- or two-component coating compositions |
| CN101243115A (en) * | 2005-08-05 | 2008-08-13 | 拜尔材料科学有限公司 | Low surface energy polyisocyanates and their use in one- or two-component coating compositions |
-
2010
- 2010-12-07 CN CN2010105770673A patent/CN102050938B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040171785A1 (en) * | 2003-02-26 | 2004-09-02 | Christoph Gurtler | Polyurethane coating systems |
| CN1712423A (en) * | 2004-06-25 | 2005-12-28 | 拜尔材料科学有限责任公司 | Polyurethane dispersions with high acid content |
| EP1609808A2 (en) * | 2004-06-25 | 2005-12-28 | Bayer MaterialScience LLC | Polyurethane dispersion prepared from a high acid functional polyester |
| CN1840559A (en) * | 2005-03-31 | 2006-10-04 | 拜尔材料科学有限公司 | Low surface energy polyisocyanates and their use in one- or two-component coating compositions |
| CN101243115A (en) * | 2005-08-05 | 2008-08-13 | 拜尔材料科学有限公司 | Low surface energy polyisocyanates and their use in one- or two-component coating compositions |
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391470A (en) * | 2011-09-07 | 2012-03-28 | 南昌航空大学 | Preparation method for ionic liquid terminated polyurethane acrylate |
| CN102391470B (en) * | 2011-09-07 | 2013-04-24 | 南昌航空大学 | Preparation method for ionic liquid terminated polyurethane acrylate |
| CN102604035A (en) * | 2012-03-13 | 2012-07-25 | 广东深展实业有限公司 | Ultraviolet cured two-degree-of-functionality polyurethane acrylic ester base coating resin for vacuum coating |
| CN102604035B (en) * | 2012-03-13 | 2014-04-02 | 广东深展实业有限公司 | Ultraviolet cured two-degree-of-functionality polyurethane acrylic ester base coating resin for vacuum coating |
| CN102659995A (en) * | 2012-04-24 | 2012-09-12 | 南昌航空大学 | Preparation method of ultraviolet-curable water-borne fluorinated paint with low surface energy |
| CN103387654A (en) * | 2012-05-08 | 2013-11-13 | 营口巨成教学科技开发有限公司 | Novel compound photo-curing material, and production method and application field thereof |
| CN103387654B (en) * | 2012-05-08 | 2015-11-18 | 营口巨成教学科技开发有限公司 | A kind of compound photocuring novel material and production method thereof and Application Areas |
| CN105218783A (en) * | 2014-06-17 | 2016-01-06 | 江南大学 | The preparation method of the water-borne UV-curing star-shaped prepolymers of a kind of high reactivity |
| CN104530789A (en) * | 2015-01-19 | 2015-04-22 | 广东希贵光固化材料有限公司 | Cationic photocureable coating for transfer printing film |
| CN107667131A (en) * | 2015-04-03 | 2018-02-06 | 铁锈子弹有限责任公司 | VOC free is painted |
| CN105199077B (en) * | 2015-10-23 | 2017-12-08 | 青岛展辰新材料有限公司 | A kind of high-ranking official it is wear-resisting can cold light source cured polyurethane acrylate preparation method |
| CN105199077A (en) * | 2015-10-23 | 2015-12-30 | 青岛展辰新材料有限公司 | Preparation method of high-functionality wear-resistant cold light source cured polyurethane acrylate |
| CN109843963B (en) * | 2016-10-14 | 2022-05-13 | 旭化成株式会社 | Isocyanate composition, method for producing isocyanate polymer, and isocyanate polymer |
| CN110869404A (en) * | 2017-07-10 | 2020-03-06 | 喜利得股份公司 | Method for producing urethane resin composition containing TEMPOL with improved storage stability |
| US11124598B2 (en) | 2017-07-10 | 2021-09-21 | Hilti Aktiengesellschaft | Method for producing a TEMPOL-containing urethane resin composition having an improved storage stability |
| CN110869404B (en) * | 2017-07-10 | 2022-03-04 | 喜利得股份公司 | Method for producing urethane resin composition containing TEMPOL with improved storage stability |
| CN110054755A (en) * | 2019-04-24 | 2019-07-26 | 广东东田转印新材料有限公司 | It is a kind of can the UV resin of surface drying, preparation method and applications |
