CN102190789A - Preparation method of polyurethane acrylate resin - Google Patents
Preparation method of polyurethane acrylate resin Download PDFInfo
- Publication number
- CN102190789A CN102190789A CN 201110070131 CN201110070131A CN102190789A CN 102190789 A CN102190789 A CN 102190789A CN 201110070131 CN201110070131 CN 201110070131 CN 201110070131 A CN201110070131 A CN 201110070131A CN 102190789 A CN102190789 A CN 102190789A
- Authority
- CN
- China
- Prior art keywords
- acrylate resin
- polyurethane acrylate
- preparation
- reaction
- mixture
- 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
- 239000004814 polyurethane Substances 0.000 title claims abstract description 29
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 29
- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 59
- 238000000034 method Methods 0.000 claims abstract description 16
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 6
- 229920005862 polyol Polymers 0.000 claims abstract description 6
- 150000003077 polyols Chemical class 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 18
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 16
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 12
- -1 polysiloxane Polymers 0.000 claims description 8
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 claims description 7
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 7
- 229920001610 polycaprolactone Polymers 0.000 claims description 7
- 239000004632 polycaprolactone Substances 0.000 claims description 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 5
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical group O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 4
- ZMARGGQEAJXRFP-UHFFFAOYSA-N 1-hydroxypropan-2-yl 2-methylprop-2-enoate Chemical compound OCC(C)OC(=O)C(C)=C ZMARGGQEAJXRFP-UHFFFAOYSA-N 0.000 claims description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 4
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 4
- 238000001514 detection method Methods 0.000 claims description 4
- 238000004817 gas chromatography Methods 0.000 claims description 4
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 claims description 4
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical group CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 claims description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 4
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 3
- ZBBLRPRYYSJUCZ-GRHBHMESSA-L (z)-but-2-enedioate;dibutyltin(2+) Chemical compound [O-]C(=O)\C=C/C([O-])=O.CCCC[Sn+2]CCCC ZBBLRPRYYSJUCZ-GRHBHMESSA-L 0.000 claims description 2
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003550 marker Substances 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920005906 polyester polyol Polymers 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 2
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims 1
- 239000012258 stirred mixture Substances 0.000 claims 1
- 238000004448 titration Methods 0.000 claims 1
- 238000009826 distribution Methods 0.000 abstract description 14
- 239000000178 monomer Substances 0.000 abstract description 11
- 239000011347 resin Substances 0.000 abstract description 9
- 229920005989 resin Polymers 0.000 abstract description 9
- 238000006116 polymerization reaction Methods 0.000 abstract description 5
- 238000000576 coating method Methods 0.000 abstract description 4
- 238000010526 radical polymerization reaction Methods 0.000 abstract description 4
- 238000007639 printing Methods 0.000 abstract description 2
- 239000003112 inhibitor Substances 0.000 abstract 2
- 239000000543 intermediate Substances 0.000 abstract 2
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 11
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 8
- 238000010907 mechanical stirring Methods 0.000 description 8
- 238000005070 sampling Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 230000001737 promoting effect Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- 238000000016 photochemical curing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical group CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 238000003483 aging Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000004260 weight control Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention relates to a preparation method of polyurethane acrylate resin with a narrow molecular weight distribution. The method includes the following steps that: with the existence of a catalyst (catalysts) and a polymerization inhibitor (polymerization inhibitors), firstly a diisocyanate monomer reacts with a hydroxy acrylate monomer to produce intermediates at a low temperature; then the intermediates react with a polyol to produce a polyurethane acrylate resin. With the coexistence of a photoinitiator and through ultraviolet (UV) irradiation, the polyurethane acrylate resin is rapidly subjected to a free radical polymerization so as to carry out a crossing and curving reaction. Thereby, the polyurethane acrylate resin possesses good rheological property. The polyurethane acrylate resin, produced through the method of the invention, is mainly used for ultraviolet curing coatings, printing ink and adhesives and has excellent mechanical properties and flexibility, excellent performances of resisting chemicals and high/low temperature and good levelling property. The polyurethane acrylate resin is a UV-curable resin with a good market prospect and superior comprehensive properties.
Description
Technical field
The present invention relates to the synthetic method of molecule amount narrow distribution, polyurethane acrylate resin that viscosity is low.
Background technology
Ultraviolet-curing paint has obtained the high speed development in recent years and has been applied to each industrial circle very soon because of its rapid moulding, environmental protection and good performance thereof.Its main component generally comprises light trigger, reactive thinner, oligopolymer and various auxiliary agent.Wherein oligopolymer (claiming prepolymer, oligopolymer etc. again) is one of component of consumption maximum, also is the basic resin of photo-cured coating prescription, has constituted the basic boom of photocuring product.Be the fundamental property of solidifying product, comprise that hardness, snappiness, sticking power, optical property, chemical resistance etc. are mainly determined by oligopolymer.Therefore, numerous at the synthetic aspect research of ultraviolet-curing resin.At present, the light-cured resin of radical polymerization mechanism commonly used is except epoxy acrylate on the market, using maximum is exactly urethane acrylate (polyurethane acrylate is called for short PUA), in field extensive application such as photo-cured coating, printing ink, tackiness agent.
