CN101173032A - Large-molecular weight polyurethane acrylic ester and synthesizing method thereof - Google Patents
Large-molecular weight polyurethane acrylic ester and synthesizing method thereof Download PDFInfo
- Publication number
- CN101173032A CN101173032A CNA2007100308309A CN200710030830A CN101173032A CN 101173032 A CN101173032 A CN 101173032A CN A2007100308309 A CNA2007100308309 A CN A2007100308309A CN 200710030830 A CN200710030830 A CN 200710030830A CN 101173032 A CN101173032 A CN 101173032A
- Authority
- CN
- China
- Prior art keywords
- molecular weight
- glycol
- polyester
- urethane acrylate
- acid
- 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.)
- Pending
Links
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses macromolecule weight urethane acrylate, which is formed by reaction on the basis of aliphatic polyester diatomic alcohol with the molecular weight of 500 to 8000, aliphatic diisocyanate and hydroxy acrylic acid monomer; wherein, polyesterglycol comprises ring-shaped resin, and the mechanical property and hydrolysis resistance property of light curing film are improved. The molecular weight of synthetic resin is 10000 to 50000 units, and acrylic ester double keys on the two ends of molecule chain enable the resin to produce high-efficiency free radical aggregation linkage under the effect of photoinitiators through the radiation of ultraviolet light. The aggregation linkage product of the finished film has good flexility and adhesive force, extremely low light curing contraction percentage, higher tensile strength and breaking elongation with hydrolysis resistance property improved. The invention can be used as the main ingredient or assistant matieral of light curing paint, light curing printing ink and light curing adhesive.
Description
Technical field
The present invention relates to a class large-molecular weight polyurethane acrylic ester and a synthetic method thereof, specifically, be the urethane acrylate of a class based on certain molecular weight aliphatic polyester binary alcohol, it is under the light trigger coexistence, through ultraviolet light irradiation, radical polymerization can take place rapidly, thus crosslinking curing.This resin is mainly used in the modulation of photo-cured coating, light-curable ink, curable adhesive, is suitable for the photocuring application of plastic cement, metal, can be cured film extremely low cure shrinkage, excellent adhesive attraction and snappiness are provided, than the high hydrolysis resistance energy.Be that a class has bright market prospects and the superior light-cured resin of over-all properties.
Background technology
Urethane acrylate be a class based on the basic structure of urethane, but, be generally the thickness liquid state by the resin of acrylate functional, be one of coating material solidified main resin of modulation high-performance optical, can give light solidifying coating certain snappiness usually.General urethane acrylate is based on polyoxyethylene glycol, polypropylene glycol or their copolymerization glycol, the molecular resin amount is also less, mostly is hundreds of greatly to several kilounits, and cure shrinkage is big, and because of more polyether structure, solidified coating is not high to some difficult base material sticking power that adhere to.And because polyurethane structural unit molecular weight own is lower, the elastic polyurethane of photocuring film forming thing and high flexibility feature often are not easy to obtain.Along with photo-cured coating applying in the vacuum plating field, require the coating matrix resin to have higher snappiness, low-shrinkage, the height of base materials such as plastic cement is adhered to and certain repairs characteristic from levelling, be that photo-cured coating is during as vacuum plating priming paint, can obtain higherly, guarantee the planarization and the high-quality imitative metal effect of vacuum plating from levelling minute surface result.Urethane acrylate material based on the polyethers trunk is not good enough owing to thermotolerance, common high vacuum, the hot environment that also is difficult to hold out against vacuum plating, and defectives such as pin hole, pit appear in light solidifying coating surface easily.
Summary of the invention
Technical problem to be solved by this invention provide a kind ofly have lower cure shrinkage deformation, higher sticking power, snappiness is repaired large-molecular weight polyurethane acrylic ester of characteristic and preparation method thereof from levelling with the surface preferably.
The present invention solves the problems of the technologies described above the technical scheme that is adopted:
Large-molecular weight polyurethane acrylic ester of the present invention is the oligopolymer that is got by aliphatic polyester binary alcohol, aliphatic diisocyanate and hydroxy acrylate monomer reaction, and molecular weight is 10000 to 50000; Its structure is as shown in the formula expression:
Wherein, R
1Be following any one group:
R
2For being selected from-CH
2CH
2OCO (CH
2)
5-,-CH
2CH
2[OCO (CH
2)
5]
2-, CH
2CH (CH
3)-,-CH
2CH
2CH
2CH
2-,-CH
2CH
2-in any one group;
R
3Be H or CH
3
Polyester is represented the part of polyester diol except that two terminal hydroxy group;
Number of repeat unit n is more than or equal to 1.
