CN117701118B - Preparation method of photo-curing aqueous epoxy acrylate emulsion - Google Patents
Preparation method of photo-curing aqueous epoxy acrylate emulsion Download PDFInfo
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- CN117701118B CN117701118B CN202311723513.0A CN202311723513A CN117701118B CN 117701118 B CN117701118 B CN 117701118B CN 202311723513 A CN202311723513 A CN 202311723513A CN 117701118 B CN117701118 B CN 117701118B
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- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000000839 emulsion Substances 0.000 title claims abstract description 31
- 238000000016 photochemical curing Methods 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 56
- 239000005011 phenolic resin Substances 0.000 claims abstract description 56
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 52
- -1 styrene-phenyl phosphate Chemical compound 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000003085 diluting agent Substances 0.000 claims abstract description 18
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims abstract description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 42
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 19
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 17
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 16
- QBFNGLBSVFKILI-UHFFFAOYSA-N 4-ethenylbenzaldehyde Chemical compound C=CC1=CC=C(C=O)C=C1 QBFNGLBSVFKILI-UHFFFAOYSA-N 0.000 claims description 12
- 239000002270 dispersing agent Substances 0.000 claims description 12
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 claims description 12
- AFIUOMNOQAIDLO-UHFFFAOYSA-N 2-bromoethyl diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(OCCBr)OC1=CC=CC=C1 AFIUOMNOQAIDLO-UHFFFAOYSA-N 0.000 claims description 11
- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 claims description 11
- 229910019142 PO4 Inorganic materials 0.000 claims description 10
- 239000010452 phosphate Substances 0.000 claims description 10
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 claims description 9
- 239000013530 defoamer Substances 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 7
- 239000012279 sodium borohydride Substances 0.000 claims description 7
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 6
- 239000012965 benzophenone Substances 0.000 claims description 6
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 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 claims description 3
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 3
- 239000002518 antifoaming agent Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 19
- 239000011248 coating agent Substances 0.000 abstract description 18
- 239000004925 Acrylic resin Substances 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 7
- 238000006116 polymerization reaction Methods 0.000 abstract description 5
- 238000004132 cross linking Methods 0.000 abstract description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 38
- 239000003208 petroleum Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 16
- 238000004821 distillation Methods 0.000 description 10
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 7
- 239000003063 flame retardant Substances 0.000 description 7
- 239000003822 epoxy resin Substances 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 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 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- LDLCZOVUSADOIV-UHFFFAOYSA-N 2-bromoethanol Chemical compound OCCBr LDLCZOVUSADOIV-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention relates to the technical field of epoxy acrylate, and discloses a preparation method of a photo-curing water-based epoxy acrylate emulsion. The styrene-phenyl phosphate phenolic resin contains active styrene groups, and is subjected to crosslinking polymerization reaction with epoxy acrylate and an active diluent under the action of ultraviolet light and a photoinitiator, so that the phenolic resin is grafted into a molecular chain of the epoxy acrylate resin, the interfacial binding force of the phenolic resin and the epoxy acrylate resin is enhanced, the phenolic resin has a good enhancement effect, and the hardness, impact resistance and flame retardance of the epoxy acrylate coating are improved.
Description
Technical Field
The invention relates to the technical field of epoxy acrylate, in particular to a preparation method of a photo-curing aqueous epoxy acrylate emulsion.
Background
The water-based light-cured coating has the advantages of high curing speed, little environmental pollution and the like, and mainly comprises light-cured coatings such as epoxy acrylate, polyurethane acrylate and the like; the application of the water-based epoxy acrylate is very wide, the preparation method is simple, and the cost is low; however, the cured paint film of the aqueous epoxy acrylate has the defects of lower hardness, poor impact resistance, easy burning of the coating and the like.
The phenolic resin has good mechanical strength, heat resistance and flame retardance, has wide application prospect in the aspects of epoxy resin and epoxy acrylate, and the patent CN103382242B discloses that the phenolic resin and aromatic phosphate are mixed for polycondensation reaction to obtain phosphorus-containing flame-retardant phenolic resin, and the halogen-free flame-retardant effect on the epoxy resin is realized by utilizing the epoxy group reaction of phenolic hydroxyl and the epoxy resin; however, the epoxy resin does not have an ultraviolet curing effect; and also does not improve the properties of the epoxy resin such as hardness and impact resistance.
