CN105820063B - A kind of 4 degree of functionality urethane acrylates based on anhydrous citric acid and its preparation method and application - Google Patents
A kind of 4 degree of functionality urethane acrylates based on anhydrous citric acid and its preparation method and application Download PDFInfo
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- CN105820063B CN105820063B CN201610236643.5A CN201610236643A CN105820063B CN 105820063 B CN105820063 B CN 105820063B CN 201610236643 A CN201610236643 A CN 201610236643A CN 105820063 B CN105820063 B CN 105820063B
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- citric acid
- polyether ester
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- acrylate
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 title claims abstract description 65
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical class OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229960004543 anhydrous citric acid Drugs 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims description 15
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 44
- 150000002148 esters Chemical class 0.000 claims abstract description 44
- 229920000570 polyether Polymers 0.000 claims abstract description 44
- JBAQRVIOIFHTCA-UHFFFAOYSA-N 1,1,2,3,3-pentahydroxypropane-1,2,3-tricarboxylic acid Chemical compound OC(C(C(C(=O)O)(O)O)(O)C(=O)O)(C(=O)O)O JBAQRVIOIFHTCA-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000003054 catalyst Substances 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000000576 coating method Methods 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000000853 adhesive Substances 0.000 claims abstract description 7
- 230000001070 adhesive effect Effects 0.000 claims abstract description 7
- 239000000976 ink Substances 0.000 claims abstract description 6
- 239000004814 polyurethane Substances 0.000 claims description 36
- 229920002635 polyurethane Polymers 0.000 claims description 36
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 32
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 28
- VPASWAQPISSKJP-UHFFFAOYSA-N ethyl prop-2-enoate;isocyanic acid Chemical compound N=C=O.CCOC(=O)C=C VPASWAQPISSKJP-UHFFFAOYSA-N 0.000 claims description 26
- 238000006116 polymerization reaction Methods 0.000 claims description 17
- 239000003112 inhibitor Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 11
- 239000004927 clay Substances 0.000 claims description 9
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 7
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 7
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical group COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 7
- 239000004280 Sodium formate Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical compound [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 claims description 6
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 6
- 235000019254 sodium formate Nutrition 0.000 claims description 6
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 5
- 235000010235 potassium benzoate Nutrition 0.000 claims description 5
- 239000004300 potassium benzoate Substances 0.000 claims description 5
- 229940103091 potassium benzoate Drugs 0.000 claims description 5
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 claims description 5
- 235000010234 sodium benzoate Nutrition 0.000 claims description 5
- 239000004299 sodium benzoate Substances 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 22
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 4
- 238000005507 spraying Methods 0.000 abstract description 4
- -1 isocyanates ethyl acrylate Chemical class 0.000 abstract description 3
- 238000007086 side reaction Methods 0.000 abstract description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 abstract 2
- 239000012948 isocyanate Substances 0.000 abstract 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 abstract 2
- 239000001294 propane Substances 0.000 abstract 1
- 238000007711 solidification Methods 0.000 abstract 1
- 230000008023 solidification Effects 0.000 abstract 1
- 239000011347 resin Substances 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- 238000001723 curing Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 239000003973 paint Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 125000001931 aliphatic group Chemical group 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000003848 UV Light-Curing Methods 0.000 description 4
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000000016 photochemical curing Methods 0.000 description 4
- 229920001610 polycaprolactone Polymers 0.000 description 4
- 239000004632 polycaprolactone Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 229960004106 citric acid Drugs 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 2
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- WVXMNBDPVYOPLX-UHFFFAOYSA-N 2-isocyanoethyl prop-2-enoate Chemical compound C=CC(=O)OCC[N+]#[C-] WVXMNBDPVYOPLX-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- ZMJBYMUCKBYSCP-UHFFFAOYSA-N Hydroxycitric acid Chemical compound OC(=O)C(O)C(O)(C(O)=O)CC(O)=O ZMJBYMUCKBYSCP-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009172 bursting Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- ZDHCZVWCTKTBRY-UHFFFAOYSA-N omega-Hydroxydodecanoic acid Natural products OCCCCCCCCCCCC(O)=O ZDHCZVWCTKTBRY-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C269/02—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups from isocyanates with formation of carbamate groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
- C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a kind of degree of functionality urethane acrylate of low viscosity 4, it is prepared via a method which to obtain：First reacted by anhydrous citric acid under catalyst action with oxirane or expoxy propane and tetrahydroxy citric acid polyether ester is made, tetrahydroxy citric acid polyether ester reacts with isocyanates ethyl acrylate again is made 4 degree of functionality urethane acrylates.The present invention is prepared using isocyanates ethyl acrylate during urethane acrylate, course of reaction is simple, easily controllable, is not easy to produce gel because of side reaction, urethane acrylate product viscosity is low, satisfaction is applied to low-viscosity dope, is not added with for UV sprayings or lacks solubilizer；After the degree of functionality UV curable urethane acrylates of low viscosity 4 solidification, there is the premium properties such as high hardness, wear-resisting, scratch resistance, heat-resisting, weatherability, can be in the raw material application as UV coating, ink, adhesive.