Described aliphatic polyester binary alcohol is by diacid and glycol polycondensation and get, and it is end group with the hydroxyl; Diacid monomer unit wherein is the diacid of selecting oneself, 1,2-cyclohexane cyclohexanedimethanodibasic (being hexahydrophthalic acid), 4-tetrahydrobenzene-1, at least a in 2-dioctyl phthalate (being tetrahydrophthalic acid), the 1,4 cyclohexanedicarboxylic acid; Diol monomer wherein is for being selected from ethylene glycol, 1,4-butyleneglycol, neopentyl glycol, 1,6-hexylene glycol, 1,4-cyclohexanedimethanol, 2-methyl isophthalic acid, 1-cyclohexanedimethanol, 3-methyl-2, at least a in 2-norcamphane dimethanol, the tristane dimethanol (CAS No.26896-48-0).Except that single diacid and single glycol polycondensation, aforementioned a kind of diacid also can with aforementioned two or more diol monomer copolycondensation, form copolyesters glycol prepolymer; Also can be aforementioned a kind of diol monomer and aforementioned two or more diacid monomer copolycondensation, form the copolyesters glycol.The copolyesters glycol also belongs to the row of polyester glycol.Diacid and diol monomer are with the better selection that is of ring texture, comprise, 1,4-cyclohexanedimethanol, 2-methyl isophthalic acid, 1-cyclohexanedimethanol, 3-methyl-2,2-norcamphane dimethanol, tristane dimethanol, 1,2-cyclohexane cyclohexanedimethanodibasic, 4-tetrahydrobenzene-1,2-dioctyl phthalate, 1,4 cyclohexanedicarboxylic acid.The monomer of tool ring texture helps improving the tensile strength and the elongation of synthetic resins photocuring film, reduces cure shrinkage, improves ester bond structure resistance to hydrolysis energy in the photocuring film.This explanation comprises being used in combination of ring-type diacid or diol monomer and above-mentioned straight chain type diacid or glycol.
Described polyester glycol also comprises the polycaprolactone glycol with cyclic diols guiding caprolactone monomer ring-opening polymerization gained, be specially 1, the caprolactone monomer ring-opening polymerization product that 4-cyclohexanediol, tristane dimethanol cause, be the aliphatics ring texture in this polyester glycol molecular chain, the molecular chain two ends are hydroxyl.
Described polyester diol molecular weight is advisable with 500～8000, is preferably 800～5000.
Particularly, polyester diol can be selected from as shown in following table, but is not limited only to following combination.
| Chinese | English abbreviation |
| The polyethylene glycol adipate poly adipate succinic acid ester | PEGA PBGA |
| Polyneopentyl glycol adipate gathers hexanodioic acid-1,6-hexylene glycol ester gathers hexanodioic acid-1, the poly-hexanodioic acid of the poly-hexanodioic acid tristane diformazan alcohol ester of 4-cyclohexanedimethanol ester-2-methyl isophthalic acid, the 1-cyclohexanedimethanoester ester gathers hexanodioic acid-3-methyl-2, the poly-hexanodioic acid butyleneglycol of the poly-adipate glycol/butanediol ester of the 2-norcamphane diformazan alcohol ester/poly-hexanodioic acid butyleneglycol of hexylene glycol ester/1,4-cyclohexanedimethanol ester gathers hexanodioic acid hexylene glycol/1,4-cyclohexanedimethanol ester gathers the poly-hexanodioic acid hexylene glycol of the hexanodioic acid butyleneglycol/tristane diformazan alcohol ester/poly-hexanodioic acid butyleneglycol of tristane diformazan alcohol ester/2-methyl isophthalic acid, the 1-cyclohexanedimethanoester ester gathers hexanodioic acid hexylene glycol/2-methyl isophthalic acid, the 1-cyclohexanedimethanoester ester gathers hexanodioic acid butyleneglycol/3-methyl-2,2-norcamphane diformazan alcohol ester gathers hexanodioic acid hexylene glycol/3-methyl-2, the poly-hexahydrophthalic acid of the poly-hexahydrophthalic acid/tetramethylene adipate of the poly-hexahydrophthalic acid hexylene glycol ester of the poly-hexahydrophthalic acid butanediol ester of 2-norcamphane diformazan alcohol ester/hexanodioic acid hexylene glycol ester poly-1,4-cyclohexane cyclohexanedimethanodibasic/tetramethylene adipate poly-1, the poly-tetrahydrophthalic acid of the poly-tetrahydrophthalic acid/tetramethylene adipate of 4-cyclohexane cyclohexanedimethanodibasic/hexanodioic acid hexylene glycol ester/hexanodioic acid hexylene glycol ester 1,4-cyclohexanedimethanol open loop polycaprolactone tristane dimethanol open loop polycaprolactone | PNGA PHGA PCHGA PTCGA PMCHGA PMNBGA PE/BGA PB/HGA PB/CHGA PH/CHGA PB/TCGA PH/TCGA PB/MCHGA PH/MCHGA PB/MNBGA PH/MNBGA PB6HP PH6HP PB6HP/A PH6HP/A PBpCHD/A PHpCHD/A PB4HP/A PH4HP/A CHG-PCL TCG-PCL |
The above vulcabond, hydroxy acrylate are commercial gained, and the polyester binary alcohol moiety is commercial, and all the other are according to general chemical process self-control.The diisocyanate monomer that is adopted is defined as aliphatic category, comprises isophorone diisocyanate (IPDI), dicyclohexyl methane diisocyanate (HMDI), hexamethylene diisocyanate (HDI) etc.Be preferable selection with isophorone diisocyanate wherein, can obtain the large-molecular weight polyurethane acrylic ester that good stability, viscosity are relatively low, be difficult for gel, anti-xanthochromia of photocuring film and ageing resistance are better.Adopting hexamethylene diisocyanate also is that the included material of the present invention is selected, but causes relatively easily that gained synthetic resins is coalescent to be frozen into white soft solid, still have melt, melting characteristic.