Disclosure of Invention
The invention solves the technical problems that: a photo-curing aqueous epoxy acrylate emulsion with high hardness, impact resistance and flame retardance is prepared.
The technical scheme of the invention is as follows:
A preparation method of a photo-curing aqueous epoxy acrylate emulsion comprises 100 parts by weight of maleic anhydride modified epoxy acrylate, 3-8 parts by weight of photoinitiator, 25-60 parts by weight of reactive diluent, 1-20 parts by weight of styrene-phenyl phosphate phenolic resin, 0.3-0.8 part by weight of defoamer and 0.1-0.4 part by weight of dispersant;
The preparation method of the photo-curing aqueous epoxy acrylate emulsion comprises the following steps:
Adding maleic anhydride modified epoxy acrylate and styrene-phenyl phosphate phenolic resin into water, dispersing uniformly, adding an active diluent, a defoaming agent and a dispersing agent, dispersing uniformly, adding a photoinitiator, and preserving in a dark place to obtain the photo-curing aqueous epoxy acrylate emulsion.
Wherein the reactive diluent comprises at least one of tripropylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate and tripropylene glycol diacrylate.
Wherein the initiator comprises at least one of Irgacure2959, irgacure1173 and benzophenone.
The preparation method of the styrene-phenyl phosphate phenolic resin comprises the following steps:
S1, adding 4-vinyl benzaldehyde and tyrosine into toluene, carrying out reflux reaction for 2-4h at 100-115 ℃, cooling to room temperature, adding sodium borohydride and ethanol, reacting for 8-16h, distilling under reduced pressure to remove a solvent, washing with petroleum ether, and recrystallizing with ethanol to obtain an intermediate 1.
S2, adding the intermediate 1, bromoethyl diphenyl phosphate and potassium carbonate into acetonitrile, stirring for reaction, distilling under reduced pressure to remove a solvent, washing with petroleum ether, and recrystallizing toluene to obtain a phenol intermediate containing phosphate and styrene groups.
S3, mixing phenol, phenol intermediate and formaldehyde aqueous solution (37% by mass) uniformly, adding sodium hydroxide at 60-70 ℃, stirring uniformly to react, distilling under reduced pressure to remove water, washing with petroleum ether, and drying to obtain the styrene-phenyl phosphate phenolic resin.
Wherein the weight ratio of 4-vinyl benzaldehyde to tyrosine is 100 (130-180).
Wherein the weight ratio of the intermediate 1 to the bromoethyl diphenyl phosphate to the potassium carbonate is 100 (110-140) to 160-220.
Wherein, the reaction temperature in S2 is controlled to be 35-50 ℃ and the reaction time is controlled to be 12-18h.
Wherein the weight ratio of phenol, phenol intermediate and formaldehyde is 100 (20-65) to 55-70.
Wherein, the reaction temperature in S2 is controlled to be 90-100 ℃ and the reaction time is controlled to be 2-4h.
The invention has the technical effects that: 4-vinyl benzaldehyde and tyrosine are used for condensation and reduction reaction to obtain an intermediate 1, then substitution reaction is carried out with bromoethyl diphenyl phosphate to obtain a novel phenol intermediate containing phosphate and styrene groups, and then polymerization reaction is carried out with phenol and formaldehyde to obtain the styrene-phenyl phosphate phenolic resin. And finally, compounding the modified epoxy acrylate with maleic anhydride, a photoinitiator, a reactive diluent and the like to obtain the photo-curing aqueous epoxy acrylate emulsion.
The styrene-phenyl phosphate phenolic resin contains hydrophilic carboxyl groups, so that the dispersibility of the phenolic resin in water is improved, and the stability of the aqueous epoxy acrylate emulsion is not affected.
The styrene-phenyl phosphate phenolic resin contains active styrene groups, and performs cross-linking polymerization reaction with epoxy acrylate and an active diluent under the action of ultraviolet light and a photoinitiator, so that the phenolic resin is grafted into a molecular chain of the epoxy acrylate resin, the interfacial binding force of the phenolic resin and the epoxy acrylate resin is enhanced, the phenolic resin has a good enhancement effect, and the hardness and the impact resistance of the epoxy acrylate coating are improved.
