CN101070329A - Phosphates acrylate and its synthesizing method and use - Google Patents
Phosphates acrylate and its synthesizing method and use Download PDFInfo
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- CN101070329A CN101070329A CN 200710023352 CN200710023352A CN101070329A CN 101070329 A CN101070329 A CN 101070329A CN 200710023352 CN200710023352 CN 200710023352 CN 200710023352 A CN200710023352 A CN 200710023352A CN 101070329 A CN101070329 A CN 101070329A
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- acrylate
- methyl
- add
- phosphates
- acrylic resin
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- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 30
- -1 Phosphates acrylate Chemical class 0.000 title claims description 34
- 235000021317 phosphate Nutrition 0.000 title claims description 26
- 238000000034 method Methods 0.000 title claims description 7
- 230000002194 synthesizing effect Effects 0.000 title description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 29
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 22
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims abstract description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 18
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 28
- 229920000178 Acrylic resin Polymers 0.000 claims description 27
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 25
- 239000012752 auxiliary agent Substances 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 19
- 239000013530 defoamer Substances 0.000 claims description 18
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 12
- 229920000728 polyester Polymers 0.000 claims description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 229920000570 polyether Chemical group 0.000 claims description 9
- 238000010907 mechanical stirring Methods 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 8
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000001723 curing Methods 0.000 claims description 7
- 239000003973 paint Substances 0.000 claims description 7
- 238000010189 synthetic method Methods 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 229920005862 polyol Polymers 0.000 claims description 5
- 150000003077 polyols Chemical class 0.000 claims description 5
- 229920000909 polytetrahydrofuran Chemical group 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 3
- 239000006096 absorbing agent Substances 0.000 claims description 3
- 230000001588 bifunctional effect Effects 0.000 claims description 3
- 230000032050 esterification Effects 0.000 claims description 3
- 238000005886 esterification reaction Methods 0.000 claims description 3
- 239000003112 inhibitor Substances 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 235000002639 sodium chloride Nutrition 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 32
- 239000000463 material Substances 0.000 abstract description 25
- 239000000758 substrate Substances 0.000 abstract description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 239000000654 additive Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 150000002148 esters Chemical class 0.000 abstract 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract 2
- 239000010452 phosphate Substances 0.000 abstract 2
- 238000013019 agitation Methods 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 239000002861 polymer material Substances 0.000 abstract 1
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical class OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 description 31
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 28
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- 238000005286 illumination Methods 0.000 description 16
- 238000000016 photochemical curing Methods 0.000 description 16
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 15
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 15
- 229910052753 mercury Inorganic materials 0.000 description 15
- 238000006116 polymerization reaction Methods 0.000 description 9
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 7
- 239000012965 benzophenone Substances 0.000 description 7
- IHAAVLXHNOZMBC-UHFFFAOYSA-N ethyl 3,5-dimethylbenzoate Chemical compound CCOC(=O)C1=CC(C)=CC(C)=C1 IHAAVLXHNOZMBC-UHFFFAOYSA-N 0.000 description 7
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical class OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 7
- 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 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- 229960005181 morphine Drugs 0.000 description 6
- ZDHCZVWCTKTBRY-UHFFFAOYSA-N omega-Hydroxydodecanoic acid Natural products OCCCCCCCCCCCC(O)=O ZDHCZVWCTKTBRY-UHFFFAOYSA-N 0.000 description 6
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 3
- DMKSVUSAATWOCU-HROMYWEYSA-N loteprednol etabonate Chemical compound C1CC2=CC(=O)C=C[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@@](C(=O)OCCl)(OC(=O)OCC)[C@@]1(C)C[C@@H]2O DMKSVUSAATWOCU-HROMYWEYSA-N 0.000 description 3
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 3
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- 238000003848 UV Light-Curing Methods 0.000 description 2
- 229920004482 WACKER® Polymers 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical class CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000008365 aromatic ketones Chemical class 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
This invention relates to phosphate ester acrylate synthesis methods, uses, belongs to environment friendly photosensitive polymer materials. Add phosphorus oxychloride to the reactor with circumfluence condenser tube, drying tube, mechanical agitation and nitrogen entrance, cooling to 0 deg.C, then add acrylic hydroxy esters and triethylamine mixture, the reaction at room temperature for 10 hours, add to the solution polyhydroxy compounds, the reaction at room temperature for 20 hours again, filtration to remove solids, use 1% hydrochloric acid, 5% saturated sodium bicarbonate salt water to wash, then by drying, remove the solvent to gain phosphate ester acrylate. The invention can be used as additives for the production of UV-curable coatings, in the general (meth) acrylate monomers and (meth) acrylate resin has good solubility, can improve materials on the substrate, especially metal substrate adhesion.