Hydroxy acrylate is meant the single acrylate monomer of hydroxy functionality, actual more dihydroxyl, the trihydroxy-component of containing of monomers such as commercially available trimethylolpropane diacrylate, in resin building-up process of the present invention, cause viscosity to increase sharply easily, even gelation.From comprising with the reactivity of NCO group, photopolymerization activity, suppressing the consideration of aspects such as gelation tendency, hydroxyethyl methylacrylate (HEMA), acrylate hydroxyl ethyl ester (HEA), omega-hydroxycaproic acid-ethyl propenoate (HHEA) are comprehensive preferable must the selection.In addition, Hydroxyethyl acrylate, Propylene glycol monoacrylate (HPA), Rocryl 410 (HPMA), vinylformic acid hydroxy butyl ester (HBA), omega-hydroxyl hexanoyl oxy hexanoic acid-ethyl propenoate (HDHEA) etc. are also in range of choice.
According to the polyester construction difference, the polyester diol that is adopted may need heating and melting for solid-state.Also can adopt two kinds of polyester glycol mixed meltings, solidify when preventing to lower the temperature.Polyester glycol is bigger to institute's synthetic urethane acrylate performance impact, adopt polyester glycol among the present invention with ring texture, the crystallization tendency that can suppress polyester itself and product resin, the raw-material resist coagulation tendency of reinforced polyester glycol makes the low temperature of product resin prevent that solidifying storge quality improves simultaneously.The tensile strength and the elongation of resin photocuring film all are improved, and the resistance to hydrolysis of solidified coating can also be enhanced.
The building-up process of indication resin of the present invention can be expressed with following chemical equation:
Building-up reactions according to ultimate principle be the hydroxyl understood thoroughly in the polymer chemistry and the reaction of isocyanate groups, generate the ammonia ester bond structure, because of polyester and isocyanic ester are the difunctionality material, but polymerization reaction take place, forming substantially be linear polyurethane prepolymer, and excessive owing to isocyanic ester, this prepolymer molecular chain-end is the NCO group substantially, wait until and the hydroxy acrylate reaction, introduce end of the chain acrylate group, be used for the photopolymerization of fast free base.
Building-up reactions specifically describes, and according to polyester diol hydroxyl value, molecular weight, polyester diol, vulcabond, hydroxy acrylate monomer is mixed with process sequence by a certain percentage, under water-removal agent, stopper, catalyzer condition condensation reaction takes place.Its general synthetic method is, the monochloro phosphoric acid ester is joined in the load weighted molten polyester dibasic alcohol in the ratio of total weight percent 0.1%～0.5% in total weight percent 0.2%～1% ratio, dibutyl tin dilaurate, and the calculating mole proportioning of vulcabond and polyester diol is 2: 1 to 1.2: 1; When the polyester diol material progressively joined in the vulcabond of stirring, reacted 3～10 hours heating systems to 50～90 ℃, and after polyester diol added, it was basicly stable to follow the tracks of in the detection architecture NCO group content, the NCO end-blocking get base polyurethane prepolymer for use as; The ratio of p methoxy phenol in total weight percent 0.2%～1.5% joined in the hydroxy acrylate monomer, the hydroxy acrylate monomer of metering mixes with gained NCO terminated prepolymer, be warming up to 80～120 ℃ of stirring reactions, follow the tracks of NCO group in the detection architecture, can not detect until infrared spectra and to contain near the charateristic avsorption band of NCO group 2270cm-1 in the system, promptly obtain the urethane acrylate of macromolecule.Described monochloro phosphoric acid ester, dibutyl tin dilaurate and p methoxy phenol also can substitute with other water-removal agents commonly used, catalyzer and stopper respectively.