According to the invention, the styrene-phenyl phosphate phenolic resin is grafted into the epoxy acrylate resin matrix, the phenolic resin has good high temperature resistance and burning char formation, and the phosphate structure is used as a flame retardant, so that the phosphate compound generated by pyrolysis can further promote the phenolic resin and the coating group to be dehydrated into char, thereby forming a continuous compact char layer on the coating matrix, and playing a good role in inhibiting burning and flame retardance.
Detailed Description
The main raw materials of the invention are as follows: 4-vinylbenzaldehyde: CAS number 1791-26-0.
Tyrosine: CAS number 556-03-6.
Defoaming agent: brand EA0660
Dispersing agent: brand number DISPERBYK-2013.
The preparation method of the maleic anhydride modified epoxy acrylate comprises the following steps: bisphenol A epoxy acrylate and a catalyst triethylamine are added into ethylene glycol monomethyl ether, maleic anhydride is added, the mixture is reacted for 5 hours at 80 ℃, and the mixture is cooled and discharged to obtain maleic anhydride modified epoxy acrylate.
The preparation method of the bromoethyl diphenyl phosphate comprises the following steps: adding diphenoxyphosphoryl chloride (structural formula) to toluene) Reacting pyridine with 2-bromoethanol at room temperature for 6h, concentrating the solvent, washing with petroleum ether, recrystallizing with toluene to obtain bromoethyl diphenyl phosphate with structural formula/>
Example 1
100 Parts by weight of 4-vinylbenzaldehyde and 160 parts by weight of tyrosine are added into toluene, reflux reaction is carried out for 4 hours at 100 ℃, the temperature is reduced to room temperature, 150 parts by weight of sodium borohydride and ethanol solvent are added for reaction for 8 hours, the solvent is distilled off under reduced pressure, petroleum ether is used for washing, and ethanol is recrystallized to obtain an intermediate 1. The reaction formula is as follows:
100 parts by weight of intermediate 1, 110 parts by weight of bromoethyl diphenyl phosphate and 220 parts by weight of potassium carbonate are added into acetonitrile, stirred and reacted for 15 hours at 35 ℃, the solvent is removed by reduced pressure distillation, petroleum ether is used for washing, and toluene is recrystallized, so that a phenol intermediate containing phosphate and styrene groups is obtained. The reaction formula is as follows:
100 parts by weight of phenol, 20 parts by weight of phenol intermediate and an aqueous solution (37% by mass) containing 55 parts by weight of formaldehyde are uniformly mixed, 3 parts by weight of sodium hydroxide is added at 60 ℃ and stirred at 100 ℃ for reaction for 3 hours, water is removed by reduced pressure distillation, petroleum ether is washed, and the styrene-phenyl phosphate phenolic resin is obtained.
100 Parts by weight of maleic anhydride modified epoxy acrylate and 1 part by weight of styrene-phenyl phosphate phenolic resin are added into 120 parts by weight of water, the mixture is uniformly dispersed, then 25 parts by weight of tripropylene glycol diacrylate as an active diluent, 0.5 part by weight of defoamer and 0.1 part by weight of dispersing agent are added, the mixture is uniformly dispersed, and finally 3 parts by weight of photoinitiator benzophenone is added, and the mixture is preserved in a dark place, so that the photocuring aqueous epoxy acrylate emulsion is obtained.
Example 2
100 Parts by weight of 4-vinylbenzaldehyde and 130 parts by weight of tyrosine are added into toluene, reflux reaction is carried out for 2 hours at 115 ℃, the temperature is reduced to room temperature, 150 parts by weight of sodium borohydride and ethanol solvent are added for reaction for 12 hours, the solvent is distilled off under reduced pressure, petroleum ether is used for washing, and ethanol is recrystallized to obtain an intermediate 1.