Description
Technical Field
The invention belongs to the field of materials, relates to a 4-functionality polyurethane acrylate based on anhydrous citric acid, and a preparation method and application thereof, and particularly relates to a low-viscosity 4-functionality polyurethane acrylate based on anhydrous citric acid, and a preparation method and application thereof.
Background
With the rapid development of science and technology and the strict limitation of environmental regulations on solvents, UV light-cured polymer materials are receiving more and more attention from people. The UV light curing material has the excellent performances of fast curing, low energy consumption, less pollution, high efficiency and the like, so the UV light curing material is widely applied to the fields of coatings, printing, electronic industry and the like, and is rapidly developed in recent years. Polyurethane acrylate (PUA) is an important photocuring oligomer, has excellent performances such as low irritation, high curing speed, high transparency, tensile resistance, high cohesive energy and the like, is widely used in the fields of photocuring ink, coating, adhesive and the like, and is widely applied in developed countries of the united states, japan and europe. In recent years, with the rise of ultraviolet curing technology in China, the novel light curing material has wider and wider application as a raw material of UV coating, printing ink and adhesive, and the usage amount is increased year by year.
The applicant discloses in chinese patent ZL201310143167.9 (grant No. CN 103242508B) a 4-functionality urethane acrylate prepared by the following method: the 4-functionality polyurethane acrylate is prepared by reacting tetrahydroxy citric acid polyether ester prepared by reacting anhydrous citric acid with ethylene oxide or propylene oxide under the action of a catalyst, and reacting the tetrahydroxy citric acid polyether ester with diisocyanate (one selected from HDI, IPDI, HMDI and MDI) and hydroxyethyl acrylate or hydroxypropyl acrylate. Because diisocyanate and hydroxyethyl acrylate or hydroxypropyl acrylate are adopted to prepare the 4-functionality polyurethane acrylate, the reaction process has more steps and is relatively complicated, the production process is not easy to control, and the risk of generating gel due to the existence of side reaction.
The light-cured resin is the matrix resin of the light-cured coating, and has various varieties and wide application. With the increasing attention on environmental issues worldwide, photocurable resins will certainly develop rapidly with the development of photocurable coatings. Development of photocurable resins with better environmental protection, low viscosity, and better overall performance is the direction of the technicians in the future.
Disclosure of Invention
The invention aims to improve 4-functionality polyurethane acrylate provided by Chinese patent ZL201310143167.9 as well as a preparation method and application thereof, and provides low-viscosity 4-functionality polyurethane acrylate based on anhydrous citric acid.
It is a further object of the present invention to provide a process for the preparation of such low-viscosity 4-functional urethane acrylates.
It is a further object of the present invention to provide the use of such low viscosity 4-functional urethane acrylates.
The purpose of the invention can be realized by the following technical scheme:
a low viscosity 4 functional urethane acrylate prepared by the following method: anhydrous citric acid reacts with ethylene oxide or propylene oxide under the action of a catalyst to prepare tetrahydroxy citric acid polyether ester, and then the tetrahydroxy citric acid polyether ester reacts with isocyanate ethyl Acrylate (2-Isocyanoethyl Acrylate, AOI for short, CAS number: 13641-96-8, molecular formula: C)6H7NO3Molecular weight: 141.12) to produce a 4 functionality urethane acrylate.