The hydroxyl value of polyester diol needs to measure in advance according to ordinary method.Institute's synthetic resin detects evaluation according to relevant national standard or industry universal method.According to the GB/T2794-1995 standard, adopt NDJ-7 rotary viscosity design determining viscosity.The molecular resin amount adopts gel chromatography.Resin adds 3%Irgacure 184 (Ciba company product), and as light trigger, mixed dissolution is even, fills with in shape of a hoof sample cell, and thickness 2mm is with 600mJ/cm
2Ultraviolet light intensity irradiation 0.5 * 4 minute, obtain the photocuring batten, according to the GB/T1040-1992 standard, on comprehensive mechanics trier, measure the photocuring film dynamic performance.On the ABS plastic rubber substrate, apply 25 micron membranes thick coatings, at 600mJ/cm
2Ultraviolet light intensity irradiation 30 seconds, according to ASTM D3359 standard, measure solidified coating sticking power by hundred lattice methods.
Compared with prior art, the invention has the advantages that:
Polyester diol with appropriate configuration replaces polyether Glycols, improve the molecular resin amount simultaneously, enlarge the weight of urethane main body in resin integral body, can obtain lower cure shrinkage deformation, higher sticking power, snappiness is repaired characteristic with the surface from levelling preferably, the existence of polyester structural units also makes the mechanical property of solidified coating be improved, and over-all properties such as wear-resisting, tensile strength also can be improved.The particularly introducing of cyclic molecular structure unit in the polyester glycol also will further improve tensile strength and elongation, reduce cure shrinkage, and can strengthen the resistance to hydrolysis energy behind the urethane acrylate photocuring.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail.
Embodiment one:
222.3 gram IPDI is added in the 1000ml four-hole reaction flask, (molecular weight is 1000 units to the PEGA that heating under vacuum is dewatered, Unipol-210, union carbide corporation) 750.0 grams are added in the feed hopper, add 0.3 gram dibutyl tin dilaurate as catalyzer, add 0.06 gram monochloro phosphoric acid ester, mix, further remove remaining moisture content with polyester glycol.Stir isocyanic ester, stream adds polyester glycol, and the heating that heats up at a slow speed, is treated that polyester glycol stream adds to finish, in 80 ℃ of stirring reactions 3 hours by controlled temperature 50-60 ℃.Stream adds 58.0 gram HEA monomers (adding 0.2 gram p methoxy phenol as stopper), is warming up to 80-90 ℃, stirring reaction 5 hours.Infrared spectra detection reaction system NCO radical reaction is complete.Viscosity 19700cps/60 ℃, number-average molecular weight 18400.
Embodiment two:
According to the description of embodiment one, but change PEGA into PBGA (molecular weight is 1000 units, Unipol-410, union carbide corporation), consumption 750 grams.Resin viscosity 21100cps/60 ℃, molecular weight 19100.
Embodiment three:
According to the description of embodiment one, but change PEGA into PHGA (molecular weight is 1000 units, Fomrez 66-112, the excellent anti-land of Uniroyal company), consumption 750 grams.Resin viscosity 23600cps/60 ℃, molecular weight 20300.
Embodiment four:
According to the description of embodiment one, but change PEGA into PB/CHGA (molecular weight is 1000 units, and butyleneglycol and 1,4 cyclohexane dimethanol mol ratio are 3: 1), consumption 750 grams.Resin viscosity 25800cps/60 ℃, molecular weight 23600.
Embodiment five:
According to the description of embodiment one, but change PEGA into PH/CHGA (molecular weight is 1000 units, and hexylene glycol and 1,4 cyclohexane dimethanol mol ratio are 3: 1), consumption 750 grams.Resin viscosity 26000cps/60 ℃, molecular weight 25700.
Embodiment six:
According to the description of embodiment one, but change PEGA into PB/TCGA (molecular weight is 1000 units, and butyleneglycol and tristane dimethanol mol ratio are 3: 1), consumption 750 grams.Resin viscosity 35000cps/60 ℃, molecular weight 20900.
Embodiment seven
According to the description of embodiment one, but change PEGA into PB6HP/A (molecular weight is 1000 units, and hexanodioic acid and hexahydrophthalic acid mol ratio are 3: 1), consumption 750 grams.Resin viscosity 38700 cps/60 ℃, molecular weight 24300.
Embodiment eight
According to the description of embodiment one, but change PEGA into PBpCHD/A (molecular weight is 1000 units, and hexanodioic acid and 1,4 cyclohexanedicarboxylic acid mol ratio are 3: 1), consumption 750 grams.Resin viscosity 36200cps/60 ℃, molecular weight 26700.
Embodiment nine
According to the description of embodiment one, but change PEGA into CHG-PCL (molecular weight is 1000 units), consumption 750 grams.Resin viscosity 30800cps/60 ℃, molecular weight 23800.
Performance test:
Above-mentioned synthetic embodiment gained urethane acrylate behind photocuring under the specified requirements, is carried out mechanical mechanics property, water resistance test, result such as table one.