Description
Technical field
The invention belongs to the environmental friendliness field of light-sensitive high molecular materials, particularly relate to the prescription of radical photoinitiator aggressiveness system and synthesizing of special additive.
Background technology
Along with people's environmental pollution problem is more and more paid attention to, national governments are more and more lower to limiting the quantity of of residual solvent in the solvent of conventional solvent type coating and the coating.For example the U.S. just carries out strict regulation (Clean air Act) to the solvent and the discharging of coating as far back as the eighties in last century, and for this reason, it is imperative to greatly develop environmental friendliness coating.Advantages such as ultraviolet (UV) photo-cured coating is owing to its environmental friendliness, and is efficient, energy-conservation have been used for every field.It is very promising at present green coating.In developed countries such as American-European Japan; the ultraviolet light polymerization development is very fast, and its Application Areas comprises: various printing technologies, various material surface glazing and protection, automotive industry, precision sizing, microelectronics industry, biomaterial, information industry, military industry equipment.
Photopolymerization is to utilize light as reaction power, on photosensitive compound, makes it that a series of optical physics take place by light action, photochemical reaction, generate active substance, thus the initiating activity monomer polymerization, and Ye Tai resin is converted into solid-state macromolecular material the most at last.Its polymerization characteristics are to save the energy, environmental friendliness, economical and efficient, photopolymerization device compactness, production efficiency height.In addition, photopolymerization compares to traditional polymerization technique outstanding advantage, and for example polymerized at room temperature helps the processing of heat-sensitive substrate material; Polymerization formula can be regulated by demand, guarantees product performance (as hardness, flexibility, gloss, weathering resistance etc.); Be easy to realize streamline operration, the level of automation height.Therefore photopolymerization is the advanced manufacturing technology of a kind of being described as " green technology ".
The distinctive technical superiority of photopolymerization not only satisfies the requirement of " 3E (Energy; Ecology; Economy) principle ", and in industrialization process, continue to keep to traditional solidified market competitiveness, make light polymerization technique be the rapid growth impetus since the sixties in 20th century: developed country (as the U.S., Japan and European various countries) annual growth rate is about 10% at present always, the rate of growth of developing country is faster, and the average annual growth rate of China can reach 25%.
The photopolymerization system mainly by light trigger, monomer and performed polymer, stopper, filler, and other additives form, polymerization takes place under illumination.Its key distinction is the initiator difference.At present the most widespread use be the UV-light light polymerization technique.Its initiator is the benzoin ether compound, acetophenones derivative, aromatic ketone/amine compound system.Monomer and performed polymer mainly are different structure (methyl) acrylic ester compounds.
Metal is because its surperficial special construction makes that its surperficial application is very difficult.General coating does not have sticking power on its surface, and for application is carried out in the metallic surface, special formulation for coating material is necessary.
Summary of the invention
First purpose of the present invention is to invent a kind of additive-phosphates acrylate of carrying coating at metallic surface sticking power.
Phosphates acrylate, its molecular structural formula is as follows:
R wherein
1For
R
2Be alkyl, or phenyl, or phenolic group,
R is an alkyl, or phenyl, or polyethers, or polytetrahydrofuran,
N is 1～5 integer.
In the phosphates acrylate of the present invention except that containing acrylic double bond, also contain bound phosphate groups, can be used as additive and be used to produce ultraviolet-curing paint, in general (methyl) vinylformic acid reactive monomer and (methyl) acrylic resin, good solvability is arranged, can improve material to base material, particularly the sticking power of metal base.
Second purpose of the present invention is to be that above-mentioned additive---phosphates acrylate provides a kind of synthetic method.
The synthetic method of phosphates acrylate is: add phosphorus oxychloride in the reactor that reflux condensing tube, drying tube, mechanical stirring and nitrogen inlet are housed, after being cooled to 0 ℃, add crylic acid hydroxy ester and triethylamine mixture, reaction is after 10 hours under the room temperature, in solution, add polyol, at room temperature reacted solids removed by filtration again 20 hours, with 1% hydrochloric acid, 5% sodium bicarbonate and saturated common salt water washing after drying, remove desolvate phosphates acrylate.