Wherein,
the first step reaction route is as follows:
when n is 2, -R is-H is ethylene oxide reacted with citric acid; when n is 3, -R is-CH3During the reaction, propylene oxide reacts with citric acid; wherein a + b + c + d is 5-8.
The preparation of the tetrahydroxy citric acid polyether ester comprises the following steps: under the action of a catalyst, dropwise adding ethylene oxide or propylene oxide into anhydrous citric acid in a high-pressure reaction kettle at 155-165 ℃ for reaction, controlling the reaction pressure to be 0.1-0.6 MPa, preserving heat for 1-3 hours at 155-165 ℃ after the ethylene oxide or the propylene oxide is dropwise added, then cooling to be below 80 ℃, adding activated clay, stirring for 0.5-2 hours, and performing circulating filter pressing until the mixture is clear and transparent to obtain tetrahydroxy citric acid polyether ester shown in the formula (I); wherein the dosage ratio of the anhydrous citric acid to the ethylene oxide or the propylene oxide is 1 mol: 5 to 8 mol.
The catalyst is one or a mixture of more than one of sodium formate, potassium formate, sodium benzoate and potassium benzoate in any proportion, and the dosage of the catalyst is 0.5-5 wt%, preferably 0.5-3 wt% of the total mass of the anhydrous citric acid and the ethylene oxide or the propylene oxide.
The dosage of the activated clay is 0.9 to 5 weight percent of the total mass of the anhydrous citric acid and the ethylene oxide or the propylene oxide.
The prepared tetrahydroxy citric acid polyether ester and isocyanate ethyl acrylate are mixed according to the proportion of 1 mol: 3.8-4.1 mol, and reacting at 60-95 ℃ to obtain the 4-functionality polyurethane acrylate.
Preferably, the prepared tetrahydroxy citric acid polyether ester and isocyanate ethyl acrylate are mixed according to the proportion of 1 mol: 3.9-4 mol, stirring and reacting for 3-6 hours at 80-95 ℃ under the action of a catalyst and a polymerization inhibitor to obtain 4-functionality polyurethane acrylate; wherein the polymerization inhibitor can be p-hydroxyanisole or hydroquinone, and the dosage of the polymerization inhibitor is 100-5000 ppm of the total mass of tetrahydroxy citric acid polyether ester and isocyanate ethyl acrylate; the catalyst is dibutyltin dilaurate, and the dosage of the catalyst is 100-3000 ppm of the total mass of the tetrahydroxy citric acid polyether ester and the isocyanate ethyl acrylate.
The second reaction route is as follows:
and (3) reacting the tetrahydroxy citric acid polyether ester with isocyanate ethyl acrylate to obtain 4-functionality polyurethane acrylate:
R1comprises the following steps:
n is 2 or 3, and a + b + c + d is 5-8.
The first step of the invention is a reaction for preparing 4-hydroxy citric acid polyether ester, namely, a ring-opening addition reaction (anionic polymerization) of 3 carboxyl groups and 1 hydroxyl group in citric acid and propylene oxide (ethylene oxide) alkane, which is a known organic chemical reaction, wherein under the reaction conditions of the invention, the propylene oxide (ethylene oxide) alkane is in a gaseous state, the continuous feeding is completed, the reaction is carried out for 1-3 hours at a constant temperature, the pressure in a high-pressure reaction kettle is reduced to be constant, namely, the propylene oxide (ethylene oxide) alkane is completely reacted, and the conversion rate is more than 99.9%; the second reaction is the reaction of isocyanate group in isocyanate ethyl acrylate and hydroxyl group, which belongs to the well-known synthetic polyurethane (polyurethane) reaction.
The preparation method of the 4-functionality polyurethane acrylate comprises the following steps: anhydrous citric acid reacts with ethylene oxide or propylene oxide under the action of a catalyst to prepare tetrahydroxy citric acid polyether ester, and then the tetrahydroxy citric acid polyether ester reacts with isocyanate ethyl acrylate to prepare 4-functionality polyurethane acrylate (namely the compound in the formula (II)).