The performance test results behind table one, the urethane acrylate photocuring
| The embodiment resin | Tensile strength (MPa) | Elongation at break (%) | 24 hours postadhesion power of photocuring | Water purification boils and boils 8 hours postadhesion power |
| Embodiment one embodiment two embodiment three embodiment four | 15.1 14.6 13.2 17.5 | 14 22 27 31 | 4B 5B 5B 5B | 0B 1B 2B 4B |
| Embodiment five embodiment six embodiment seven embodiment eight embodiment nine | 15.7 18.4 17.8 17.0 17.9 | 34 36 34 34 33 | 5B 5B 5B 5B 5B | 4B 5B 4B 4B 3B |
Above-mentioned example shows that in order to introduce ring-type diacid or glycol monomer units in the polyester glycol of synthetic macromolecule weight polyurethane acrylic ester, resin photocuring film mechanical mechanics property and resistance to hydrolysis can be improved significantly.
Claims (10)
1. a class large-molecular weight polyurethane acrylic ester is the oligopolymer that is got by aliphatic polyester binary alcohol, aliphatic diisocyanate and hydroxy acrylate monomer reaction; Its structure is as shown in the formula expression:
Wherein, R
1Be following any one group:
R
2For being selected from-CH
2CH
2OCO (CH
2)
5-,-CH
2CH
2[OCO (CH
2)
5]
2-, CH
2CH (CH
3)-,-CH
2CH
2CH
2CH
2-,-CH
2CH
2-in any one group;
R
3Be H or CH
3
Polyester is represented the part of polyester diol except that two terminal hydroxy group;
Number of repeat unit n is more than or equal to 1.
2. urethane acrylate according to claim 1 is characterized in that described aliphatic polyester binary alcohol is by diacid and glycol polycondensation and get, and it is end group with the hydroxyl; Diacid monomer unit wherein is the diacid of selecting oneself, 1,2-cyclohexane cyclohexanedimethanodibasic (being hexahydrophthalic acid), 4-tetrahydrobenzene-1, at least a in 2-dioctyl phthalate (being tetrahydrophthalic acid), the 1,4 cyclohexanedicarboxylic acid; Diol monomer wherein is for being selected from ethylene glycol, 1,4-butyleneglycol, neopentyl glycol, 1,6-hexylene glycol, 1,4-cyclohexanedimethanol, 2-methyl isophthalic acid, 1-cyclohexanedimethanol, 3-methyl-2, at least a in 2-norcamphane dimethanol, the tristane dimethanol (CAS No.26896-48-0).
3. urethane acrylate according to claim 1, it is characterized in that described polyester glycol also comprises the polycaprolactone glycol with cyclic diols guiding caprolactone monomer ring-opening polymerization gained, be the aliphatics ring texture in this polycaprolactone glycol molecular chain, the molecular chain two ends are hydroxyl.
4. urethane acrylate according to claim 3 is characterized in that described cyclic diols is specially 1,4-cyclohexanediol, tristane dimethanol.
5. according to the described urethane acrylate of arbitrary claim in the claim 1～4, the molecular weight that it is characterized in that described oligopolymer is 10000 to 50000.
6. according to the described urethane acrylate of arbitrary claim in the claim 2～4, it is characterized in that described polyester diol molecular weight is 500～8000.
7. urethane acrylate according to claim 6 is characterized in that described polyester diol molecular weight is 800～5000.
8. according to the described urethane acrylate of arbitrary claim in the claim 1～4, it is characterized in that described aliphatic diisocyanate monomer comprises isophorone diisocyanate (IPDI), dicyclohexyl methane diisocyanate (HMDI), hexamethylene diisocyanate (HDI) etc.
9. according to the described urethane acrylate of arbitrary claim in the claim 1～4, it is characterized in that described hydroxy acrylate monomer comprises Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate, vinylformic acid hydroxy butyl ester, omega-hydroxycaproic acid-ethyl propenoate (affixture of Hydroxyethyl acrylate-caprolactone) etc.
