CN117986588A - Photocurable tertiary amine polysiloxane polyacrylate resin, coating and preparation method thereof - Google Patents
Photocurable tertiary amine polysiloxane polyacrylate resin, coating and preparation method thereof Download PDFInfo
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- CN117986588A CN117986588A CN202410183322.8A CN202410183322A CN117986588A CN 117986588 A CN117986588 A CN 117986588A CN 202410183322 A CN202410183322 A CN 202410183322A CN 117986588 A CN117986588 A CN 117986588A
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- tertiary amine
- polysiloxane
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- 150000003512 tertiary amines Chemical class 0.000 title claims abstract description 88
- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 87
- -1 polysiloxane Polymers 0.000 title claims abstract description 79
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 57
- 238000000576 coating method Methods 0.000 title claims abstract description 46
- 239000011248 coating agent Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000000016 photochemical curing Methods 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 239000003960 organic solvent Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 14
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000007822 coupling agent Substances 0.000 claims abstract description 12
- 229920002545 silicone oil Polymers 0.000 claims abstract description 12
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 9
- 239000002981 blocking agent Substances 0.000 claims abstract description 6
- 239000010936 titanium Substances 0.000 claims description 34
- 150000003141 primary amines Chemical group 0.000 claims description 29
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 20
- 229910052719 titanium Inorganic materials 0.000 claims description 20
- LTYBJDPMCPTGEE-UHFFFAOYSA-N (4-benzoylphenyl) prop-2-enoate Chemical compound C1=CC(OC(=O)C=C)=CC=C1C(=O)C1=CC=CC=C1 LTYBJDPMCPTGEE-UHFFFAOYSA-N 0.000 claims description 15
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 14
- 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 14
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- 230000035484 reaction time Effects 0.000 claims description 10
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 claims description 9
- 229920000178 Acrylic resin Polymers 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 claims description 5
- AFGLOYYSQHFZDG-UHFFFAOYSA-M C(C=C)(=O)O[Ti] Chemical compound C(C=C)(=O)O[Ti] AFGLOYYSQHFZDG-UHFFFAOYSA-M 0.000 claims description 5
- 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 5
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 5
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 4
- 229940090181 propyl acetate Drugs 0.000 claims description 4
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 claims description 2
- SZEBGAQWWSUOHT-UHFFFAOYSA-N 2-(4-bromophenoxy)acetic acid Chemical compound OC(=O)COC1=CC=C(Br)C=C1 SZEBGAQWWSUOHT-UHFFFAOYSA-N 0.000 claims description 2
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 claims description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 2
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 2
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 claims description 2
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 claims description 2
- 125000006606 n-butoxy group Chemical group 0.000 claims description 2
- 238000001723 curing Methods 0.000 abstract description 10
- 239000002210 silicon-based material Substances 0.000 abstract description 7
- 238000003756 stirring Methods 0.000 abstract description 7
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract 2
- 239000008199 coating composition Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 230000002209 hydrophobic effect Effects 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000006845 Michael addition reaction Methods 0.000 description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 7
- 238000005286 illumination Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 5
- 238000002329 infrared spectrum Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000009423 ventilation Methods 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 229920013822 aminosilicone Polymers 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000003517 fume Substances 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 239000005028 tinplate Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011086 glassine Substances 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
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- DRRZZMBHJXLZRS-UHFFFAOYSA-N n-[3-[dimethoxy(methyl)silyl]propyl]cyclohexanamine Chemical compound CO[Si](C)(OC)CCCNC1CCCCC1 DRRZZMBHJXLZRS-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Silicon Polymers (AREA)
Abstract
The invention belongs to the technical field of advanced organic silicon materials, and discloses a photo-curing tertiary amine polysiloxane polyacrylate resin, a coating and a preparation method thereof. The preparation method of the photo-curing tertiary amine polysiloxane polyacrylate resin comprises the following steps: uniformly mixing an aminosilane coupling agent containing primary amine groups and a blocking agent, heating and stirring for reaction, adding hydroxyl-terminated silicone oil for continuous reaction, distilling under reduced pressure to obtain primary amine-containing oligosiloxane, and adding the oligosiloxane into an organic solvent and polyacrylate for reaction to obtain tertiary amine polysiloxane polyacrylate resin. The cured coating is obtained by mixing the synthesized high-stability tertiary amine polysiloxane polyacrylate resin with alkoxy (methyl) acryloxytitanium and quickly curing under the condition of adding a photoinitiator. The tertiary amine polysiloxane-polyacrylate resin prepared by the invention has good stability, and the cured coating of the coating composition after being irradiated by ultraviolet light is high in hardness and has good hydrophobicity.