Urethane acrylate be a class based on the basic structure of urethane, but, be generally thick liquid by the resin of acrylate functional.Its synthesis technique simple and flexible, raw material type is numerous, can pass through molecular designing, selects different raw materials to synthesize, thereby product property is regulated.Therefore, can design control in advance with regard to many-sided indexs such as snappiness, hardness, chemically-resistant agings, the resin structure design flexibility is quite strong.
Urethane acrylate synthetic mainly by polyvalent alcohol and crylic acid hydroxy ester-OH and vulcabond-NCO reaction realization.The synthetic route that most of patent and academic documents adopt is as follows:
In this route vulcabond at first with diol reaction, after reacting completely, add hydroxyalkyl acrylate.This method makes hydroxyalkyl acrylate reduce exposure in thermal environment, and when adding hydroxyalkyl acrylate, half reaction heat of entire reaction discharges, thereby has reduced the possibility of radical polymerization.But in the first step reaction, the functionality of two raw materials is 2, easily produces polycondensation, causes the quantitative change of final product molecule big, and viscosity rises.The molecular weight distribution broad influences its use properties simultaneously, and particularly flow leveling is relatively poor.
Summary of the invention
In order to overcome the polyurethane acrylate resin molecular weight distribution broad that conventional path of preparing obtains, viscosity is bigger, the relatively poor shortcoming of flow leveling when prescription is used, the technical problem that the present invention will tie solution provides a kind of preparation method of new polyurethane acrylate resin, it is lower to be intended to make viscosity, the polyurethane acrylate resin that flow leveling has clear improvement.
In order to solve the problems of the technologies described above, the preparation method of polyurethane acrylate resin provided by the invention is in the presence of catalyzer, stopper, at first obtain intermediate by aliphatic diisocyanate and hydroxy acrylate monomer reaction, and then the oligopolymer that gets with polyol reaction.
Its molecular structure is:
Wherein, R is the part except that two isocyanate group in the vulcabond
R1 is-CH2CH2-,-CH2CH2CH2CH2-,-CH2CH (CH3)-,-CH2CH2[OCO (CH2) 5] any one group among the 2-
R2 is the part except that two terminal hydroxy group in the polyvalent alcohol
Described aliphatic diisocyanate monomer comprises isophorone diisocyanate (IPDI), dicyclohexyl methane diisocyanate (HMDI), hexamethylene diisocyanate (HDI), tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI) etc.Be preferable selection with isophorone diisocyanate (IPDI) wherein, it has package stability preferably, yellowing resistance.Simultaneously, the two-NCO activity difference that is positioned at different positions among the IPDI is bigger, is beneficial to obtain narrow molecular weight distribution, viscosity is lower, flow leveling is better urethane acrylate.
Described polyvalent alcohol comprises polyester polyol, polyether glycol, polyurethane polyol, polymeric amide polyvalent alcohol, polycarbonate polyol, polysiloxane polyhydric alcohol, or two or more mixtures similar or the inhomogeneity polyvalent alcohol.By taking all factors into consideration, think that polypropylene glycol (PPG), PCDL (PCD) and polycaprolactone dibasic alcohol (PCL) are preferable selection, molecular weight control is about 500～5000.
Described hydroxy acrylate comprises Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate, Rocryl 410, vinylformic acid hydroxy butyl ester etc.From comprising with reactivity, the photopolymerization activity of-NCO group, suppressing aspect such as gelation proneness and consider that Rocryl 410 (HPMA), Propylene glycol monoacrylate (HPA), Hydroxyethyl acrylate (HEA) be comprehensively preferable selection.In addition, hydroxyethyl methylacrylate (HEMA), Rocryl 410 (HPMA), vinylformic acid hydroxy butyl ester (HBA) etc. are also in range of choice.
Described catalyzer is selected from one or more the mixture in stannous octoate, dibutyl tin laurate, triethylenediamine, two acetic acid tin methides, dibutyl tin maleate, the zinc octoate.Wherein dibutyl tin laurate is preferable selection, and its catalytic efficiency is higher, and can obviously increase different positions among the IPDI-activity difference of NCO.Catalyst consumption is 0.01～5.0% (mass percent) of vulcabond and hydroxy acrylate total mass, is preferably 0.05～0.1% (mass percent).
Described stopper is selected from one or more the mixture in Resorcinol, p methoxy phenol, adjacent methyl hydroquinone, para benzoquinone, the thiodiphenylamine.In reaction process, the amount of stopper crosses that I haven't seen you for ages causes polymerization inhibition effect not obvious, causes the local polymerization of reactant, and the amount of stopper too much can influence product color.Consider that from factors such as polymerization inhibition effect, product color p methoxy phenol is preferable selection, consumption is 0.005～0.05% (mass percent) of vulcabond and hydroxy acrylate total mass.
The synthetic route of polyurethane acrylate resin of the present invention is as follows:
This synthetic route is that with the difference of common synthetic method order of addition(of ingredients) is opposite, at first allows equimolar hydroxyalkyl acrylate and di-isocyanate reaction, makes the acrylate of band monoisocyanates base, adds dibasic alcohol again.The advantage of this method is, when adding dibasic alcohol, has only monoisocyanates functional group's molecule and its reaction in the system basically, helps obtaining narrow molecular weight distribution, product that viscosity is lower.Simultaneously can avoid residual small molecules volatile substances.