10. method for preparing described large-molecular weight polyurethane acrylic ester is characterized in that:
The monochloro phosphoric acid ester is joined in the load weighted molten polyester dibasic alcohol in the ratio of total weight percent 0.1%～0.5% in total weight percent 0.2%～1% ratio, dibutyl tin dilaurate, and the calculating mole proportioning of vulcabond and polyester diol is 2: 1 to 1.2: 1; When the polyester diol material progressively joined in the vulcabond of stirring, reacted 3～10 hours heating systems to 50～90 ℃, and after polyester diol added, it was basicly stable to follow the tracks of in the detection architecture NCO group content, the NCO end-blocking get base polyurethane prepolymer for use as; The ratio of p methoxy phenol in total weight percent 0.2%～1.5% joined in the hydroxy acrylate monomer, the hydroxy acrylate monomer of metering mixes with gained NCO terminated prepolymer, be warming up to 80～120 ℃ of stirring reactions, tracking detects that the conversion of NCO group finishes to the system, promptly obtains the urethane acrylate of macromolecule.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100308309A CN101173032A (en) | 2007-10-15 | 2007-10-15 | Large-molecular weight polyurethane acrylic ester and synthesizing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100308309A CN101173032A (en) | 2007-10-15 | 2007-10-15 | Large-molecular weight polyurethane acrylic ester and synthesizing method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101173032A true CN101173032A (en) | 2008-05-07 |
Family
ID=39421798
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007100308309A Pending CN101173032A (en) | 2007-10-15 | 2007-10-15 | Large-molecular weight polyurethane acrylic ester and synthesizing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101173032A (en) |
Cited By (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101824152A (en) * | 2010-04-13 | 2010-09-08 | 深圳职业技术学院 | Preparation method and application of resin having double curing groups |
| CN101899236A (en) * | 2009-06-01 | 2010-12-01 | 钟文军 | High-temperature digestion resistant ink and preparation method thereof |
| CN101519480B (en) * | 2009-01-22 | 2011-11-30 | 广东天银化工实业有限公司 | Method for preparing self-cross linking type water-based acrylic resin and polyurethane hybrid |
| JP2011241314A (en) * | 2010-05-19 | 2011-12-01 | Toyobo Co Ltd | Aliphatic polyester polyurethane |
| 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 |
| CN102633984A (en) * | 2012-04-06 | 2012-08-15 | 长兴（广州）电子材料有限公司 | Polyurethane-acrylate oligomer, and synthesis method and application thereof |
| CN101475681B (en) * | 2008-11-25 | 2012-10-10 | 无锡博强高分子材料科技有限公司 | Synthesis of high stretching high tenacity polyurethane acrylic ester |
| CN101768419B (en) * | 2008-12-31 | 2013-06-12 | 上海康达化工新材料股份有限公司 | Non-solvent polyurethane laminating adhesive with high initial stick force and preparation method and application thereof |
| CN103497669A (en) * | 2013-09-23 | 2014-01-08 | 迪爱生合成树脂（中山）有限公司 | Activated energy ray curing waterborne resin composition |
| CN103497667A (en) * | 2013-09-12 | 2014-01-08 | 天津冯德亦康新材料科技有限公司 | Laser coating for laser card and preparation method thereof |
| CN104558499A (en) * | 2013-10-23 | 2015-04-29 | 湖南岁丰新材料科技发展有限公司 | UV-curable elastic polyurethane acrylate emulsion and synthesis method thereof |
| CN104629022A (en) * | 2014-12-31 | 2015-05-20 | 海聚高分子材料科技（广州）有限公司 | Hydrolysis resistant polyester polyol, hydrolysis resistant and weather resistant aqueous polyurethane dispersion and use thereof |
| CN106189802A (en) * | 2016-07-13 | 2016-12-07 | 旭川化学（苏州）有限公司 | A kind of UV solidification solvent-free height saturating non-yellow stain polyurethane minute surface resin and preparation method thereof |
| CN106810670A (en) * | 2017-01-06 | 2017-06-09 | 浙江新迪在龙涂料科技有限公司 | A kind of preparation method of urethane acrylate oligomer |
| CN108026245A (en) * | 2015-09-18 | 2018-05-11 | 日本化药株式会社 | Urethanes and the resin combination containing it |
| CN108727550A (en) * | 2018-04-23 | 2018-11-02 | 浙江锐胜新材料有限公司 | A kind of photosensitive resin and its application |
| CN109135646A (en) * | 2018-07-05 | 2019-01-04 | 吕莉 | A kind of preparation method of ultraviolet cured adhesive |
| CN110092885A (en) * | 2019-05-27 | 2019-08-06 | 江苏睿浦树脂科技有限公司 | A kind of UV curable urethane acrylate resin and preparation method thereof |
| CN112220969A (en) * | 2020-12-18 | 2021-01-15 | 北京大学第三医院（北京大学第三临床医学院） | Photocuring 3D printing preparation method of degradable meniscus support |
| CN112796000A (en) * | 2021-01-20 | 2021-05-14 | 东华大学 | High-gel-content high-crystallinity aliphatic polyester and preparation method thereof |