Description
Technical Field
The invention belongs to the field of photo-curing advanced organic silicon materials, and particularly relates to a photo-curing tertiary amine polysiloxane polyacrylate resin, a coating and a preparation method thereof.
Background
The photo-curing advanced organosilicon material has the advantages of high molecular polymer, environmental protection and the like, does not need to be cured by heat curing, moisture curing and other complex and complicated curing modes like other materials, can be rapidly crosslinked and cured only under ultraviolet radiation, has the advantages of high efficiency, green environmental protection and the like, and is one of research and development hot spots in various research and development directions. The acrylic acid-esterified organic silicon material is one of main development directions of advanced photo-curing organic silicon materials, and has the advantages of high photo-curing activity, high curing rate, stable cured material, oxidation resistance, polymerization inhibition capability, high reactivity, easiness in preparation, low cost, controllable structure, high acid-base resistance, high temperature resistance and the like. Is the photo-curing organic silicon material with the largest dosage and the most research at the present stage. However, the acrylic resin has poor stability and easy crosslinking due to more double bonds, and can be crosslinked into colloid by itself after long storage time. The hardness of the organic silicon material after photo-curing is generally about H-2H, and the organic silicon material can only meet the practical production and life applications of the requirements of low-hardness coating, but is limited in the fields requiring high-hardness coating. The existing preparation methods such as hydrolysis-polycondensation method, free radical polymerization method, hydrosilylation method, michael addition method, isocyanate method and other synthesis methods are all single functional group reactions, and the application range is limited. In 2017, xu Kang et al modified acrylic resin with amino silicone oil to improve impact resistance and adhesion, but after adding 3% amino silicone oil, the coating hardness was reduced from 3H to 6B. In 2009 Liu Gongbo, lin Feng et al prepared photocurable silicon-containing modified acrylates by the michael addition reaction of N-cyclohexyl-3-aminopropyl methyldimethoxysilane (CAMS) with pentaerythritol triacrylate (PETA). The coating hardness was 4H, but was hydrophilic due to the bare hydroxyl groups. Therefore, it remains a challenge to produce coatings that have excellent properties in terms of hardness, hydrophobicity, etc.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the primary purpose of the invention is to provide a preparation method of a photo-curing tertiary amine polysiloxane polyacrylate resin.
It is yet another object of the present invention to provide a photocurable tertiary amine polysiloxane polyacrylate resin.
It is still another object of the present invention to provide a photocurable titanium reinforced tertiary amine type polysiloxane polyacrylate resin coating.
The invention further aims to provide a preparation method of the photo-cured titanium reinforced tertiary amine type polysiloxane polyacrylate resin coating.
The aim of the invention is achieved by the following technical scheme:
a preparation method of photo-curing tertiary amine polysiloxane polyacrylate resin comprises the following steps:
(1) Uniformly mixing an aminosilane coupling agent containing primary amine groups and a blocking agent, reacting, adding hydroxyl-terminated silicone oil, continuously reacting, and distilling under reduced pressure to obtain primary amine-containing oligosiloxane;
(2) And (3) adding the primary amine-containing oligosiloxane obtained in the step (1) into an organic solvent and polyacrylate for reaction to obtain the photo-curing tertiary amine polysiloxane polyacrylate resin.
Preferably, the aminosilane coupling agent containing primary amine groups in the step (1) is at least one of 3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyl methyldiethoxysilane and 3-aminopropyl methyldimethoxysilane;
The end capping agent in the step (1) is at least one of trimethylethoxysilane and methoxytrimethylsilane;
The hydroxyl-terminated silicone oil in the step (1) is industrial-grade pure hydroxyl-terminated silicone oil with the average molecular weight of 300-2000.