The weigh ratio of phosphorus oxychloride, crylic acid hydroxy ester, triethylamine mixture, polyol, 1% hydrochloric acid, 5% sodium bicarbonate, saturated aqueous common salt is: 10～50: 3～20: 10～40: 10～60: 30～100: 50～200: 10～300.
This synthetic method is simple, and the phosphates acrylate of formation has good solvability in general (methyl) vinylformic acid reactive monomer and (methyl) acrylic resin.
The 3rd purpose of the present invention provides the purposes of described phosphates acrylate.
Phosphates acrylate is used to make ultraviolet-curing paint.
The method of making ultraviolet-curing paint is: in being provided with the container of whipping device, add and account for gross weight 10%～50% reactive thinner, 5%～15% phosphates acrylate, 1%～5% auxiliary agent, 5%～10% light trigger, after the stirring and dissolving, add 20%～50% light reactive resin again, under 20～50 ℃ of temperature, mix and promptly obtain ultraviolet-curing paint.
The above-mentioned light reactive resin of the present invention can be in epoxy (methyl) acrylic resin or urethane (methyl) acrylic resin or polyester (methyl) acrylic resin or polyethers (methyl) acrylic resin or poly-(methyl) acrylic resin of acroleic acid esterification any.
Described reactive thinner can be simple function group, or bifunctional, or in polyfunctional group (methyl) acrylate monomer any.
Described auxiliary agent can have flow agent, defoamer, oxidation inhibitor, uv-absorbing agent.
Described light trigger is a radical photoinitiator.
When using UV coating of the present invention and carrying out polymerization, can adopt light sources such as mercuryarc lamp, electrodeless lamp source, xenon lamp, metal halide lamp, LED lamp.The UV coating that contains phosphates acrylate can carry out the light solidifying coating material of quick photocuring as metal.
Embodiment
One, the synthetic method of phosphates acrylate:
Reflux condensing tube is being housed, drying tube, the phosphorus oxychloride and the anhydrous diethyl ether that add metering in the reactor of mechanical stirring and nitrogen inlet, be cooled to 0 ℃ after, add the crylic acid hydroxy ester and the triethylamine mixture of metering, reaction is after 10 hours under the room temperature, in solution, add the polyol of metering, at room temperature reacted solids removed by filtration again 20 hours, with certain density hydrochloric acid, 5% sodium bicarbonate and saturated common salt water washing after drying, remove desolvate product.
Synthetic example 1
Reflux condensing tube is being housed, drying tube, add 100 gram phosphorus oxychloride and 300ml anhydrous diethyl ethers in the reactor of mechanical stirring and nitrogen inlet, after being cooled to 0 ℃, add 30 gram hydroxyethyl acrylate, 100ml triethylamine mixture, reaction is after 10 hours under the room temperature, in solution, add 200 gram polyethers (molecular weight 3000), at room temperature reacted again 20 hours, solids removed by filtration, use 50ml, concentration is 1% hydrochloric acid and 100ml, concentration is 5% sodium bicarbonate and 200ml saturated common salt water washing after drying, remove desolvate product, promptly the Phosphation acrylate 1.
(molecular weight can conversion and obtain different products)
Synthetic example 2
Reflux condensing tube is being housed, drying tube, add phosphorus oxychloride and 300ml anhydrous diethyl ether in the reactor of mechanical stirring and nitrogen inlet, after being cooled to 0 ℃, add 3 gram hydroxyethyl acrylate, 50 gram triethylamine mixtures, reaction is after 10 hours under the room temperature, in solution, add 150 gram polytetrahydrofurans (molecular weight 2000), at room temperature reacted again 20 hours, solids removed by filtration, 100ml, concentration are that 1% hydrochloric acid and 50ml, concentration are 5% sodium bicarbonate and 200ml saturated common salt water washing after drying, remove desolvate product, promptly the Phosphation acrylate 2.