100 Parts by weight of intermediate 1, 125 parts by weight of bromoethyl diphenyl phosphate and 200 parts by weight of potassium carbonate are added into acetonitrile, stirred and reacted for 18 hours at 35 ℃, the solvent is removed by reduced pressure distillation, petroleum ether is used for washing, toluene is used for recrystallization, and the phenol intermediate containing phosphate and styrene groups is obtained.
100 Parts by weight of phenol, 35 parts by weight of phenol intermediate and 58 parts by weight of formaldehyde-containing aqueous solution (37% by mass) are uniformly mixed, 3.5 parts by weight of sodium hydroxide is added at 70 ℃ and stirred at 100 ℃ for reaction for 2 hours, water is removed by reduced pressure distillation, petroleum ether is washed, and the styrene-phenyl phosphate phenolic resin is obtained.
100 Parts by weight of maleic anhydride modified epoxy acrylate and 7 parts by weight of styrene-phenyl phosphate phenolic resin are added into 120 parts by weight of water, the mixture is uniformly dispersed, then 40 parts by weight of reactive diluent tripropylene glycol diacrylate, 0.3 part by weight of defoamer and 0.4 part by weight of dispersant are added, the mixture is uniformly dispersed, and finally 4.5 parts by weight of photoinitiator Irgacure2959 is added, and the mixture is preserved in a dark place, so that the photocuring aqueous epoxy acrylate emulsion is obtained.
Example 3
100 Parts by weight of 4-vinylbenzaldehyde and 180 parts by weight of tyrosine are added into toluene, reflux reaction is carried out for 4 hours at 100 ℃, the temperature is reduced to room temperature, 140 parts by weight of sodium borohydride and ethanol solvent are added for reaction for 8 hours, the solvent is distilled off under reduced pressure, petroleum ether is used for washing, and ethanol is used for recrystallization, thus obtaining the intermediate 1.
100 Parts by weight of intermediate 1, 140 parts by weight of bromoethyl diphenyl phosphate and 180 parts by weight of potassium carbonate are added into acetonitrile, stirred and reacted for 12 hours at 50 ℃, the solvent is removed by reduced pressure distillation, petroleum ether is used for washing, and toluene is recrystallized, so that a phenol intermediate containing phosphate and styrene groups is obtained.
100 Parts by weight of phenol, 50 parts by weight of phenol intermediate and 63 parts by weight of formaldehyde-containing aqueous solution (37% by mass) are uniformly mixed, 4 parts by weight of sodium hydroxide is added at 65 ℃ and stirred at 100 ℃ for reaction for 2 hours, water is removed by reduced pressure distillation, petroleum ether is washed, and the styrene-phenyl phosphate phenolic resin is obtained by drying.
100 Parts by weight of maleic anhydride modified epoxy acrylate and 14 parts by weight of styrene-phenyl phosphate phenolic resin are added into 120 parts by weight of water, uniformly dispersed, 45 parts by weight of trimethylolpropane triacrylate as an active diluent, 0.8 part by weight of defoamer and 0.2 part by weight of dispersant are added, uniformly dispersed, and finally 6 parts by weight of photoinitiator Irgacure1173 is added, and the mixture is preserved in a dark place, so that the photocuring aqueous epoxy acrylate emulsion is obtained.
Example 4
100 Parts by weight of 4-vinylbenzaldehyde and 145 parts by weight of tyrosine are added into toluene, reflux reaction is carried out for 2 hours at 115 ℃, the temperature is reduced to room temperature, 120 parts by weight of sodium borohydride and ethanol solvent are added for reaction for 16 hours, the solvent is distilled off under reduced pressure, petroleum ether is used for washing, and ethanol is recrystallized to obtain an intermediate 1.
100 Parts by weight of intermediate 1, 140 parts by weight of bromoethyl diphenyl phosphate and 160 parts by weight of potassium carbonate are added into acetonitrile, stirred and reacted for 15 hours at 50 ℃, the solvent is removed by reduced pressure distillation, petroleum ether is used for washing, and toluene is recrystallized, so that a phenol intermediate containing phosphate and styrene groups is obtained.
100 Parts by weight of phenol, 65 parts by weight of phenol intermediate and 70 parts by weight of formaldehyde-containing aqueous solution (37% by mass) are uniformly mixed, 4 parts by weight of sodium hydroxide is added at 70 ℃, the mixture is stirred and reacted for 3 hours at 100 ℃, water is removed by reduced pressure distillation, petroleum ether is used for washing, and the mixture is dried to obtain the styrene-phenyl phosphate phenolic resin.