Preferably, the molar ratio of the primary amine-containing aminosilane coupling agent and the capping agent of step (1) is 1:0.5 to 1, more preferably 1:0.9 to 1;
The molar ratio of the hydroxyl-terminated silicone oil to the primary amine-containing aminosilane coupling agent in the step (1) is 1:1 to 2;
the reaction temperature in the step (1) is 40-55 ℃, the reaction time is 0.5-2 h, and the continuous reaction time is 2-4 h.
Preferably, the polyacrylate in the step (2) is at least one of trimethylolpropane triacrylate, pentaerythritol tetraacrylate and pentaerythritol triacrylate;
The organic solvent in the step (2) is at least one of ethyl acetate, propyl acetate, butyl acetate and benzotrifluoride.
Preferably, the reaction temperature in the step (2) is 50-60 ℃ and the reaction time is 1-6 h;
The temperature of the reduced pressure distillation in the step (1) is 50-60 ℃, and the vacuum degree is minus 0.08 to minus 0.095MPa;
The molar ratio of the polyacrylate in the step (2) to the aminosilane coupling agent containing primary amine groups in the step (1) is 1-2: 1, a step of;
the mass of the organic solvent in the step (2) is 10% -40% of the mass of the total reaction system, and the mass of the total reaction system is the mass sum of the amino silane coupling agent containing primary amine groups, the end capping agent, the hydroxyl-terminated silicone oil, the polyacrylate and the organic solvent.
A photo-curing tertiary amine polysiloxane polyacrylate resin is prepared by the method.
The light-cured titanium reinforced tertiary amine type polysiloxane polyacrylic resin coating comprises the light-cured tertiary amine type polysiloxane polyacrylic resin, and comprises the following components:
Tertiary amine polysiloxane polyacrylate resin, alkoxy (methyl) acryloxytitanium, photoinitiator and organic solvent;
wherein the amount of the photoinitiator is 2 to 9 weight percent of the mass of the tertiary amine type polysiloxane acrylic resin, and the amount of the alkoxy (methyl) acryloxytitanium is 1 to 25 weight percent of the mass of the tertiary amine type polysiloxane acrylic resin, and more preferably 2.5 to 10 weight percent.
Preferably, the alkoxy in the alkoxy (methyl) acryloyloxy titanium (RO) mTi(OOCC(R`)＝CH2)n comprises isopropoxy and n-butoxy, wherein 2 is more than or equal to m is more than or equal to 0; (meth) acryloyloxy includes methacryloyloxy and acryloyloxy, 4.gtoreq.n.gtoreq.2;
The alkoxy (methyl) acryloyloxy titanium is a product obtained by reacting isopropyl titanate and methacrylic acid according to a molar ratio of 1:2, wherein the reaction temperature is 40-70 ℃ and the reaction time is 1-5 h;
the photoinitiator is a type I photoinitiator or a type II photoinitiator;
The organic solvent is at least one of butyl acetate, propyl acetate, ethyl acetate and benzotrifluoride.
The preparation method of the photo-cured titanium reinforced tertiary amine polysiloxane polyacrylate resin coating comprises the following steps:
Dissolving tertiary amine type polysiloxane polyacrylate resin and a photoinitiator in an organic solvent, adding alkoxy (methyl) acryloxytitanium, uniformly mixing, volatilizing the solvent, and performing photo-curing to obtain the photo-curing titanium reinforced tertiary amine type polysiloxane polyacrylate resin coating.
Preferably, the ultraviolet light used for photo-curing has the wavelength of 365nm, the power of 2kW and the irradiation time of 30-50 s;
the photoinitiator is photoinitiator 754 or 4-acryloxybenzophenone 4-BPA.