(molecular weight can conversion and obtain different products)
Synthetic example 3
Reflux condensing tube is being housed, drying tube, add phosphorus oxychloride and 300ml anhydrous diethyl ether in the reactor of mechanical stirring and nitrogen inlet, after being cooled to 0 ℃, add 50 gram hydroxyethyl acrylate, 200ml triethylamine mixture, reaction is after 10 hours under the room temperature, in solution, add 100 gram polytetroxide furans (molecular weight 2000), at room temperature reacted again 20 hours, solids removed by filtration is used 100ml, concentration is 1% hydrochloric acid and 100ml, concentration is 5% sodium bicarbonate and 200ml saturated common salt water washing after drying, remove desolvate product, be Phosphation acrylate 3, (molecular weight can conversion and obtain different products).
Synthetic example 4
Reflux condensing tube is being housed, drying tube, add phosphorus oxychloride and 100ml anhydrous diethyl ether in the reactor of mechanical stirring and nitrogen inlet, after being cooled to 0 ℃, add 10 gram hydroxyethyl acrylate, 100ml triethylamine mixture, reaction is after 10 hours under the room temperature, in solution, add 20 gram dihydroxyphenyl propanes, at room temperature reacted again 20 hours, solids removed by filtration, with 50ml, concentration is that 1% hydrochloric acid and 100ml, concentration are 5% sodium bicarbonate and 100ml saturated common salt water washing after drying, remove desolvate product, promptly the Phosphation acrylate 4.
Synthetic example 5
Reflux condensing tube is being housed, drying tube, add phosphorus oxychloride and 200ml anhydrous diethyl ether in the reactor of mechanical stirring and nitrogen inlet, after being cooled to 0 ℃, add 5 gram hydroxyethyl acrylate, 40ml triethylamine mixture, reaction is after 10 hours under the room temperature, in solution, add 15 grams 1,6 hexylene glycols, at room temperature reacted 20 hours, solids removed by filtration is that 1% hydrochloric acid and 20ml, concentration are 5% sodium bicarbonate and 100ml saturated common salt water washing after drying with 50ml, concentration again, remove desolvate product, promptly the Phosphation acrylate 5.
(can be different polyvalent alcohols and obtain different products)
As follows by the products molecule structural formula that above each synthetic example makes:
R wherein
1For
R
2Be alkyl, or phenyl, or phenolic group,
R is an alkyl, or phenyl, or polyethers, or polytetrahydrofuran,
N is 1～5 integer.
Two, the UV curing metal prescription of coating:
Compound method when phosphates acrylate is used for the photo-cured coating prescription: (weight percentage)
Light reactive resin 20%～50%
Phosphates acrylate 5～15%
Reactive thinner 10%～50%
Initiator 5%～10%
Auxiliary agent 1%～5%
Light reactive resin can be epoxy (methyl) acrylic resin or urethane (methyl) acrylic resin or polyester (methyl) acrylic resin or polyethers (methyl) acrylic resin or poly-(methyl) acrylic resin of acroleic acid esterification.
Described reactive thinner can be simple function group, or bifunctional, or polyfunctional group (methyl) acrylate monomer.
Described auxiliary agent is flow agent, defoamer, oxidation inhibitor, uv-absorbing agent.
Described light trigger is a radical photoinitiator.
Three, the UV curing metal production method of coating:
In the container of whipping device is housed, add 10%～50% reactive thinner, 5%～15% additive phosphates acrylate, 1%～5% auxiliary agent, 5%～10% initiator, after the stirring and dissolving, add 20%～50% light reactive resin again, under 20～50 ℃ of temperature, stirring makes it to mix and promptly obtains radical polymerization light solidifying coating material.
Can adopt light sources such as mercuryarc lamp, electrodeless lamp source, xenon lamp, metal halide lamp, LED lamp to solidify.
Embodiment 1
Under the lucifuge condition, in being housed, the container of agitator adds 1% benzophenone, 1% mesitylenic acid ethyl ester, 1173 (2-hydroxy-2-methyls-1-phenyl-acetone-1) 3%, TPGDA (tripropylene glycol double methacrylate) 40%, TMPTA (Viscoat 295) 5%, auxiliary agent (flow agent Tego flow 300, defoamer Deuchem 2700, moistened surface agent BYK2700) 1%, 40 ℃ of following stirring and dissolving, add 34% bisphenol A epoxy acrylate again, the product of 15% synthetic example 1 mixes.Can obtain the light solidifying coating material.
The solution for preparing is applied on the substrate, placed under the 500W high voltage mercury lamp illumination 1 minute, photocuring is filmed.