The preparation method of the tetrahydroxy citric acid polyether ester comprises the following steps: under the action of a catalyst, dropwise adding ethylene oxide or propylene oxide into anhydrous citric acid in a high-pressure reaction kettle at 155-165 ℃ for reaction, controlling the reaction pressure to be 0.1-0.6 MPa, preserving heat for 1-3 hours at 155-165 ℃ after the ethylene oxide or the propylene oxide is dropwise added, then cooling to be below 80 ℃, adding activated clay, stirring for 0.5-2 hours, and performing circulating pressure filtration until the mixture is clear and transparent to obtain tetrahydroxy citric acid polyether ester (formula (I)), wherein the dosage ratio of the anhydrous citric acid to the ethylene oxide or the propylene oxide is 1 mol: 5 to 8 mol.
The catalyst is one or a mixture of more than one of sodium formate, potassium formate, sodium benzoate and potassium benzoate in any proportion, and the dosage of the catalyst is 0.5-5 wt%, preferably 0.5-3 wt% of the total mass of the anhydrous citric acid and the ethylene oxide or the propylene oxide.
According to the preparation method of the 4-functionality polyurethane acrylate, the prepared tetrahydroxy citric acid polyether ester and isocyanate ethyl acrylate are mixed according to the proportion of 1 mol: 3.8-4.1 mol, and reacting at 60-95 ℃ to obtain the 4-functionality polyurethane acrylate.
Preferably, the prepared tetrahydroxy citric acid polyether ester and isocyanate ethyl acrylate are mixed according to the proportion of 1 mol: 3.9-4 mol, stirring and reacting for 3-6 hours at 80-95 ℃ under the action of a catalyst and a polymerization inhibitor to obtain 4-functionality polyurethane acrylate; wherein the polymerization inhibitor can be p-hydroxyanisole or hydroquinone, and the dosage of the polymerization inhibitor is 100-5000 ppm of the total mass of tetrahydroxy citric acid polyether ester and isocyanate ethyl acrylate; the catalyst is dibutyltin dilaurate, and the dosage of the catalyst is 100-3000 ppm of the total mass of the tetrahydroxy citric acid polyether ester and the isocyanate ethyl acrylate.
The invention relates to the use of low-viscosity 4-functional urethane acrylates for producing UV coatings, inks or adhesives.
Has the advantages that:
the catalyst used for preparing the polyether ester is different from the traditional method, the catalyst used in the traditional method is sodium hydroxide and potassium hydroxide, after the polymerization reaction is finished, phosphoric acid aqueous solution is added for neutralization treatment, and then high vacuum dehydration and filter pressing are carried out to obtain the polyether ester; the invention adopts one or more than one of sodium formate, potassium formate, sodium benzoate and potassium benzoate in any proportion, after polymerization, acid is not needed to be added, water is not needed to be added for neutralization, high vacuum dehydration is not needed, only activated clay is needed to be added for filtration, filter residue is subjected to water dissolution, catalyst is dissolved, the activated clay is filtered out, the water solution of the catalyst is evaporated and crystallized to realize recycling, and the reaction process belongs to green catalysis and clean production. The anhydrous citric acid is adopted, so that the reaction of water and ethylene oxide or propylene oxide in the reaction process is avoided, and a byproduct, namely ethylene glycol or propylene glycol is generated.
The polyurethane acrylate is prepared by adopting the isocyanate ethyl acrylate, so that the reaction steps are reduced, the reaction process is simple and easy to control, gel is not easy to generate due to side reaction, the viscosity of the polyurethane acrylate product is low, the requirement of applying the polyurethane acrylate product to low-viscosity paint is met, and no or little solvent is added when the polyurethane acrylate product is used for UV spraying; after being cured, the low-viscosity 4-functionality UV photocuring polyurethane acrylate has excellent performances of high hardness, wear resistance, scratch resistance, heat resistance, weather resistance and the like, and can be applied as raw materials of UV coatings, printing ink and adhesives.