The mechanism of the invention is as follows:
The preparation method comprises the steps of firstly mixing and heating an aminosilane coupling agent and a blocking agent to obtain a reaction raw material, then adding low-molecular-weight hydroxyl-terminated silicone oil to carry out hydrolytic condensation to obtain oligosiloxane with primary amine groups at two ends (as shown in a structure (I) of a formula (1)), and carrying out Michael addition on-N-H on the oligosiloxane and trimethylolpropane triacrylate with the molar quantity twice that of the oligosiloxane to form tertiary amine polysiloxane-polyacrylic resin (as shown in a structure (II) of the formula (1)). Mixing the modified polyurethane with alkoxy acryloyloxy titanium (RO) mTi(OOCC(R`)＝CH2)n, adding a photoinitiator, and then carrying out random combined crosslinking on the double bond (as shown in a formula (2) structure (III)) of acryloyloxy titanium (RO) mTi(OOCC(R`)＝CH2)n and the double bond (as shown in a formula (2) structure (IV)) of tertiary amine polysiloxane polyacrylate resin under the action of the photoinitiator (the crosslinking mode of the formula (2) is only a part and only one of the double bonds), so that a dense network structure is formed, and the hardness of the photocuring coating is improved.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) The synthesis method is simple, and the tertiary amine polysiloxane polyacrylate resin can be prepared directly by using hydrolytic condensation and Michael addition without adding a catalyst.
(2) The trimethylolpropane triacrylate has more double bonds, the crosslinking degree is high, and the mechanical property can be ensured.
(3) The hardness and hydrophobicity of the coating are further enhanced by adding titanium alkoxy-acryloyloxy (RO) mTi(OOCC(R`)＝CH2)n, the pencil hardness is 4H, the water contact angle can reach 92.31 degrees, and meanwhile, the stability and the peeling strength are not greatly influenced (shown in figures 9 and 10).
(4) The end capping agent is used for treating the reaction raw materials, so that the stability of the synthesized product is greatly improved, the sample is not solidified within three months, the viscosity is not obviously changed, and the problems of multiple double bonds and easy crosslinking of the polyacrylic resin are solved.
(5) The prepared tertiary amine polysiloxane polyacrylate resin can be suitable for type I photoinitiators and type II photoinitiators.
Drawings
FIG. 1 is a HNMR (CDCl 3) chart of a starting material of 3-aminopropyl methyldimethoxy silane (sample 1) and an oligosiloxane containing primary amines at both ends (sample 2) obtained in step (2) of example 1.
FIG. 2 is a HNMR (CDCl 3) diagram of the raw material trimethylolpropane triacrylate (sample 3) and the tertiary amine type oligosiloxane-polyacrylic resin of step (2) (sample 4).
FIG. 3 is a pencil hardness test result of the tertiary amine type polysiloxane polyacrylate resin coating without titanium reinforcement in comparative example 1.
FIG. 4 shows the pencil hardness test results of the titanium reinforced tertiary amine type polysiloxane polyacrylate resin coating in step (3) of example 1.
FIG. 5 is a pencil hardness test result of the tertiary amine polysiloxane polyacrylate resin coating without titanium reinforcement of comparative example 3.
FIG. 6 shows the pencil hardness test result of the titanium reinforced tertiary amine type polysiloxane polyacrylate resin coating in step (3) of example 2.
FIG. 7 shows the hydrophobic angle test after comparative example 1 was not modified with Ti and example 1 was modified with Ti.
FIG. 8 shows the hydrophobic angle test after comparative example 3 was not modified with Ti and example 2 was modified with Ti.
Fig. 9 shows the peel force test result before Ti addition in example 1.
FIG. 10 shows the peel force test results after Ti addition in example 1.
FIG. 11 is an infrared spectrum of isopropyl titanate.
FIG. 12 is an infrared spectrum of titanium oxyacryloyloxide.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but embodiments of the present invention are not limited thereto. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The reagents used in the examples are commercially available as usual unless otherwise specified.
Alkoxy (meth) acryloyloxy titanium is prepared by the following method:
0.1mol (28.42 g) of isopropyl titanate (infrared spectrum is shown in FIG. 11) is added into a four-mouth bottle of a mechanical stirring device under the dry and ventilated environment, 0.2mol (17.22 g) of methacrylic acid is added into a dropping funnel, gradually dropwise added into the four-mouth bottle for reaction, the temperature is 50 ℃ for reaction for 1h, and then the temperature is raised to 60 ℃ for continuous reaction for 3h. The product (infrared spectrum, see figure 12) was taken out and cooled to room temperature, and the product was diluted to 5wt% using tetrahydrofuran as a solvent and stored to obtain the alkoxy (meth) acryloxytitanium required for the subsequent experiments. The alkoxy (meth) acryloyloxy titanium added after the experiment was a 5wt% solution. As is evident from a comparison of fig. 12 and fig. 11, a carbonyl stretching vibration peak of-c=o appears at 1720cm -1, and an unsaturated bond hydrocarbon vibration peak of-ch=ch-appears at 3340cm -1, which indicates that methacrylic acid is successfully substituted with isopropyl titanate, resulting in titanium (meth) acryloyloxy alkoxide.