Embodiment 2
Under the lucifuge condition, in being housed, the container of agitator adds 3% benzophenone, 2% mesitylenic acid ethyl ester, 184 (1-hydroxyls-cyclohexyl benzophenone) 5%, auxiliary agent (flow agent BYK-UV3510, defoamer Dow Corning163, moistened surface agent BYK2700) 3%, HDDA (1,6-hexylene glycol double methacrylate) 20%, TMPTA (Viscoat 295) 17%, stirring and dissolving under 50oC, add 45% bisphenol A epoxy acrylate again, the product of 5% synthetic example 2 mixes.Can obtain the light solidifying coating material.
The solution for preparing is applied on the substrate, placed under the 500W high voltage mercury lamp illumination 1 minute, photocuring is filmed.
Embodiment 3
Under the lucifuge condition, in being housed, the container of agitator adds 1% benzophenone, 1% mesitylenic acid ethyl ester, 1173 (2-hydroxy-2-methyls-1-phenyl-acetone-1) 5%, HDDA (1,6-hexylene glycol double methacrylate) 20%, TMPTA (Viscoat 295) 10%, auxiliary agent (flow agent BKY361, defoamer Airex 900, moistened surface agent BYK-200) 3%, 20 ℃ of following stirring and dissolving, add 50% urethane acrylate again, the product of 10% synthetic example 3 mixes.Can obtain the light solidifying coating material.
The solution for preparing is applied on the substrate, placed under the 500W high voltage mercury lamp illumination 1 minute, photocuring is filmed.
Embodiment 4
Under the lucifuge condition, in being housed, the container of agitator adds 907 (2-methyl isophthalic acids-[4-first sulfydryl phenyl]-2-morphine acetone-1) 3%, auxiliary agent (flow agent Tego 2100, defoamer Solutia PC-1344, moistened surface agent BYK2700) 2%, DPGDA (two contract propylene glycol double methacrylate) 15%, TMPTA (Viscoat 295) 20%, stirring and dissolving under 20oC adds 50% polyester (methyl) acrylic resin again, the product of 10% synthetic example 4 mixes.Can obtain the light solidifying coating material.
The solution for preparing is applied on the substrate, placed under the 500W high voltage mercury lamp illumination 1 minute, photocuring is filmed.
Embodiment 5
Under the lucifuge condition, in being housed, the container of agitator adds 1% benzophenone, 1% mesitylenic acid ethyl ester, 184 (1-hydroxyls-cyclohexyl benzophenone) 5%, HDDA (1,6-hexylene glycol double methacrylate) 30%, auxiliary agent (flow agent Tego 2250, defoamer Dow Corning 163) 3%, TMPTA (Viscoat 295) 10% 30 ℃ of following stirring and dissolving, adds 45% polyoxyalkylene acrylate resin again, the product of 5% synthetic example 5 mixes.Can obtain the light solidifying coating material.
The solution for preparing is applied on the substrate, placed under the 500W high voltage mercury lamp illumination 1 minute, photocuring is filmed.
Embodiment 6
Under the lucifuge condition, in being housed, the container of agitator adds 907 (2-methyl isophthalic acids-[4-first sulfydryl phenyl]-2-morphine acetone-1) 5%, DPGDA (two contract propylene glycol double methacrylate) 20%, auxiliary agent (flow agent Wacker Addid 130, defoamer Solutia PC-1344) 3%, TMPTA (Viscoat 295) 17%, 40 ℃ of following stirring and dissolving, add 40% polyester (methyl) acrylic resin again, the product of 15% synthetic example 3 mixes.Can obtain the light solidifying coating material.
The solution for preparing is applied on the substrate, placed under the 500W high voltage mercury lamp illumination 1 minute, photocuring is filmed.
Embodiment 7
Under the lucifuge condition, in being housed, the container of agitator adds 173 (2-hydroxy-2-methyls-1-phenyl-acetone-1) 9%, DPGDA (two contract propylene glycol double methacrylate) 11%, auxiliary agent (flow agent BYK3510, defoamer Deuchem 2700, moistened surface agent BYK2700) 1%, TMPTA (Viscoat 295) 29% 50 ℃ of following stirring and dissolving, adds 45% polyethers (methyl) acrylic resin again, the product of 5% synthetic example 1 mixes.Can obtain the light solidifying coating material.
The solution for preparing is applied on the substrate, placed under the 500W high voltage mercury lamp illumination 1 minute, photocuring is filmed.