Certainly, in the first step reaction of this route, also exist side reaction, promptly two hydroxyalkyl acrylate molecules and a diisocyanate molecules reaction not with the acrylate of isocyanate group, can't participate in the reaction of second step.Simultaneously, the diisocyanate monomer of remained unreacted contacts with the dibasic alcohol that adds subsequently, easily produces homopolymerization, thereby influences product viscosity and molecular weight distribution.So, in the first step reaction process, to control reaction conditions, be positioned at the two-NCO activity difference of different positions to increase in the vulcabond, thereby make a diisocyanate molecules only with a hydroxyalkyl acrylate molecular reaction.Simultaneously, there is effective analysis means to determine to have neither part nor lot in the reaction diisocyanate monomer.
Building-up reactions specifically describes, at first the ratio of catalyzer in total mass per-cent 0.05～0.1% joined in the load weighted vulcabond, the ratio of stopper in total mass per-cent 0.005～0.05% joined in the load weighted hydroxy acrylate, and the calculating mole proportioning of vulcabond and hydroxy acrylate is 1: 1 to 1: 10.Hydroxy acrylate is slowly joined in the vulcabond of stirring with constant pressure funnel, controlled temperature reacted 1～24 hour at-10 ℃ to 30 ℃.After hydroxy acrylate adds, follow the tracks of NCO group content in the detection architecture, when reaching 11%～12% (mass percent), finish reaction.
Use the quality percentage composition of unreacted vulcabond in the gas-chromatography marker method assay products simultaneously.Used internal standard substance is selected from p-Xylol, dinoctyl phthalate, dibutyl phthalate etc.Comprehensive each factor considers that p-Xylol is best.
Used gas chromatograph adopts good fortune upright 9790, and the temperature programming condition is, since 40 ℃ of intensification, per minute rises 20 ℃, and promotion to 260 ℃ begins to lower the temperature after top temperature stops two minutes.P-Xylol goes out the peak about 4 minutes, IPDI feature occurs about 11 minutes bimodal.
Be that 1: 1 mixed stirs with the first step reaction product and polyvalent alcohol by-NCO and-OH mol ratio then, controlled temperature reacted 2～12 hours at 30 ℃ to 80 ℃.Follow the tracks of NCO group content in the detection architecture in the reaction process, when its content＜0.1% (mass percent), reaction is reached home, polyurethane acrylate resin.
Institute's synthetic resin detects evaluation according to relevant national standard or industry universal method.With Brookfield RV ∏+type viscometer determining viscosity, measure its molecular weight with Waters GPCV2000.It is even that resin adds the light trigger mixed dissolution, on spraying and the ABS plate.In the process of spray, observe the speed of levelling speed, use ultra-violet curing instrument film-forming then.Under natural daylight, appearance of film is observed, seen its surfacing slickness with eyes.Compare with standard jig simultaneously.Embodiment subsequently will prove that the polyurethane acrylate resin viscosity that makes by the inventive method is lower, and flow leveling has clear improvement.In addition, because molecular chain two ends acrylic double bond makes this resin under the initiator effect, through ultraviolet light irradiation, it is crosslinked that high efficiency radical polymerization can take place, thereby the polyurethane acrylate resin that makes by the inventive method can be used as the main component and the subsidiary material of photo-cured coating, light-curable ink and the agent of photocuring gluing.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.These embodiment are interpreted as only being used to the present invention is described and are not used in restriction protection scope of the present invention.After the content of having read the present invention's record, those skilled in the art can make various changes or modifications the present invention, and these equivalences change and modify and fall into claim of the present invention institute restricted portion equally.
Embodiment one
0.28g dibutyl tin laurate adds in the 44.48g isophorone diisocyanate, joins 500ml then together and is equipped with in the four-hole reaction flask of mechanical stirring, prolong, thermometer and constant pressure funnel, begins to stir.The 0.28g Resorcinol is joined among the 200gPCL (polycaprolactone dibasic alcohol, molecular weight is about 1000), treat solid dissolving after, drip in isocyanic ester by constant pressure funnel, the control rate of addition dropwises in 1 to 1.5h.Begin to heat up, the control oil bath temperature stirs 1h at 80 ℃, and sampling titration-NCO content arrives the reaction requirement, stopped reaction.
In addition accurately take by weighing sample 0.05g, add the 0.005g p-Xylol again, add toluene and dissolve laggard promoting the circulation of qi analysis of hplc, obtain having neither part nor lot in the mass percent of the different fluorine diketone diisocyanate monomer of reaction.
Then, 122.2g the first step reaction product and 13g Propylene glycol monoacrylate are joined in the four-hole reaction flask that mechanical stirring, prolong and thermometer are housed, begin to stir.Oil bath is stabilized to 80 ℃, stirs 5 hours, and sampling titration-NCO content arrives the reaction requirement, and stopped reaction promptly obtains urethane acrylate.With its viscosity of viscometer determining.
Embodiment two
0.28g dibutyl tin laurate adds in the 111.2g isophorone diisocyanate, joins 500ml then together and is equipped with in the four-hole reaction flask of mechanical stirring, prolong, thermometer and constant pressure funnel, begins to stir.The 0.28g Resorcinol is joined in the 65g Propylene glycol monoacrylate, treat solid dissolving after, drip in isocyanic ester by constant pressure funnel, the control rate of addition dropwises in 1 to 1.5h.Begin to heat up, the control oil bath temperature stirs 1h at 80 ℃, and sampling titration-NCO content arrives the reaction requirement, stopped reaction.