The peel force test method is as follows:
The resin was coated on glassine paper and tested with a tesa7475 tape (25 mm) adhered to the coating using a 180 peel force tester (GB/T2792-1998).
Example 1
(1) To a 250mL four-necked flask with reflux, dropwise addition, stirring and temperature control in a hood environment where dryness was ensured were added 0.1mol (16.33 g) of 3-aminopropyl methyldimethoxysilane (sample 1) and 0.1mol (11.83 g) of trimethylethoxysilane as a capping agent, and the mixture was reacted at 50℃for 0.5 hours under nitrogen protection with stirring. Then 0.05mol (17 g) of hydroxyl-terminated polysiloxane is dripped into a four-necked flask for reaction, wherein the dripping time is 45min, and the reaction time is 3h. Sample 1 test HNMR: peaks with chemical shift values of 2.5-2.6 ppm are assigned to H peaks of CH 2CH2CH2-NH2 underlined CH 2 and peaks with chemical shift values of 3.6-3.7 ppm are assigned to H peaks of Si-OCH 3 underlined OCH 3.
(2) The temperature was raised to 60℃and distillation under reduced pressure was carried out for 30 minutes to remove by-products, the degree of vacuum under reduced pressure was-0.095 MPa, and the oligosiloxane (sample 2) having primary amines at both ends was obtained after distillation under reduced pressure. Taking out the oligosiloxane with primary amine, placing the oligosiloxane with primary amine into a dropping funnel, adding a uniform mixed solution of 0.2mol (59.26 g) of trimethylolpropane triacrylate (sample 3) and 20wt% (26 g) of butyl acetate into a four-mouth bottle under the condition of drying and ventilation, gradually dropping the oligosiloxane with primary amine into the four-mouth bottle for continuous reaction for 1h, continuously reacting for 2h after the dropping, reacting at 50 ℃, then raising the reaction temperature to 60 ℃ for 3h, reacting for 6h in total, and cooling to obtain the tertiary amine polysiloxane-polyacrylic resin (sample 4). HNMR of sample 2: peaks with chemical shift values of 2.5-2.6 ppm are assigned to H peaks of CH 2CH2CH2-NH2 underlined CH 2 and peaks with chemical shift values of 3.6-3.7 ppm are assigned to H peaks of Si-OCH 3 underlined OCH 3. Since H of CH 2 in CH 2-NH2 does not participate in the reaction, the H peak area is unchanged, and this is taken as a reference value 1, and it is apparent from fig. 1 that the ratio of the H peak area of CH 2 to the H peak area of OCH 3 is represented by 2:1 becomes 1 after the reaction: 1, the peak area of methoxy is reduced by half, which indicates that the methoxy and hydroxyl-terminated small molecular silicone oil is condensed successfully. Raw material trimethylolpropane triacrylate as sample 3 HNMR: peaks with chemical shift values of 5.7 to 5.8, 6.0 to 6.1, 6.3 to 6.4ppm are assigned to H peaks on CH 2 =CH-underlined double bonds, and peaks with chemical shift values of 0.8 to 0.9ppm are assigned to H peaks on CH 3-CH2 -underlined CH 3. The resulting tertiary amine oligosiloxane polyacrylate resin was used as HNMR for sample 4: peaks with chemical shift values of 5.8 to 5.9, 6.1 to 6.2, 6.3 to 6.4ppm are assigned to H peaks on CH 2 = CH-underlined double bonds, and peaks with chemical shift values of 0.9 to 1.0ppm are assigned to H peaks on CH 3-CH2 -underlined CH 3. As the trimethylolpropane triacrylate CH 3-CH2 -underlined CH 3 does not participate in the reaction in fig. 2, the H peak area is unchanged, and based on this as reference 1, it is obvious from fig. 2 that the ratio of the H peak on CH 2 =ch-underlined double bond to the H peak on CH 3-CH2 -underlined CH 3 is significantly reduced, which indicates that the double bond is consumed by successful Michael addition reaction of trimethylolpropane triacrylate with amino groups.