| CN112812265A (en) * | 2020-12-31 | 2021-05-18 | 安庆飞凯新材料有限公司 | Polyurethane acrylate oligomer, preparation method thereof, coating composition and application thereof |
| CN112831021A (en) * | 2020-12-31 | 2021-05-25 | 安庆飞凯新材料有限公司 | Polyurethane acrylate oligomer, preparation method thereof, coating composition and application thereof |
| CN113045805A (en) * | 2021-03-16 | 2021-06-29 | 无锡市中惠橡胶科技有限公司 | High-strength tear-resistant rubber track and preparation method thereof |
| CN114057950A (en) * | 2020-07-30 | 2022-02-18 | 湖北远大生命科学与技术有限责任公司 | Spherical polyurethane graft modified polyacrylate macroporous anion resin, preparation method thereof and application thereof in taurine production |
| CN114316203A (en) * | 2021-12-21 | 2022-04-12 | 郑州轻工业大学 | Polyurethane acrylate photocuring resin material, preparation method thereof and preparation method of polyurethane acrylate prepolymer |
| CN115593029A (en) * | 2021-07-08 | 2023-01-13 | 上海海优威新材料股份有限公司（Cn） | High-interface bonding force multi-layer structure leather |
| CN117683201A (en) * | 2023-12-12 | 2024-03-12 | 南昌航空大学 | Photo-curing degradable zwitterionic polyurethane acrylate resin and preparation method thereof |
-
2007
- 2007-10-15 CN CNA2007100308309A patent/CN101173032A/en active Pending
Cited By (36)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101475681B (en) * | 2008-11-25 | 2012-10-10 | 无锡博强高分子材料科技有限公司 | Synthesis of high stretching high tenacity polyurethane acrylic ester |
| CN101768419B (en) * | 2008-12-31 | 2013-06-12 | 上海康达化工新材料股份有限公司 | Non-solvent polyurethane laminating adhesive with high initial stick force and preparation method and application thereof |
| CN101519480B (en) * | 2009-01-22 | 2011-11-30 | 广东天银化工实业有限公司 | Method for preparing self-cross linking type water-based acrylic resin and polyurethane hybrid |
| CN101899236A (en) * | 2009-06-01 | 2010-12-01 | 钟文军 | High-temperature digestion resistant ink and preparation method thereof |
| CN101824152B (en) * | 2010-04-13 | 2012-05-23 | 深圳职业技术学院 | Preparation method and application of resin having double curing groups |
| CN101824152A (en) * | 2010-04-13 | 2010-09-08 | 深圳职业技术学院 | Preparation method and application of resin having double curing groups |
| JP2011241314A (en) * | 2010-05-19 | 2011-12-01 | Toyobo Co Ltd | Aliphatic polyester polyurethane |
| 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 |
| CN102633984B (en) * | 2012-04-06 | 2013-12-25 | 长兴（广州）电子材料有限公司 | Polyurethane-acrylate oligomer, and synthesis method and application thereof |
| CN102633984A (en) * | 2012-04-06 | 2012-08-15 | 长兴（广州）电子材料有限公司 | Polyurethane-acrylate oligomer, and synthesis method and application thereof |
| CN103497667A (en) * | 2013-09-12 | 2014-01-08 | 天津冯德亦康新材料科技有限公司 | Laser coating for laser card and preparation method thereof |
| CN103497667B (en) * | 2013-09-12 | 2016-01-27 | 天津冯德亦康新材料科技有限公司 | A kind of laser coating for radium-shine card and preparation method thereof |
| CN103497669A (en) * | 2013-09-23 | 2014-01-08 | 迪爱生合成树脂（中山）有限公司 | Activated energy ray curing waterborne resin composition |
| CN103497669B (en) * | 2013-09-23 | 2015-02-25 | 迪爱生合成树脂（中山）有限公司 | Activated energy ray curing waterborne resin composition |
| CN104558499A (en) * | 2013-10-23 | 2015-04-29 | 湖南岁丰新材料科技发展有限公司 | UV-curable elastic polyurethane acrylate emulsion and synthesis method thereof |
| CN104629022A (en) * | 2014-12-31 | 2015-05-20 | 海聚高分子材料科技（广州）有限公司 | Hydrolysis resistant polyester polyol, hydrolysis resistant and weather resistant aqueous polyurethane dispersion and use thereof |
| CN108026245A (en) * | 2015-09-18 | 2018-05-11 | 日本化药株式会社 | Urethanes and the resin combination containing it |
| CN106189802B (en) * | 2016-07-13 | 2018-12-25 | 旭川化学（苏州）有限公司 | A kind of solvent-free high non-yellow stain polyurethane mirror surface resin and preparation method thereof thoroughly of UV solidification |
| CN106189802A (en) * | 2016-07-13 | 2016-12-07 | 旭川化学（苏州）有限公司 | A kind of UV solidification solvent-free height saturating non-yellow stain polyurethane minute surface resin and preparation method thereof |
| CN106810670A (en) * | 2017-01-06 | 2017-06-09 | 浙江新迪在龙涂料科技有限公司 | A kind of preparation method of urethane acrylate oligomer |
| CN108727550A (en) * | 2018-04-23 | 2018-11-02 | 浙江锐胜新材料有限公司 | A kind of photosensitive resin and its application |
| CN109135646A (en) * | 2018-07-05 | 2019-01-04 | 吕莉 | A kind of preparation method of ultraviolet cured adhesive |
| CN110092885A (en) * | 2019-05-27 | 2019-08-06 | 江苏睿浦树脂科技有限公司 | A kind of UV curable urethane acrylate resin and preparation method thereof |