In addition accurately take by weighing sample 0.05g, add the 0.005g p-Xylol again, add toluene and dissolve laggard promoting the circulation of qi analysis of hplc, obtain having neither part nor lot in the mass percent of the different fluorine diketone diisocyanate monomer of reaction.
Then, 22.19g the first step reaction product and 252.12gPCL (polycaprolactone dibasic alcohol, molecular weight is about 1000) are joined in the four-hole reaction flask that mechanical stirring, prolong and thermometer are housed, begin to stir.Oil bath is stabilized to 80 ℃, stirs 5 hours, and sampling titration-NCO content arrives the reaction requirement, and stopped reaction promptly obtains urethane acrylate.With its viscosity of viscometer determining.
Embodiment three
0.28g dibutyl tin laurate adds in the 111.2g isophorone diisocyanate, joins 500ml then together and is equipped with in the four-hole reaction flask of mechanical stirring, prolong, thermometer and constant pressure funnel, begins to stir.The 0.28g Resorcinol is joined in the 65g Propylene glycol monoacrylate, treat solid dissolving after, drip in isocyanic ester by constant pressure funnel, the control rate of addition dropwises in 1 to 1.5h.Begin to heat up, the control oil bath temperature stirs 1h at 40 ℃, and sampling titration-NCO content arrives the reaction requirement, stopped reaction.
In addition accurately take by weighing sample 0.05g, add the 0.005g p-Xylol again, add toluene and dissolve laggard promoting the circulation of qi analysis of hplc, obtain having neither part nor lot in the mass percent of the different fluorine diketone diisocyanate monomer of reaction.
Then, 22.19g the first step reaction product and 252.12gPCL (polycaprolactone dibasic alcohol, molecular weight is about 1000) are joined in the four-hole reaction flask that mechanical stirring, prolong and thermometer are housed, begin to stir.Oil bath is stabilized to 80 ℃, stirs 5 hours, and sampling titration-NCO content arrives the reaction requirement, and stopped reaction promptly obtains urethane acrylate.With its viscosity of viscometer determining.
Embodiment four
0.28g dibutyl tin laurate adds in the 111.2g isophorone diisocyanate, joining 500ml then together is equipped with in the four-hole reaction flask of mechanical stirring, prolong, thermometer and constant pressure funnel, four-hole boiling flask places ice-water bath, begins to stir.The 0.28g Resorcinol is joined in the 65g Propylene glycol monoacrylate, treat solid dissolving after, drip in isocyanic ester by constant pressure funnel, the control rate of addition dropwises in 1 to 1.5h.Continuation is stirred 10h under ice bath, sampling titration-NCO content arrives the reaction requirement, stopped reaction.
In addition accurately take by weighing sample 0.05g, add the 0.005g p-Xylol again, add toluene and dissolve laggard promoting the circulation of qi analysis of hplc, obtain having neither part nor lot in the mass percent of the different fluorine diketone diisocyanate monomer of reaction.
Then, 22.19g the first step reaction product and 252.12gPCL (polycaprolactone dibasic alcohol, molecular weight is about 2000) are joined in the four-hole reaction flask that mechanical stirring, prolong and thermometer are housed, begin to stir.Oil bath is stabilized to 80 ℃, stirs 5 hours, and sampling titration-NCO content arrives the reaction requirement, and stopped reaction promptly obtains urethane acrylate.With its viscosity of viscometer determining.
Data analysis:
Carry out in the process at above-mentioned synthetic embodiment one to four, need mass percent with unreacted isophorone diisocyanate in the gas-chromatography internal mark method determination reaction process.In this method, adopting p-Xylol is internal standard substance matter.At first need to prepare the dimethylbenzene of different mass ratio and the mixture of pure IPDI carries out gas chromatographic analysis, it is as follows to obtain working curve:
Y＝0.4452x?R
2＝0.9965
This shows that the gained curve linear is better.According to this curve, measure the mass percent of unreacted isophorone diisocyanate then.The result is as follows under the different condition:
| The first step reaction product among the embodiment | Unreacted IPDI monomer content (wt%) |
| Embodiment two | 18.36％ |
| Embodiment three | 10.79％ |
| Embodiment four | 4.13％ |
By table as seen, along with the reduction of the first step temperature of reaction, the mass percent of not participating in the isophorone diisocyanate of reaction also descends thereupon.
Above-mentioned synthetic embodiment gained urethane acrylate is measured its molecular weight and molecular weight distribution thereof with GPC, and the result is as shown in the table:
| The embodiment resin | D＝M w/M n |
| Embodiment one | 2.78 |
| Embodiment two | 1.86 |
| Embodiment three | 1.32 |
| Embodiment four | 1.15 |
Wherein: M
nBe number-average molecular weight, M
wBe weight-average molecular weight, D represents the molecular weight distribution width.
Embodiment one is different with the order of addition(of ingredients) of embodiment two, and temperature is identical in the two-step reaction, and the molecular weight distribution diversity ratio of the finished product is bigger.As shown in embodiment one, adding the D value that polyvalent alcohol adds the urethane acrylate that vinylformic acid hydroxyl ester obtains again earlier is 2.78, belongs to wide distribution.And reinforced conversely words to obtain product D value be 1.86, belong to narrow distribution.
Simultaneously, from embodiment two to embodiment three, along with the decline of the first step temperature of reaction, the molecular weight distribution of the finished product is also more and more narrow.This shows that reaction can obtain the narrower polyurethane acrylic resin of molecular weight distribution under the low temperature.