| CN110054755B (en) * | 2019-04-24 | 2021-04-20 | 广东东田转印新材料有限公司 | UV resin capable of being surface-dried, preparation method and application thereof |
| CN110903459A (en) * | 2019-11-25 | 2020-03-24 | 重庆沥智路桥工程有限公司 | Hydroxyl-terminated polyurethane methacrylic resin, preparation method and application thereof |
| CN110903459B (en) * | 2019-11-25 | 2022-06-07 | 重庆沥智路桥工程有限公司 | Hydroxyl-terminated polyurethane methacrylic resin, preparation method and application thereof |
| CN112266457A (en) * | 2020-11-06 | 2021-01-26 | 广州市嵩达新材料科技有限公司 | Photocuring hydrophilic polyurea nano particle and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102050938B (en) | 2012-08-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102050938B (en) | Method for preparing ultraviolet photocuring polyurethane resin based on polybasic isocyanate and polybasic hydroxy polyacrylate | |
| CN106397719B (en) | Hyperbranched UV cured polyurethane acrylate of castor oil-base and its preparation method and application | |
| CN107254251B (en) | A kind of aqueous UV urethane acrylate dispersoid and preparation method thereof with self-initiating function | |
| CA1297489C (en) | Process for producing low molecular weight, hydroxy functional (meth)acrylate polymers, their use for producing isocyanate terminal group-containing prepolymers as well as sealants and adhesives produced therefrom | |
| CN105419624B (en) | UV-curable water-borne plastic coating and preparation method thereof | |
| CN104558503B (en) | A kind of preparation method of diaphragm polyurethane adhesive | |
| CN101274977B (en) | Curing agent 1,6- hexamethylene diisocyanate prepolymer and preparation thereof | |
| CN106905504B (en) | Water-based ultraviolet-curing polyurethane resin and preparation method and application thereof | |
| CN103833956A (en) | High molecular weight urethane acrylate resin and preparation method thereof | |
| CN105801829B (en) | 2 degree of functionality polycaprolactone polyurethane acrylate of one kind and its preparation method and application | |
| CN104119543B (en) | A kind of preparation method of nonionic ultraviolet light solidfication water polyurethane acrylate | |
| CN105440260A (en) | Ultraviolet curing urethane acrylate and preparation method thereof | |
| CN105505197B (en) | Ultraviolet-curing paint and preparation method thereof | |
| CN111410732B (en) | Water-based UV resin and preparation method thereof | |
| Narute et al. | Study of the performance of polyurethane coatings derived from cottonseed oil polyol | |
| CN105418853A (en) | Hydroxyl type water-borne cationic polyurethane-acrylic acid resin and preparation method thereof | |
| CN108912296A (en) | A kind of crosslinked aqueous polyurethane and preparation method thereof | |
| CN104292419B (en) | A kind of preparation method of High-performance green environmental protection coatings for furniture two component polyurethane modified unsaturated polyester | |
| CN111205810A (en) | Photo-thermal dual-curing adhesive and preparation method thereof | |
| CN107353865A (en) | A kind of modified polyurethane acrylic resin and preparation method thereof | |
| CN114230766A (en) | Preparation method of stain-resistant polyurethane modified epoxy acrylate | |
| CN102712733A (en) | Solvent borne two-component polyurethane coating composition | |
| CN115710342A (en) | Citric acid-based UV (ultraviolet) curing polyurethane acrylate as well as preparation method and application thereof | |
| CN108341922B (en) | Preparation method and application of low-Tg polyurethane acrylate prepolymer | |
| CN105294970A (en) | Bio-based thermoplastic polyurethane elastomer material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120808 Termination date: 20121207 |