Detailed Description
Example 1
1920 g of anhydrous citric acid (C) are put into a 6L high-pressure reaction kettle6H8O7Molecular weight 192), 40 g of sodium formate, heating to 155 deg.C, and starting to add ethylene oxide (C)2H4O, molecular weight 44)2200 g, controlling the temperature to 155-165 ℃ and the pressure to 0.10-0.40 MPa, dropwise adding for 3-4 hours, preserving the heat for 2-3 hours at 155-165 ℃ after finishing dropping, then cooling to below 80 ℃, and discharging to obtain a crude product; adding 40 g of active clay into the crude product, stirring for 30 minutes, and filtering to obtain clear and transparent tetrahydroxy citric acid polyether ester (C)16H28O12Molecular weight 412)4037.6 g, having the structure shown in formula (I), wherein: n is 2, a + b + c + d is 5.
The resulting tetrahydroxy citric acid polyether ester (C) was put into a 1000mL four-necked flask16H28O12Molecular weight 412)206 g, isocyanate ethyl acrylate 282.24 g (2mol), catalyst dibutyltin dilaurate 0.3 g, polymerization inhibitor p-hydroxyanisole 1 g, slowly heating to 80-85 ℃ for 0.5-4 hours, carrying out heat preservation reaction for 3-5 hours, and discharging to obtain the 4-functionality polyurethane acrylate, wherein the structure is shown as formula (II):
R1comprises the following steps:
n＝2，a+b+c+d＝5。
example 2
1920 g of anhydrous citric acid (C) are put into a 6L high-pressure reaction kettle6H8O7Molecular weight 192), 60 g of potassium formate, heating to 155 ℃, and starting to dropwise add propylene oxide (C)3H6O, molecular weight 58)3480 g, controlling the temperature to 155-165 ℃ and the pressure to 0.10-0.40 MPa, dropwise adding for 3-4 hours, keeping the temperature at 155-165 ℃ for 2-3 hours after dropwise adding, then cooling to below 80 ℃, and discharging to obtain a crude product; adding 60 g of active clay into the crude product, stirring for 30 minutes, and filtering to obtain clear and transparent tetrahydroxy citric acid polyether ester (C)24H44O13Molecular weight 540)5292 g, the structure is shown in formula (I), wherein: n is 3, a + b + c + d is 6.
The resulting tetrahydroxy citric acid polyether ester (C) was put into a 1000mL four-necked flask24H44O13The molecular weight is 540), the isocyanate ethyl acrylate is 280 g (1.984mol), the catalyst dibutyltin dilaurate is 0.3 g, the polymerization inhibitor p-hydroxyanisole is 1 g, the temperature is slowly raised to 80-85 ℃ within 0.5-4 hours, the heat preservation reaction is carried out for 3-5 hours, and the material is discharged, so that the 4-functionality polyurethane acrylate is prepared, and the structure is shown as the formula (II), wherein:
R1comprises the following steps:
n＝3，a+b+c+d＝6。
example 3
The viscosities of the 4-functional urethane acrylates obtained in examples 1-2 of the present invention and comparative examples 1-2 were examined with reference to the 4-functional urethane acrylates obtained in examples 1-2 of Chinese patent ZL201310143167.9 as comparative examples 1-2, respectively.
The test method comprises the following steps: model NDJ-1 rotational viscometer, spindle 4, 60 rpm. The concrete operation steps refer to the NDJ-1 type rotational viscometer use instruction book.
TABLE 14 viscosity of functional urethane acrylates
| Comparative example 1 | Example 1 | Comparative example 2 | Example 2 | |
| Viscosity of the oil | 12000mPa.s@60℃ | 6200mPa.s@60℃ | 15000mPa.s@60℃ | 8000mPa.s@60℃ |
The viscosity of the product of example 1 decreased 5800mPa.s @60 ℃ compared to the product of comparative example 1 by 48.33%.
The viscosity of the product of example 2 decreased by 7000mPa.s @60 ℃ compared to the product of comparative example 2, by 46.67%.