Above-mentioned synthetic embodiment gained urethane acrylate with its viscosity of viscometer determining, behind the photocuring, is carried out the test of flow leveling then under specified requirements.The result is as follows:
As seen from the above table, the product viscosity that obtains of the used synthetic method of the present invention than ordinary method obtain low.Simultaneously, along with the reduction of the first step temperature of reaction, its viscosity can further reduce.And in concrete use, then show as levelling to speed up, solidify the rear surface planeness and obviously improve.
Claims (7)
1. the preparation method of a polyurethane acrylate resin is characterized in that, comprises the steps:
According to the mole proportioning of vulcabond and hydroxy acrylate is that 1: 1 to 1: 10 ratio takes by weighing vulcabond and hydroxy acrylate;
With catalyzer in the ratio of total mass per-cent 0.05～0.1% join in the vulcabond mixture 1, catalyzer is selected from one or more the mixture in stannous octoate, dibutyl tin laurate, triethylenediamine, two acetic acid tin methides, dibutyl tin maleate, the zinc octoate;
With stopper in the ratio of total mass per-cent 0.005～0.05% join in the hydroxy acrylate mixture 2, stopper is selected from one or more the mixture in Resorcinol, p methoxy phenol, adjacent methyl hydroquinone, para benzoquinone, the thiodiphenylamine;
With constant pressure funnel mixture 2 is joined in the stirred mixture 1, reacted 1～24 hour down at-20 ℃～30 ℃, with gas-chromatography internal mark method determination unreacted diisocyanate content, and reach at 11%～12% o'clock with the quality percentage composition that chemical titration is followed the tracks of NCO group in the detection reaction system and finish reaction, obtain intermediate;
Is that 1: 1 mixed stirs with intermediate and polyvalent alcohol by-NCO and-OH mol ratio, reacted 2～12 hours down at 30 ℃-80 ℃, follow the tracks of the quality percentage composition＜0.1% o'clock end of NCO group in the detection reaction system with the gas-chromatography marker method and react, make polyurethane acrylate resin.
2. the preparation method of polyurethane acrylate resin according to claim 1, it is characterized in that described vulcabond is isophorone diisocyanate IPDI, dicyclohexyl methane diisocyanate HMDI, hexamethylene diisocyanate HDI, tolylene diisocyanate TDI or diphenylmethanediisocyanate MDI.
3. the preparation method of polyurethane acrylate resin according to claim 1 is characterized in that, described hydroxyl acrylic is Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate, Rocryl 410 or vinylformic acid hydroxy butyl ester.
4. the preparation method of polyurethane acrylate resin according to claim 1, it is characterized in that, described polyvalent alcohol is polyester polyol, polyether glycol, polyurethane polyol, polymeric amide polyvalent alcohol, polycarbonate polyol, polysiloxane polyhydric alcohol, or the mixture of two or more aforementioned similar or inhomogeneity polyvalent alcohols.
5. according to the preparation method of the polyurethane acrylate resin described in the claim 4, it is characterized in that,, described polyvalent alcohol is polypropylene glycol, PCDL or polycaprolactone dibasic alcohol.
6. according to the preparation method of the polyurethane acrylate resin described in claim 4 or 5, it is characterized in that the molecular weight of described polyvalent alcohol is 500～5000.
7. polyurethane acrylate resin preparation method according to claim 1 is characterized in that, catalyst consumption is 0.05～0.1% of vulcabond and a hydroxy acrylate total mass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110070131 CN102190789B (en) | 2011-03-23 | 2011-03-23 | Preparation method of polyurethane acrylate resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110070131 CN102190789B (en) | 2011-03-23 | 2011-03-23 | Preparation method of polyurethane acrylate resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102190789A true CN102190789A (en) | 2011-09-21 |
| CN102190789B CN102190789B (en) | 2012-07-04 |
Family
ID=44599726
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110070131 Active CN102190789B (en) | 2011-03-23 | 2011-03-23 | Preparation method of polyurethane acrylate resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102190789B (en) |
Cited By (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102516907A (en) * | 2011-12-13 | 2012-06-27 | 烟台德邦电子材料有限公司 | Preparation method of ultraviolet-curable organosilicone-modified pressure-sensitive adhesive |
| 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 |
| CN102766248A (en) * | 2012-07-25 | 2012-11-07 | 广州市博兴化工科技有限公司 | Method for preparing liquid urethane acrylate resin by recovered solid polyurethane |