100 Parts by weight of maleic anhydride modified epoxy acrylate and 20 parts by weight of styrene-phenyl phosphate phenolic resin are added into 120 parts by weight of water, uniformly dispersed, then 60 parts by weight of pentaerythritol triacrylate as an active diluent, 0.8 part by weight of defoamer and 0.4 part by weight of dispersing agent are added, uniformly dispersed, and finally 8 parts by weight of photoinitiator Irgacure2959 is added, and the mixture is preserved in a dark place, so that the photocuring aqueous epoxy acrylate emulsion is obtained.
Comparative example 1
100 Parts by weight of maleic anhydride modified epoxy acrylate is added into 120 parts by weight of water to be uniformly dispersed, then 25 parts by weight of tripropylene glycol diacrylate as a reactive diluent, 0.5 part by weight of defoamer and 0.1 part by weight of dispersant are added to be uniformly dispersed, and finally 3 parts by weight of photoinitiator benzophenone is added to be preserved in a dark place to obtain the photo-curing aqueous epoxy acrylate emulsion.
Comparative example 2
100 Parts by weight of phenol and 48 parts by weight of formaldehyde-containing aqueous solution (37% by mass) are uniformly mixed, 3 parts by weight of sodium hydroxide is added at 60 ℃, the mixture is stirred at 100 ℃ for reaction for 3 hours, water is removed by reduced pressure distillation, petroleum ether is washed, and the phenolic resin is obtained by drying.
100 Parts by weight of maleic anhydride modified epoxy acrylate and 1 part by weight of phenolic resin are added into 120 parts by weight of water to be uniformly dispersed, then 25 parts by weight of tripropylene glycol diacrylate as an active diluent, 0.5 part by weight of defoamer and 0.1 part by weight of dispersing agent are added to be uniformly dispersed, and finally 3 parts by weight of photoinitiator benzophenone is added to be preserved in a dark place to obtain the photocuring water-based epoxy acrylate emulsion.
Comparative example 3
Adding 100 weight parts of 4-vinylbenzaldehyde and 160 weight parts of tyrosine into toluene, carrying out reflux reaction at 100 ℃ for 4 hours, cooling to room temperature, adding 150 weight parts of sodium borohydride and ethanol solvent, reacting for 8 hours, distilling under reduced pressure to remove the solvent, washing with petroleum ether, recrystallizing with ethanol to obtain an intermediate 1 with a structural formula of
100 Parts by weight of phenol, 20 parts by weight of intermediate 1 and an aqueous solution (mass fraction: 37%) containing 55 parts by weight of formaldehyde are uniformly mixed, 3 parts by weight of sodium hydroxide is added at 60 ℃, the mixture is stirred at 100 ℃ for reaction for 3 hours, water is removed by reduced pressure distillation, petroleum ether is washed, and the mixture is dried to obtain the styryl phenolic resin.
100 Parts by weight of maleic anhydride modified epoxy acrylate and 1 part by weight of styryl phenolic resin are added into 120 parts by weight of water, the mixture is uniformly dispersed, then 25 parts by weight of tripropylene glycol diacrylate as an active diluent, 0.5 part by weight of defoamer and 0.1 part by weight of dispersant are added, the mixture is uniformly dispersed, and finally 3 parts by weight of photoinitiator benzophenone is added, and the mixture is preserved in a dark place, so that the photocuring aqueous epoxy acrylate emulsion is obtained.
And (3) placing the photo-curing aqueous epoxy acrylate emulsion in a dark place for 1-30 days, and observing the emulsion state.
Table 1 photo-curing waterborne epoxy acrylate emulsion State test
The styrene-phenyl phosphate phenolic resin added in each embodiment of the invention contains hydrophilic carboxyl groups, so that the dispersibility of the phenolic resin in water is improved, and the stability of the aqueous epoxy acrylate emulsion is not affected.