| CN114057950B (en) * | 2020-07-30 | 2024-03-22 | 湖北远大生命科学与技术有限责任公司 | Spherical polyurethane grafted modified polyacrylate macroporous anion resin, preparation method thereof and application thereof in taurine production |
| CN114057950A (en) * | 2020-07-30 | 2022-02-18 | 湖北远大生命科学与技术有限责任公司 | Spherical polyurethane graft modified polyacrylate macroporous anion resin, preparation method thereof and application thereof in taurine production |
| CN112220969A (en) * | 2020-12-18 | 2021-01-15 | 北京大学第三医院（北京大学第三临床医学院） | Photocuring 3D printing preparation method of degradable meniscus support |
| CN112831021A (en) * | 2020-12-31 | 2021-05-25 | 安庆飞凯新材料有限公司 | Polyurethane acrylate oligomer, preparation method thereof, coating composition and application thereof |
| CN112812265A (en) * | 2020-12-31 | 2021-05-18 | 安庆飞凯新材料有限公司 | Polyurethane acrylate oligomer, preparation method thereof, coating composition and application thereof |
| CN112831021B (en) * | 2020-12-31 | 2023-03-10 | 安庆飞凯新材料有限公司 | Polyurethane acrylate oligomer, preparation method thereof, coating composition and application thereof |
| CN112796000A (en) * | 2021-01-20 | 2021-05-14 | 东华大学 | High-gel-content high-crystallinity aliphatic polyester and preparation method thereof |
| CN113045805A (en) * | 2021-03-16 | 2021-06-29 | 无锡市中惠橡胶科技有限公司 | High-strength tear-resistant rubber track and preparation method thereof |
| CN115593029A (en) * | 2021-07-08 | 2023-01-13 | 上海海优威新材料股份有限公司（Cn） | High-interface bonding force multi-layer structure leather |
| CN115593029B (en) * | 2021-07-08 | 2023-11-24 | 上海海优威新材料股份有限公司 | Leather with high interface adhesion and multilayer structure |
| CN114316203A (en) * | 2021-12-21 | 2022-04-12 | 郑州轻工业大学 | Polyurethane acrylate photocuring resin material, preparation method thereof and preparation method of polyurethane acrylate prepolymer |
| CN117683201A (en) * | 2023-12-12 | 2024-03-12 | 南昌航空大学 | Photo-curing degradable zwitterionic polyurethane acrylate resin and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101173032A (en) | Large-molecular weight polyurethane acrylic ester and synthesizing method thereof | |
| CN103703038B (en) | Aqueous polyurethane resin dispersion and application thereof | |
| JP2002537454A5 (en) | ||
| TW202112890A (en) | Polyether polycarbonate diol and method for producing same | |
| JPH05262808A (en) | Production of polymer containing hydroxyl at each terminal, composition containing the same polymer, use of the same composition, polymer derived from the same composition and use of the same polymer | |
| CN103080164A (en) | Aqueous polyurethane resin dispersion, manufacturing method therefor, and use therefor | |
| CN105482060A (en) | Hyperbranched waterborne polyurethane acrylate emulsion as well as preparation method and application thereof | |
| JPWO2009060838A1 (en) | Polyurethane for printing ink binder, its production method and printing ink | |
| CN109293866B (en) | Humic acid modified waterborne polyurethane material and preparation method thereof | |
| UA110782C2 (en) | Two-component water-based polyurethane compositions and coatings | |
| TW201307416A (en) | Thermoplastic polyurethane with reduced tendency to bloom from a bio-based glycol | |
| CN107903372A (en) | A kind of UV photocurings flexibility ultra-branched polyurethane acrylate resin and preparation method and application | |
| CN114075322A (en) | Waterborne polyurethane resin emulsion and preparation method thereof | |
| CN113980230A (en) | Moisture-resistant thermoplastic polyurethane elastomer material and preparation method thereof | |
| CN114085353B (en) | Photo-thermal dual-curing resin and preparation method thereof | |
| WO2015174187A1 (en) | Polyurethane resin | |
| WO2014004596A1 (en) | Water-based coating compositions | |
| JPS6044561A (en) | Rapidly-drying coating composition | |
| JP6801125B2 (en) | Paint composition | |
| CN115304996B (en) | Water-based environment-friendly high-performance UV surface treating agent | |
| JPH101524A (en) | Acryl-urethane copolymer, production thereof, and coating composition containing the same | |
| JPWO2002057332A1 (en) | RESIN COMPOSITION, SHEET USING SAME, SHEET MANUFACTURING METHOD, AND MOLDED BODY | |
| WO2014004598A2 (en) | Process for multi-layer coating | |
| EP3856813B1 (en) | Use of polyvinylacetate polymers or copolymers to increase the viscosity of the isocyanate component of a two-component curable polymeric system | |
| JP2006104315A (en) | Aqueous acrylic-modified urethane resin and method for producing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20080507 |