Example 4
Raw material
UV resin (i): the low viscosity 4-functional aliphatic urethane acrylate prepared in example 1 (the 4-functional aliphatic urethane acrylate is used for the purpose of increasing the hardness, strength, abrasion resistance, etc. of the coating film);
UV resin (II): the low-viscosity 2-functionality aliphatic urethane acrylate (the 2-functionality aliphatic urethane acrylate is adopted for the purpose of improving the flexibility, the bursting resistance and the cold-hot cycle resistance of a coating film) is prepared by the following steps:
500 g of polycaprolactone diol (Bestton CAPA2209, molecular weight 2000), 70.5 g (0.5mol) of isocyanate ethyl acrylate, 0.1 g of dibutyltin dilaurate serving as a catalyst and 0.6 g of p-hydroxyanisole serving as a polymerization inhibitor are put into a 1000mL four-neck flask, the temperature is slowly raised to 80-85 ℃ for 0.5-4 hours, the heat preservation reaction is carried out for 3-5 hours, and the 2-functionality polycaprolactone polyurethane acrylate with the structure shown in the following formula is obtained.
R is 1, 2-ethylene: -CH2CH2Namely, the dihydric alcohol initiator in the polycaprolactone diol is glycol;
a+b＝(2000-62)/114＝17。
the viscosity of the 2-functionality polycaprolactone urethane acrylate was measured to be 4100mpa.s @60 ℃ using the viscosity test method of example 3.
UV monomer: dipentaerythritol hexaacrylate (DPHA, jiangsu lika); 1, 6-hexanediol diacrylate (HDDA, Jiangsu Rida).
Photoinitiator (2): 1173, Nanjing Waals chemical technology, Inc.
Auxiliary agent: tego432, Tego92, Germany Digao.
Mixing solvent: butyl acetate, toluene and methyl isobutyl ketone in a mass ratio of 1: 1: 1 and mixing.
Apparatus and device
LT-1002 type ultraviolet curing machine, blue sky lamp development Co., Ltd; QFZ type paint film adhesion tester, Tianjin department union materials testing machine factory; RCA paper tape wear-resisting instrument, Shanghai modern environmental engineering technical research institute; a water bath kettle; and (4) a cold-hot circulating device.
Preparation of coating
Weighing a certain mass of UV resin, then adding the UV monomer, the mixed solvent, the photoinitiator and the auxiliary agent, uniformly stirring, and preparing the coating. The coating formulation is shown in Table 2.
TABLE 2 coating composition
Preparation and curing of coating films
Selecting an ABS plastic plate of 10cm multiplied by 10cm, firstly spraying a layer of thermoplastic acrylic resin white primer on the surface of the ABS plastic plate, baking the ABS plastic plate at 60 ℃ for 3 hours, then spraying UV coating prepared according to the table 2 on the surface of the ABS plastic plate, wherein the thickness of the coating film is about 20 mu m, curing the coating film on a photocuring machine to ensure that the cured film is surface-dried, characterizing the cured film by a finger-touch dry method, and recording the curing time.
Performance testing
Curing time: the test was conducted by a dry-to-touch method in which the surface of the paint film was touched with a finger and was considered to be cured if it did not feel sticky.
Pencil hardness: the test is carried out according to a GB 6739-86 coating pencil hardness method.
Adhesion force: the test is carried out according to a GB/T1720-88 coating adhesion test method. The classification is 7 grades, the best grade 1 and the worst grade 7.
Wear resistance: RCA test, 175g, 500. + -. 50 times.
Boiling in water: refer to the national standard GB/T1733 "determination of Water resistance of paint film".
Cold and heat cycle resistance:
(1) scope and description: the tendency of plastic paints to crack, due to damp heat cycles or loss of plasticizer, or both, is determined by the alternating exposure of the paint films to hot and cold chambers, and the extent of cracking.
(2) The instrument comprises the following steps: the device comprises a wet and hot box, a freezing box, a color measuring instrument and a grid drawing device.