The phenolic resin added in comparative example 2 and the styryl phenolic resin added in comparative example 3 do not contain hydrophilic carboxyl groups, so that the dispersibility and the solubility of the phenolic resin in the emulsion are poor, a large amount of precipitate is formed, and the storage stability of the emulsion is seriously affected.
Uniformly coating the photo-curing aqueous epoxy acrylate emulsion on the surface of a glass plate, improving an ultraviolet curing agent, and irradiating for 60s to obtain the epoxy acrylate coating. The hardness of the coating was tested according to the method of GB/T6739-2006. Impact resistance was measured according to the method of GB/T1732-2020.
TABLE 2 epoxy acrylate coating Performance test
| Hardness of | Impact resistance (cm) | |
| Example 1 | 3H | 40 |
| Example 2 | 5H | 50 |
| Example 3 | 5H | 50 |
| Example 4 | 4H | 50 |
| Comparative example 1 | 1H | 30 |
| Comparative example 2 | 1H | 20 |
| Comparative example 3 | 3H | 40 |
The flame retardant properties of the epoxy acrylate coating were measured according to GB/T2406.1-2008 and UL-94 fire rating methods.
The styrene-phenyl phosphate phenolic resin added in each embodiment of the invention contains active styrene groups, and carries out cross-linking polymerization reaction with epoxy acrylate and active diluent under the action of ultraviolet light and a photoinitiator, so that the phenolic resin is grafted into the molecular chain of the epoxy acrylate resin, the interfacial binding force of the phenolic resin and the epoxy acrylate resin is enhanced, the phenolic resin has good enhancement effect, and the hardness and the impact resistance of the epoxy acrylate coating are improved.
Comparative example 1 was poor in mechanical properties without the addition of a styrene-phenyl phosphate based phenolic resin; the phenolic resin added in comparative example 2 contains no alkenyl groups and cannot be crosslinked and polymerized with epoxy acrylate, so that the phenolic resin has poor dispersibility in the epoxy acrylate resin, and the phenolic resin and the epoxy acrylate resin are incompatible, and the hardness and impact resistance of the coating cannot be effectively improved.
The styrene-based phenolic resin added in the comparative example 3 contains active styrene groups, and can carry out crosslinking polymerization reaction with epoxy acrylate and an active diluent, so that the phenolic resin has a good reinforcing effect, and the hardness and impact resistance of the coating are improved.
Table 3 epoxy acrylate coating flame retardant performance test
| Limiting oxygen index (%) | UL-94 rating | |
| Example 1 | 26.4 | V-1 |
| Example 2 | 27.1 | V-0 |
| Example 3 | 28.5 | V-0 |
| Example 4 | 30.2 | V-0 |
| Comparative example 1 | 21.8 | V-2 |
| Comparative example 2 | 22.8 | V-2 |
| Comparative example 3 | 24.6 | V-2 |
According to the invention, the styrene-phenyl phosphate phenolic resin is grafted into the epoxy acrylate resin matrix, the phenolic resin has good high temperature resistance and burning char formation, and the phosphate structure is used as a flame retardant, and the phosphoric acid compound generated by pyrolysis can further promote dehydration of the phenolic resin and the coating group to char, so that a continuous compact char layer is formed on the coating matrix, and good effects of inhibiting burning and flame retardance are achieved.
The phenolic resins added in comparative example 2 and comparative example 3 do not contain a phosphate flame retardant structure, and the flame retardant performance of the epoxy acrylate coating cannot be effectively improved.