| CN102924747A (en) * | 2012-10-22 | 2013-02-13 | 澳达树熊涂料(惠州)有限公司 | Method for degrading and recycling waste solid polyurethane |
| WO2013131251A1 (en) * | 2012-03-06 | 2013-09-12 | 江苏苏博特新材料股份有限公司 | Polyether macromonomer containing double-bond carbamate functional group and method for preparing same |
| CN103483905A (en) * | 2013-08-22 | 2014-01-01 | 广东理想彩色印务有限公司 | Ultraviolet (UV) curing ink and preparation method thereof |
| CN103483537A (en) * | 2013-09-26 | 2014-01-01 | 湖南本安亚大新材料有限公司 | UV curing resin, preparation method thereof and coating prepared therefrom |
| CN103833956A (en) * | 2014-03-03 | 2014-06-04 | 黎明化工研究设计院有限责任公司 | High molecular weight urethane acrylate resin and preparation method thereof |
| CN103992438A (en) * | 2014-05-26 | 2014-08-20 | 周杰 | Preparation method of acrylic polymer |
| CN105462449A (en) * | 2015-12-08 | 2016-04-06 | 南通金源智能技术有限公司 | Graphene conductive coating and preparation method thereof |
| CN106188497A (en) * | 2016-08-11 | 2016-12-07 | 安庆飞凯高分子材料有限公司 | A kind of synthetic method of modified epoxy acrylate resin |
| CN106397718A (en) * | 2016-06-23 | 2017-02-15 | 汕头市东田转印有限公司 | UV resin capable of being dried by heating, a preparing process thereof and applications of the resin |
| CN106833357A (en) * | 2017-01-16 | 2017-06-13 | 哈尔滨工业大学无锡新材料研究院 | A kind of ultraviolet light cured burnished paint and preparation method thereof |
| CN108276948A (en) * | 2017-12-21 | 2018-07-13 | 宁波凯耀电器制造有限公司 | A kind of efficient UV solidification glues |
| CN108383974A (en) * | 2018-01-22 | 2018-08-10 | 武汉理工大学 | A kind of ultraviolet light solidification high-strength polyurethane acrylate and preparation method thereof |
| CN108752555A (en) * | 2018-06-25 | 2018-11-06 | 江苏科琪高分子材料研究院有限公司 | It is a kind of to be used to bond polyurethane acrylate resin of PC plastic and preparation method thereof |
| CN109735289A (en) * | 2018-12-26 | 2019-05-10 | 深圳日高胶带新材料有限公司 | A kind of polymer composite gluing agent prescription and its manufacture craft |
| CN110684503A (en) * | 2019-11-20 | 2020-01-14 | 山东益丰生化环保股份有限公司 | Preparation method of UV-cured polyurethane modified acrylate adhesive |
| CN112250831A (en) * | 2020-10-12 | 2021-01-22 | 深圳飞扬兴业科技有限公司 | UV resin and preparation method thereof |
| CN112250854A (en) * | 2020-10-13 | 2021-01-22 | 河南科技大学 | UV ink oligomer resin for heat transfer film and preparation method and application thereof |
| CN112266375A (en) * | 2020-11-09 | 2021-01-26 | 广东石油化工学院 | Xylitol-containing radiation-curable urethane (meth) acrylate compound and preparation method thereof |
| CN112745462A (en) * | 2019-10-29 | 2021-05-04 | 上海飞凯光电材料股份有限公司 | Edge sealing material, preparation method and application thereof |
| CN113248684A (en) * | 2020-02-12 | 2021-08-13 | 李皞丹 | Preparation method of urethane acrylate |
| CN114685748A (en) * | 2022-04-29 | 2022-07-01 | 上海三桐材料科技有限公司 | High-refraction UV (ultraviolet) photocuring polyurethane acrylate resin and preparation method thereof |
| CN115873497A (en) * | 2022-12-08 | 2023-03-31 | 来安县扬子地板有限公司 | Sun-proof anti-tarnishing composite wood floor |
| CN116063647A (en) * | 2023-02-01 | 2023-05-05 | 惠州市惠阳聚晟化工涂料有限公司 | Hardening liquid for mobile phone rear shell and application thereof |
| CN116716035A (en) * | 2023-06-09 | 2023-09-08 | 江苏视科新材料股份有限公司 | Filtering coating material capable of accurately regulating and controlling protection |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007081186A1 (en) * | 2006-01-13 | 2007-07-19 | Sscp Co., Ltd. | Uv-curable aqueous emulsion, preparation thereof and solventless coating compostion comprising the same |
| CN101475679A (en) * | 2009-01-16 | 2009-07-08 | 中山大桥化工集团有限公司 | Aqueous polyurethane acrylate resin, and preparation and use thereof |
| CN101724218A (en) * | 2009-12-08 | 2010-06-09 | 中国铁道科学研究院金属及化学研究所 | Unsaturated resin composition as well as preparation method and a purpose thereof |
| CN101935385A (en) * | 2010-09-10 | 2011-01-05 | 烟台德邦电子材料有限公司 | Method for synthesizing low-hardness polyurethane acrylate |
| CN101974307A (en) * | 2010-08-13 | 2011-02-16 | 上海材料研究所 | Polyurethane acrylate adhesive containing ionic groups and preparation method thereof |
-
2011
- 2011-03-23 CN CN 201110070131 patent/CN102190789B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007081186A1 (en) * | 2006-01-13 | 2007-07-19 | Sscp Co., Ltd. | Uv-curable aqueous emulsion, preparation thereof and solventless coating compostion comprising the same |
| CN101475679A (en) * | 2009-01-16 | 2009-07-08 | 中山大桥化工集团有限公司 | Aqueous polyurethane acrylate resin, and preparation and use thereof |
| CN101724218A (en) * | 2009-12-08 | 2010-06-09 | 中国铁道科学研究院金属及化学研究所 | Unsaturated resin composition as well as preparation method and a purpose thereof |