(3) The determination method comprises the following steps: putting the test sample into an incubator hot box with the relative temperature of 100% and the temperature of 38 ℃ for 24 hours. The sample plates should be placed at an angle of 0-30 degrees from the vertical and the plates should not touch each other during the test. ② after 24h, immediately transferring the sample plate into a freezer at (-23 +/-1.5) DEG C for 20h, wherein the transfer time is not more than 30S at most. Thirdly, the sample plate is taken out and placed for 4 hours at room temperature, so that 48 hours in total are a cycle, and the period can be subjected to stage evaluation. Fourthly, 15 cycles are carried out, and then the appearance, the color and the adhesive force of the sample plate are tested.
(4) The results show that: the coating should be free of cracking, discoloration, adhesion loss, or other defects.
(5) Reference standard: U.S. Standard AAMA 615-02 trade Specification, Performance requirements and test methods for high Performance organic coatings for Plastic profiles.(1)
Results and discussion of the Effect of the resin on coating Performance
The UV resin is the main body of the UV coating, and the performance of the UV resin basically determines the main performance of a coating film after being cured. In the experiment, different formulas are formed by adopting 4-functionality aliphatic polyurethane acrylate and 2-functionality aliphatic polyurethane acrylate resin, the dosage of various components is shown in table 2, and the coating performance is shown in table 3.
TABLE 34 Effect of different ratios of functional urethane acrylate to 2-functional urethane acrylate on coating Properties
Reference documents: (1) yu yingying, inspection methods and instruments for paint industry are all the same, Beijing: chemical industry publishers, 2007: 525.
description of additional photoinitiator 1173:
the manufacturer: nanjing Wa chemical technology Co Ltd
Chemical name: 2-hydroxy-2-methyl-1-phenyl-1-propanone
English name: 2-Hydroxy-2-methyl-1-phenyl-propan-1-one
CAS NO：7473-98-5
The molecular formula is as follows: C10H12O
Molecular weight: 164.2
Chemical structural formula:
the technical indexes are as follows:
appearance: colorless to pale yellow transparent liquid
Purity: not less than 99.0 percent
Boiling point: 80-81 deg.C (centigrade)
Light transmittance: 425nm is more than or equal to 99.0 percent; 500nm is more than or equal to 99.3 percent
Volatile components: less than or equal to 0.2 percent
Ash content: less than or equal to 0.10 percent
The application comprises the following steps:
1173 are suitable for use in acrylic photocurable varnish systems, such as the varnishes of wood, metal, paper, plastics, and the like. 1173 particularly recommends that in the UV-curing coating which needs to be exposed to long-term sunlight and is yellowing-resistant, as 1173 is liquid and is very easy to blend, the UV-curing coating is suitable for being compounded with other photoinitiators, and the recommended addition amount is 1-4% w/w.
Claims (10)
1. 4-functional polyurethane acrylates based on anhydrous citric acid, characterized in that: the 4-functionality polyurethane acrylate is prepared by the following method: anhydrous citric acid reacts with ethylene oxide or propylene oxide under the action of a catalyst to prepare tetrahydroxy citric acid polyether ester, and then the tetrahydroxy citric acid polyether ester reacts with isocyanate ethyl acrylate to prepare the 4-functionality polyurethane acrylate.
2. The 4-functional urethane acrylate according to claim 1, characterized in that: the preparation of the tetrahydroxy citric acid polyether ester comprises the following steps: under the action of a catalyst, dropwise adding ethylene oxide or propylene oxide into anhydrous citric acid in a high-pressure reaction kettle at 155-165 ℃ for reaction, controlling the reaction pressure to be 0.1-0.6 MPa, preserving heat for 1-3 hours at 155-165 ℃ after the ethylene oxide or the propylene oxide is dropwise added, then cooling to be below 80 ℃, adding activated clay, stirring for 0.5-2 hours, and performing circulating filter pressing until the mixture is clear and transparent to obtain tetrahydroxy citric acid polyether ester; wherein the dosage ratio of the anhydrous citric acid to the ethylene oxide or the propylene oxide is 1 mol: 5 to 8 mol.
3. The 4-functional urethane acrylate according to claim 2, characterized in that: the catalyst is one or a mixture of more than one of sodium formate, potassium formate, sodium benzoate and potassium benzoate in any proportion, and the dosage of the catalyst is 0.5-5 wt% of the total mass of the anhydrous citric acid and the ethylene oxide or the propylene oxide.