Claims (5)
1. The preparation method of the photo-curing aqueous epoxy acrylate emulsion is characterized by comprising 100 parts by weight of maleic anhydride modified epoxy acrylate, 3-8 parts by weight of photoinitiator, 25-60 parts by weight of reactive diluent, 1-20 parts by weight of styrene-phenyl phosphate phenolic resin, 0.3-0.8 part by weight of defoamer and 0.1-0.4 part by weight of dispersant;
the preparation method of the photo-curing aqueous epoxy acrylate emulsion comprises the following steps:
Adding maleic anhydride modified epoxy acrylate and styrene-phenyl phosphate phenolic resin into water, dispersing uniformly, then adding an active diluent, a defoaming agent and a dispersing agent, dispersing uniformly, finally adding a photoinitiator, and preserving in a dark place to obtain a photo-curing aqueous epoxy acrylate emulsion;
the preparation method of the styrene-phenyl phosphate phenolic resin comprises the following steps:
s1, adding 4-vinyl benzaldehyde and tyrosine into toluene, carrying out reflux reaction for 2-4 hours at 100-115 ℃, cooling to room temperature, adding sodium borohydride and ethanol, reacting for 8-16 hours, removing a solvent, washing, and recrystallizing to obtain an intermediate 1;
S2, adding the intermediate 1, bromoethyl diphenyl phosphate and potassium carbonate into acetonitrile, stirring for reaction, removing a solvent, washing, and recrystallizing to obtain a phenol intermediate containing phosphate and styrene groups;
s3, mixing phenol, a phenol intermediate and a formaldehyde aqueous solution uniformly, adding sodium hydroxide into the mixture at 60-70 ℃, stirring the mixture uniformly to react, removing water, washing and drying the mixture to obtain styrene-phenyl phosphate phenolic resin;
The weight ratio of the 4-vinyl benzaldehyde to the tyrosine is 100 (130-180);
The weight ratio of the intermediate 1 to the bromoethyl diphenyl phosphate to the potassium carbonate is 100 (110-140) (160-220);
The weight ratio of the phenol to the phenol intermediate to formaldehyde is 100 (20-65) to 55-70.
2. The method for preparing a photocurable aqueous epoxy acrylate emulsion according to claim 1 wherein said reactive diluent comprises at least one of tripropylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, tripropylene glycol diacrylate.
3. The method for preparing a photo-curable aqueous epoxy acrylate emulsion according to claim 1 wherein said initiator comprises at least one of Irgacure2959, irgacure1173, benzophenone.
4. The method for preparing the photo-curing aqueous epoxy acrylate emulsion according to claim 1, wherein the reaction temperature is controlled to be 35-50 ℃ and the reaction time is controlled to be 12-18h in the step S2.
5. The method for preparing the photo-curing aqueous epoxy acrylate emulsion according to claim 1, wherein the reaction temperature is controlled to be 90-100 ℃ and the reaction time is controlled to be 2-4h in the step S3.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1363617A (en) * | 2001-01-12 | 2002-08-14 | 财团法人工业技术研究院 | Photosensitive phosphotidic phenol resin, its composition and its preparing process |
| CN109749619A (en) * | 2018-12-28 | 2019-05-14 | 东来涂料技术（上海）股份有限公司 | A kind of super-hydrophobicity and stain resistance waterborne UV coating and preparation method thereof |
| CN111349377A (en) * | 2020-04-28 | 2020-06-30 | 中科院广州化学有限公司 | Organic silicon modified waterborne epoxy acrylate UV curing coating and preparation and application thereof |
| CN115074017A (en) * | 2021-03-12 | 2022-09-20 | 北京钢研新冶环科科技有限公司 | UV metal exterior wall coating for metal carved board and preparation method thereof |
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| WO2003029322A1 (en) * | 2001-09-28 | 2003-04-10 | Mitsui Chemicals, Inc. | Curing agent composition for epoxy resins, epoxy resin composition and use thereof |
| WO2020153048A1 (en) * | 2019-01-21 | 2020-07-30 | Dic株式会社 | Phenolic hydroxyl group-containing resin, photosensitive composition, resist film, curable composition, and cured product |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1363617A (en) * | 2001-01-12 | 2002-08-14 | 财团法人工业技术研究院 | Photosensitive phosphotidic phenol resin, its composition and its preparing process |
| CN109749619A (en) * | 2018-12-28 | 2019-05-14 | 东来涂料技术（上海）股份有限公司 | A kind of super-hydrophobicity and stain resistance waterborne UV coating and preparation method thereof |
| CN111349377A (en) * | 2020-04-28 | 2020-06-30 | 中科院广州化学有限公司 | Organic silicon modified waterborne epoxy acrylate UV curing coating and preparation and application thereof |
| CN115074017A (en) * | 2021-03-12 | 2022-09-20 | 北京钢研新冶环科科技有限公司 | UV metal exterior wall coating for metal carved board and preparation method thereof |
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