Embodiment 8
Under the lucifuge condition, in being housed, the container of agitator adds 2% benzophenone, 1% mesitylenic acid ethyl ester, 1173 (2-hydroxy-2-methyls-1-phenyl-acetone-1) 4%, auxiliary agent (flow agent BYK345, defoamer Airex 900, moistened surface agent BYK2700) 3%, TPGDA (tripropylene glycol double methacrylate) 30%, TMPTA (Viscoat 295) 20% 25 ℃ of following stirring and dissolving, adds 30% bisphenol A epoxy acrylate again, the product of 10% synthetic example 1 mixes.Can obtain the light solidifying coating material.
The solution for preparing is applied on the substrate, placed under the 500W high voltage mercury lamp illumination 1 minute, photocuring is filmed.
Embodiment 9
Under the lucifuge condition, in being housed, the container of agitator adds 2% benzophenone, 2% mesitylenic acid ethyl ester, 907 (2-methyl isophthalic acids-[4-first sulfydryl phenyl]-2-morphine acetone-1) 5%, auxiliary agent (flow agent BYK-UV-3510, defoamer Dow Corning 163, moistened surface agent BYK2700) 1%, HDDA (1,6-hexylene glycol double methacrylate) 20%, TMPTA (Viscoat 295) 30%, 35 ℃ of following stirring and dissolving, add 30% polyester (methyl) acrylic resin again, the product of 10% synthetic example 5 mixes.Can obtain the light solidifying coating material.
The solution for preparing is applied on the substrate, placed under the 500W high voltage mercury lamp illumination 1 minute, photocuring is filmed.
Embodiment 10
Under the lucifuge condition, in being housed, the container of agitator adds 907 (2-methyl isophthalic acids-[4-first sulfydryl phenyl]-2-morphine acetone-1) 5%, HDDA (1,6-hexylene glycol double methacrylate) 30%, auxiliary agent (flow agent BYK361, defoamer Deuchem 3600) 1%, TMPTA (Viscoat 295) 14% 25 ℃ of following stirring and dissolving, adds 40% polyester (methyl) acrylic resin again, the product of 10% synthetic example 2 mixes.Can obtain the light solidifying coating material.
The solution for preparing is applied on the substrate, placed under the 500W high voltage mercury lamp illumination 1 minute, photocuring is filmed.
Embodiment 11
Under the lucifuge condition, in being housed, the container of agitator adds 1% benzophenone, 1% mesitylenic acid ethyl ester, 1173 (2-hydroxy-2-methyls-1-phenyl-acetone-1) 3%, HDDA (1,6-hexylene glycol double methacrylate) 38%, auxiliary agent (flow agent Tego Flow 300, defoamer Solutia PC-1344, moistened surface agent BKY2700) 2%, 40 ℃ of following stirring and dissolving, add 50% polyester (methyl) acrylic resin again, the product of 5% synthetic example 3 mixes.Can obtain the light solidifying coating material.
The solution for preparing is applied on the substrate, placed under the 500W high voltage mercury lamp illumination 1 minute, photocuring is filmed.
Embodiment 12
Under the lucifuge condition, in being housed, the container of agitator adds 907 (2-methyl isophthalic acids-[4-first sulfydryl phenyl]-2-morphine acetone-1) 3%, auxiliary agent (flow agent BYK 361, defoamer Airex 900) 3%, DPGDA (two contract propylene glycol double methacrylate) 30%, TMPTA (Viscoat 295) 14%, 50 ℃ of following stirring and dissolving, add 40% polyester (methyl) acrylic resin again, the product of 10% synthetic example 1 mixes.Can obtain the light solidifying coating material.
The solution for preparing is applied on the substrate, placed under the 500W high voltage mercury lamp illumination 1 minute, photocuring is filmed.
Embodiment 13
Under the lucifuge condition, in being housed, the container of agitator adds 184 (1-hydroxyls-cyclohexyl benzophenone) 3%, auxiliary agent (flow agent Tego 2250, defoamer Solutia PC-1344, moistened surface agent BYK2700) 3%, DPGDA (two contract propylene glycol double methacrylate) 29%, TMPTA (Viscoat 295) 20% 30 ℃ of following stirring and dissolving, adds 40% polyethers (methyl) acrylic resin again, the product of 5% synthetic example 3 mixes.Can obtain the light solidifying coating material.
The solution for preparing is applied on the substrate, placed under the 500W high voltage mercury lamp illumination 1 minute, photocuring is filmed.