4. The 4-functional urethane acrylate according to claim 1, characterized in that: the prepared tetrahydroxy citric acid polyether ester and isocyanate ethyl acrylate are mixed according to the proportion of 1 mol: 3.8-4.1 mol, and reacting at 60-95 ℃ to obtain the 4-functionality polyurethane acrylate.
5. The 4-functional urethane acrylate according to claim 4, characterized in that: the prepared tetrahydroxy citric acid polyether ester and isocyanate ethyl acrylate are mixed according to the proportion of 1 mol: 3.9-4 mol, stirring and reacting for 3-6 hours at 80-95 ℃ under the action of a catalyst and a polymerization inhibitor to obtain the 4-functionality polyurethane acrylate. Wherein the polymerization inhibitor is p-hydroxyanisole or hydroquinone, and the dosage of the polymerization inhibitor is 100-5000 ppm of the total mass of tetrahydroxy citric acid polyether ester and isocyanate ethyl acrylate; the catalyst is dibutyltin dilaurate, and the dosage of the catalyst is 100-3000 ppm of the total mass of the tetrahydroxy citric acid polyether ester and the isocyanate ethyl acrylate.
6. The process for preparing 4-functional urethane acrylates according to claim 1, wherein: the method comprises the following steps: anhydrous citric acid reacts with ethylene oxide or propylene oxide under the action of a catalyst to prepare tetrahydroxy citric acid polyether ester, and then the tetrahydroxy citric acid polyether ester reacts with isocyanate ethyl acrylate to prepare the 4-functionality polyurethane acrylate.
7. The method for preparing 4-functional urethane acrylate according to claim 6, wherein: the preparation of the tetrahydroxy citric acid polyether ester comprises the following steps: under the action of a catalyst, dropwise adding ethylene oxide or propylene oxide into anhydrous citric acid in a high-pressure reaction kettle at 155-165 ℃ for reaction, controlling the reaction pressure to be 0.1-0.6 MPa, preserving heat for 1-3 hours at 155-165 ℃ after the ethylene oxide or the propylene oxide is dropwise added, then cooling to be below 80 ℃, adding activated clay, stirring for 0.5-2 hours, and performing circulating filter pressing until the mixture is clear and transparent to obtain tetrahydroxy citric acid polyether ester; wherein the dosage ratio of the anhydrous citric acid to the ethylene oxide or the propylene oxide is 1 mol: 5-8 mol;
the catalyst is one or a mixture of more than one of sodium formate, potassium formate, sodium benzoate and potassium benzoate in any proportion, and the dosage of the catalyst is 0.5-5 wt% of the total mass of the anhydrous citric acid and the ethylene oxide or the propylene oxide.
8. The method for preparing 4-functional urethane acrylate according to claim 6, wherein: the prepared tetrahydroxy citric acid polyether ester and isocyanate ethyl acrylate are mixed according to the proportion of 1 mol: 3.8-4.1 mol, and reacting at 60-95 ℃ to obtain the 4-functionality polyurethane acrylate.
9. The method for preparing 4-functional urethane acrylate according to claim 8, wherein: the prepared tetrahydroxy citric acid polyether ester and isocyanate ethyl acrylate are mixed according to the proportion of 1 mol: 3.9-4 mol, stirring and reacting for 3-6 hours at 80-95 ℃ under the action of a catalyst and a polymerization inhibitor to obtain 4-functionality polyurethane acrylate; wherein the polymerization inhibitor is p-hydroxyanisole or hydroquinone, and the dosage of the polymerization inhibitor is 100-5000 ppm of the total mass of tetrahydroxy citric acid polyether ester and isocyanate ethyl acrylate; the catalyst is dibutyltin dilaurate, and the dosage of the catalyst is 100-3000 ppm of the total mass of the tetrahydroxy citric acid polyether ester and the isocyanate ethyl acrylate.
10. Use of the 4-functional urethane acrylates according to claim 1 for the preparation of UV coatings, inks or adhesives.
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