(3) Taking 10g of tertiary amine type oligosiloxane polyacrylic resin obtained in the step (2), dissolving 0.7g of photoinitiator 4-acryloyloxy benzophenone in 3g of butyl acetate, uniformly mixing the three materials, adding 5.0g of 5wt% alkoxy (methyl) acryloyloxy titanium (RO) mTi(OOCC(R`)＝CH2)n solution, uniformly mixing the three materials again, taking 1.0g of the mixture to coat on tin, coating the tin with the thickness of 30 mu m, and using an ultraviolet curing machine to carry out photo-curing after the solvent volatilizes, wherein the wavelength of ultraviolet light is 365nm, the power is 2kW, and the illumination time is 40s, so as to obtain the titanium reinforced tertiary amine type polysiloxane polyacrylic resin coating after photo-curing. The coating was subjected to pencil hardness, peel force, hydrophobic angle test, and stability observation was performed on the tertiary amine type polysiloxane polyacrylate resin component obtained in step (2). The results obtained are as follows: the pencil hardness was 4H (see FIG. 4), the peel force was about 120N, the water contact angle was 92.31 ° (see FIG. 7), the sample did not solidify within three months, and the viscosity did not change significantly, and the peel force of the tertiary amine polysiloxane-polyacrylate resin component was about 106N.
Comparative example 1
A tertiary amine polysiloxane polyacrylate resin without the addition of the blocking agent trimethylethoxysilane was prepared again as in steps (1) - (2) of example 1 (without the addition of trimethylethoxysilane having no effect on the hardness of the coating). 10g of the prepared tertiary amine polysiloxane-polyacrylate resin is taken, 0.7g of the photoinitiator 4-acryloxybenzophenone is dissolved in 3g of butyl acetate, after the three materials are uniformly mixed, 1.0g of the tertiary amine polysiloxane-polyacrylate resin is coated on tin plate, the thickness is 30 mu m, after the solvent volatilizes, an ultraviolet light curing machine is used for photo-curing, the wavelength of the ultraviolet light is 365nm, the power is 2kW, and the illumination time is 40s, so that the cured tertiary amine polysiloxane-polyacrylate resin coating is obtained. The coatings were tested for pencil hardness, hydrophobic angle, and stability observations were made with respect to the components of the tertiary amine polysiloxane-polyacrylate resin product that was prepared again. The results obtained are as follows: pencil hardness was 2H (see fig. 3), water contact angle was 84.38 ° (see fig. 7), and the product solidified into a solid within 2 days.
Comparative example 2
Taking 10g of tertiary amine polysiloxane polyacrylate resin obtained in the step (2) of the example 1 as a sample 1, dividing the sample into two equal parts, and respectively adding a photoinitiator 754 (type I) and a photoinitiator 4-acryloxybenzophenone (type II) for photo-curing;
and (2) taking 10g of trimethylolpropane triacrylate as a raw material used in the step (2), dividing the raw material into two equal parts, and respectively adding a photoinitiator 754 (type I) and a photoinitiator 4-acryloxybenzophenone (type II) for photo-curing.
As a result, both groups of sample 1 were successfully cured, one group of sample 2 with the addition 754 of the photoinitiator was successfully cured, and one group with the addition of 4-acryloxybenzophenone was not cured. This further demonstrates that the successful Michael addition of trimethylolpropane triacrylate to an amino group results in a tertiary amine structure, and that the product is suitable for both cleavage type (I) and hydrogen abstraction type (II) photoinitiators due to the unique tertiary amine structure.
Example 2
(1) To a 250mL four-necked flask with reflux, dropwise addition, stirring and temperature control in a fume hood environment ensuring dryness, 0.1mol (16.33 g) of 3-aminopropyl methyldimethoxy silane and 0.1mol (11.83 g) of trimethylethoxy silane as a capping agent were added, and the mixture was reacted at 50℃for 0.5 hours under nitrogen protection with stirring. Then 0.05mol (17 g) of hydroxyl-terminated polysiloxane is added dropwise into the four-necked flask for reaction, wherein the dropwise adding time is 45min, and the reaction time is 3h.