| CN101974307A (en) * | 2010-08-13 | 2011-02-16 | 上海材料研究所 | Polyurethane acrylate adhesive containing ionic groups and preparation method thereof |
| CN101935385A (en) * | 2010-09-10 | 2011-01-05 | 烟台德邦电子材料有限公司 | Method for synthesizing low-hardness polyurethane acrylate |
Non-Patent Citations (2)
| Title |
|---|
| 《包装学报》 彭威等 紫外光固化聚氨酯丙烯酸酯的研究进展 , 第02期 * |
| 《聚氨酯工业》 20070428 赵建国等 影响光固化聚氨酯丙烯酸酯合成反应进程的因素探讨 , 第02期 * |
Cited By (36)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102516907A (en) * | 2011-12-13 | 2012-06-27 | 烟台德邦电子材料有限公司 | Preparation method of ultraviolet-curable organosilicone-modified pressure-sensitive adhesive |
| WO2013131251A1 (en) * | 2012-03-06 | 2013-09-12 | 江苏苏博特新材料股份有限公司 | Polyether macromonomer containing double-bond carbamate functional group and method for preparing same |
| 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 |
| 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 |
| CN102766248A (en) * | 2012-07-25 | 2012-11-07 | 广州市博兴化工科技有限公司 | Method for preparing liquid urethane acrylate resin by recovered solid polyurethane |
| CN102924747A (en) * | 2012-10-22 | 2013-02-13 | 澳达树熊涂料(惠州)有限公司 | Method for degrading and recycling waste solid polyurethane |
| CN102924747B (en) * | 2012-10-22 | 2015-05-27 | 澳达树熊涂料(惠州)有限公司 | Method for degrading and recycling waste solid polyurethane |
| CN103483905A (en) * | 2013-08-22 | 2014-01-01 | 广东理想彩色印务有限公司 | Ultraviolet (UV) curing ink and preparation method thereof |
| CN103483537A (en) * | 2013-09-26 | 2014-01-01 | 湖南本安亚大新材料有限公司 | UV curing resin, preparation method thereof and coating prepared therefrom |
| CN103483537B (en) * | 2013-09-26 | 2015-09-16 | 湖南本安亚大新材料有限公司 | A kind of UV-cured resin, its preparation method and with the coating prepared by it |
| CN103833956A (en) * | 2014-03-03 | 2014-06-04 | 黎明化工研究设计院有限责任公司 | High molecular weight urethane acrylate resin and preparation method thereof |
| CN103992438A (en) * | 2014-05-26 | 2014-08-20 | 周杰 | Preparation method of acrylic polymer |
| CN105462449A (en) * | 2015-12-08 | 2016-04-06 | 南通金源智能技术有限公司 | Graphene conductive coating and preparation method thereof |
| CN106397718A (en) * | 2016-06-23 | 2017-02-15 | 汕头市东田转印有限公司 | UV resin capable of being dried by heating, a preparing process thereof and applications of the resin |
| CN106188497A (en) * | 2016-08-11 | 2016-12-07 | 安庆飞凯高分子材料有限公司 | A kind of synthetic method of modified epoxy acrylate resin |
| CN106833357A (en) * | 2017-01-16 | 2017-06-13 | 哈尔滨工业大学无锡新材料研究院 | A kind of ultraviolet light cured burnished paint and preparation method thereof |
| CN106833357B (en) * | 2017-01-16 | 2019-06-28 | 哈尔滨工业大学无锡新材料研究院 | A kind of ultraviolet light cured burnished paint and preparation method thereof |
| CN108276948A (en) * | 2017-12-21 | 2018-07-13 | 宁波凯耀电器制造有限公司 | A kind of efficient UV solidification glues |
| CN108276948B (en) * | 2017-12-21 | 2020-11-13 | 宁波凯耀电器制造有限公司 | Efficient UV curing adhesive |
| CN108383974A (en) * | 2018-01-22 | 2018-08-10 | 武汉理工大学 | A kind of ultraviolet light solidification high-strength polyurethane acrylate and preparation method thereof |
| CN108752555A (en) * | 2018-06-25 | 2018-11-06 | 江苏科琪高分子材料研究院有限公司 | It is a kind of to be used to bond polyurethane acrylate resin of PC plastic and preparation method thereof |
| CN109735289A (en) * | 2018-12-26 | 2019-05-10 | 深圳日高胶带新材料有限公司 | A kind of polymer composite gluing agent prescription and its manufacture craft |
| CN112745462B (en) * | 2019-10-29 | 2023-04-21 | 上海飞凯材料科技股份有限公司 | Edge sealing material, preparation method and application thereof |
| CN112745462A (en) * | 2019-10-29 | 2021-05-04 | 上海飞凯光电材料股份有限公司 | Edge sealing material, preparation method and application thereof |
| CN110684503A (en) * | 2019-11-20 | 2020-01-14 | 山东益丰生化环保股份有限公司 | Preparation method of UV-cured polyurethane modified acrylate adhesive |
| CN113248684A (en) * | 2020-02-12 | 2021-08-13 | 李皞丹 | Preparation method of urethane acrylate |
| CN112250831B (en) * | 2020-10-12 | 2022-11-25 | 深圳飞扬骏研新材料股份有限公司 | UV resin and preparation method thereof |
| CN112250831A (en) * | 2020-10-12 | 2021-01-22 | 深圳飞扬兴业科技有限公司 | UV resin and preparation method thereof |
| CN112250854A (en) * | 2020-10-13 | 2021-01-22 | 河南科技大学 | UV ink oligomer resin for heat transfer film and preparation method and application thereof |
| CN112266375A (en) * | 2020-11-09 | 2021-01-26 | 广东石油化工学院 | Xylitol-containing radiation-curable urethane (meth) acrylate compound and preparation method thereof |
| CN114685748A (en) * | 2022-04-29 | 2022-07-01 | 上海三桐材料科技有限公司 | High-refraction UV (ultraviolet) photocuring polyurethane acrylate resin and preparation method thereof |
| CN115873497A (en) * | 2022-12-08 | 2023-03-31 | 来安县扬子地板有限公司 | Sun-proof anti-tarnishing composite wood floor |
| CN116063647A (en) * | 2023-02-01 | 2023-05-05 | 惠州市惠阳聚晟化工涂料有限公司 | Hardening liquid for mobile phone rear shell and application thereof |