Embodiment 14
Under the lucifuge condition, in being housed, the container of agitator adds 907 (2-methyl isophthalic acids-[4-first sulfydryl phenyl]-2-morphine acetone-1) 3%, auxiliary agent (flow agent BYK361, defoamer Deuchem 3600) 2%, DPGDA (two contract propylene glycol double methacrylate) 20%, TMPTA (Viscoat 295) 15%, 40 ℃ of following stirring and dissolving, add 50% polyester (methyl) acrylic resin again, the product of 10% synthetic example 5 mixes.Can obtain the light solidifying coating material.
The solution for preparing is applied on the substrate, placed under the 500W high voltage mercury lamp illumination 1 minute, photocuring is filmed.
Embodiment 15
Under the lucifuge condition, in being housed, the container of agitator adds 184 (1-hydroxyls-cyclohexyl benzophenone) 4%, DPGDA (two contract propylene glycol double methacrylate) 20%, auxiliary agent (flow agent Wacker Addid 200, defoamer BYK380, moistened surface agent BYK200) 1%, TMPTA (Viscoat 295) 15% 20 ℃ of following stirring and dissolving, adds 50% polyester (methyl) acrylic resin again, the product of 10% synthetic example 2 mixes.Can obtain the light solidifying coating material.
The solution for preparing is applied on the substrate, placed under the 500W high voltage mercury lamp illumination 1 minute, photocuring is filmed.
Claims (9)
1, phosphates acrylate, its molecular structural formula is as follows:
R wherein
1For
R
2Be alkyl, or phenyl, or phenolic group;
R is an alkyl, or phenyl, or polyethers, or polytetrahydrofuran;
N is 1～5 integer.
2, the synthetic method of the described phosphates acrylate of a kind of claim 1, after it is characterized in that the adding phosphorus oxychloride is cooled to 0 ℃ in the reactor that reflux condensing tube, drying tube, mechanical stirring and nitrogen inlet are housed, add crylic acid hydroxy ester and triethylamine mixture, reaction is after 10 hours under the room temperature, in solution, add polyol, at room temperature reacted again 20 hours, solids removed by filtration, with 1% hydrochloric acid, 5% sodium bicarbonate and saturated common salt water washing after drying, remove desolvate phosphates acrylate.
3,, it is characterized in that the weigh ratio of phosphorus oxychloride, crylic acid hydroxy ester, triethylamine mixture, polyol, 1% hydrochloric acid, 5% sodium bicarbonate, saturated aqueous common salt is: 10～50: 3～20: 10～40: 10～60: 30～100: 50～200: 10～300 according to the synthetic method of the described phosphates acrylate of claim 2.
4, phosphates acrylate is used to make ultraviolet-curing paint according to claim 1.
5, according to the purposes of the described phosphates acrylate of claim 4, it is characterized in that the method for making ultraviolet-curing paint is: in being provided with the container of whipping device, add and account for gross weight 10%～50% reactive thinner, 5%～15% phosphates acrylate, 1%～5% auxiliary agent, 5%～10% light trigger after the stirring and dissolving, adds 20%～50% light reactive resin again, under 20～50 ℃ of temperature, mix and promptly obtain ultraviolet-curing paint.
6,, it is characterized in that described light reactive resin is any in epoxy (methyl) acrylic resin or urethane (methyl) acrylic resin or polyester (methyl) acrylic resin or polyethers (methyl) acrylic resin or poly-(methyl) acrylic resin of acroleic acid esterification according to the purposes of the described phosphates acrylate of claim 5.
7, according to the purposes of the described phosphates acrylate of claim 5, it is characterized in that described reactive thinner is a simple function group, or bifunctional, or in polyfunctional group (methyl) acrylate monomer any.
8,, it is characterized in that described auxiliary agent comprises flow agent, defoamer, oxidation inhibitor, uv-absorbing agent according to the purposes of the described phosphates acrylate of claim 5.
9,, it is characterized in that described light trigger is a radical photoinitiator according to the purposes of the described phosphates acrylate of claim 5.
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| CN 200710023352 CN101070329A (en) | 2007-06-11 | 2007-06-11 | Phosphates acrylate and its synthesizing method and use |
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| CN 200710023352 CN101070329A (en) | 2007-06-11 | 2007-06-11 | Phosphates acrylate and its synthesizing method and use |
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