| CN116063647B (en) * | 2023-02-01 | 2024-01-05 | 惠州市惠阳聚晟化工涂料有限公司 | Hardening liquid for mobile phone rear shell and application thereof |
| CN116716035A (en) * | 2023-06-09 | 2023-09-08 | 江苏视科新材料股份有限公司 | Filtering coating material capable of accurately regulating and controlling protection |
| CN116716035B (en) * | 2023-06-09 | 2023-12-15 | 江苏视科新材料股份有限公司 | Filtering coating material capable of accurately regulating and controlling protection |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102190789B (en) | 2012-07-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102190789B (en) | Preparation method of polyurethane acrylate resin | |
| TWI257932B (en) | Urethane (meth)acrylate oligomer, process for its production and photocurable composition | |
| EP1914255B1 (en) | Aliphatic polyisocyanate prepolymers and polyurethane resin coating compositions using the same | |
| CN101372530B (en) | Aqueous photo-curing polyurethane resin and preparation thereof | |
| CN101899247B (en) | Woodenware polishing paint and preparation method thereof | |
| US6573398B2 (en) | Secondary aspartic acid amide esters | |
| CN103833956A (en) | High molecular weight urethane acrylate resin and preparation method thereof | |
| CN103703038B (en) | Aqueous polyurethane resin dispersion and application thereof | |
| JP6275144B2 (en) | Binder having a cyclic carbonate structure | |
| CN104086742B (en) | A kind of preparation method of glass baseplate acid and alkali-resistance ultraviolet light solidified glue film resin | |
| CN102585163B (en) | Polyurethane coating compositions comprising isocyanurate compositions from bis(isocyanatomethyl) cyclohexane and tertiary amine catalysts | |
| JP6165419B2 (en) | Aqueous two-component coating composition, ink composition, adhesive composition, and method of using the same | |
| CN112334553B (en) | Polyurethane composition with long processing time and high strength | |
| US20130210998A1 (en) | Two-part polyurethanes based on hyperbranched polymers | |
| KR102672870B1 (en) | Curable composition for use as an adhesive having properties that can be deformed based on external stimulation, and methods of making and using the same | |
| CN105801791B (en) | A kind of castor oil-base UV cured polyurethane acrylates and its preparation method and application | |
| ES2311865T3 (en) | PROCEDURE TO MAKE AMIDA-ACETALES. | |
| CN102712733A (en) | Solvent borne two-component polyurethane coating composition | |
| CN106947053A (en) | A kind of modified urethane acrylate copolymer, photoresist and preparation method thereof | |
| CN104693994A (en) | Ultraviolet photocuring coating containing inorganic pigment and filler and preparation method thereof | |
| EP3666811A1 (en) | A coating composition | |
| EP3877437B1 (en) | A coating composition | |
| US11566145B2 (en) | Polyurethane coating compositions and their use as gel coats | |
| CN104031227A (en) | Aqueous polyurethane preparation method | |
| ES2655695T3 (en) | Mixed polycycloaliphatic amines (MPCA) and MPCA alkylates |
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 | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20110921 Assignee: Shanghai PhiChem Photoelectric Material Co., Ltd. Assignor: Anqing Feikai Polymer Material Co., Ltd. Contract record no.: 2014310000092 Denomination of invention: Preparation method of polyurethane acrylate resin Granted publication date: 20120704 License type: Exclusive License Record date: 20140509 |
|
| LICC | Enforcement, change and cancellation of record of contracts on the licence for exploitation of a patent or utility model | ||
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 246005 No. 9, Xiang Zhang Road, Daguan Economic Development Zone, Anqing, Anhui Patentee after: Anqing flying Kaixin Materials Co., Ltd. Address before: 246005 No. 9, Xiang Zhang Road, Daguan Economic Development Zone, Anqing, Anhui Patentee before: Anqing Feikai Polymer Material Co., Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20200309 Address after: Room 711, Building 2, Courtyard 1, Jinhang Middle Road, Shunyi District, Beijing 101300 Patentee after: Beijing culture science and technology finance leasing Limited by Share Ltd Address before: 246005, No. 9, camphor Road, Daguan Economic Development Zone, Anhui, Anqing Patentee before: Anqing flying Kaixin Materials Co., Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210712 Address after: 246000 No. 9, Xiang Zhang Road, Daguan District Economic Development Zone, Anqing, Anhui Patentee after: ANQING FEIKAI NEW MATERIAL Co.,Ltd. Address before: Room 711, Building 2, Courtyard 1, Jinhang Middle Road, Shunyi District, Beijing 101300 Patentee before: Beijing culture science and technology finance leasing Limited by Share Ltd. |