(2) Heating to 60deg.C, distilling under reduced pressure for 30min to remove byproduct, and distilling under reduced pressure to give oligosiloxane containing primary amine at two ends; taking out the oligosiloxane with primary amine, placing the oligosiloxane with primary amine into a dropping funnel, adding a uniform mixed solution of 0.2mol (59.26 g) of trimethylolpropane triacrylate and 20wt% (26 g) of butyl acetate into a four-mouth bottle under the condition of drying and ventilation, gradually dripping the oligosiloxane with primary amine into the four-mouth bottle for continuous reaction for 1h, continuously reacting for 2h after dripping, reacting at 50 ℃, then continuously reacting at 60 ℃ for 3h, reacting for 6h in total, and cooling to obtain the tertiary amine polysiloxane-poly-acrylic resin.
(3) 8G of tertiary amine type oligosiloxane polyacrylic resin obtained in the step (2) is taken, 0.56g of photoinitiator 4-acryloyloxy benzophenone is dissolved in 2g of butyl acetate, after the three materials are uniformly mixed, 7g of 5wt% alkoxy (methyl) acryloyloxy titanium (RO) mTi(OOCC(R`)＝CH2)n solution is added, after the three materials are uniformly mixed again, 1.0g of tertiary amine type oligosiloxane polyacrylic resin is taken to be coated on tin plate, the thickness is 30 mu m, after the solvent volatilizes, an ultraviolet light curing machine is used for photo-curing, the wavelength of the ultraviolet light is 365nm, the power is 2kW, and the illumination time is 40s, so that the photo-cured titanium reinforced tertiary amine type polysiloxane polyacrylic resin coating is obtained. The coating was tested for pencil hardness, hydrophobic angle, and stability observations were made for the tertiary amine polysiloxane-polyacrylate resin obtained in step (2). The results obtained are as follows: the pencil hardness was 4H (see fig. 6), the water contact angle was 91.44 ° (see fig. 8), the sample did not solidify within three months, and the viscosity did not change significantly.
Comparative example 3
The tertiary amine polysiloxane polyacrylate resin without the addition of the end-capping agent trimethylethoxysilane was prepared again as in steps (1) - (2) of example 2.8 g of the prepared tertiary amine polysiloxane-polyacrylate resin is taken, 0.56g of the photoinitiator 4-acryloxybenzophenone is dissolved in 2g of butyl acetate, after the three materials are uniformly mixed, 1.0g of the tertiary amine polysiloxane-polyacrylate resin is coated on tin, after the solvent volatilizes, an ultraviolet curing machine is used for photo-curing, the wavelength of the ultraviolet light is 365nm, the power is 2kW, the illumination time is 40s, the thickness is 30 mu m, and the cured tertiary amine polysiloxane-polyacrylate resin coating is obtained. The coatings were tested for pencil hardness, hydrophobic angle, and stability observations were made for the tertiary amine polysiloxane-polyacrylate resin products that were re-made. The results obtained are as follows: pencil hardness was 2H (see fig. 5), water contact angle was 85.82 ° (see fig. 8), and the product solidified to a solid within 3 days.
Comparative example 4
Taking 10g of tertiary amine polysiloxane polyacrylate resin obtained in the step (2) of the example 2 as a sample 3, dividing the sample into two equal parts, and respectively adding a photoinitiator 754 (type I) and a photoinitiator 4-acryloxybenzophenone (type II) for photo-curing;
Taking 10g of trimethylolpropane triacrylate as a sample 4, dividing the sample into two equal parts, and adding a photoinitiator 754 (type I) and a photoinitiator 4-acryloxybenzophenone (type II) respectively for photo-curing.
As a result, both groups of sample 3 were successfully cured, one group of sample 4 with the addition 754 of the photoinitiator was successfully cured, and one group with the addition of 4-acryloxybenzophenone was not cured. This further demonstrates that the successful Michael addition of trimethylolpropane triacrylate to an amino group results in a tertiary amine structure, and that the product is suitable for both type I and type II photoinitiators due to the unique tertiary amine structure.
Example 3
(1) To a 250mL four-necked flask with reflux, dropwise addition, stirring and temperature control in a fume hood environment ensuring dryness, 0.1mol (22.14 g) of 3-aminopropyl triethoxysilane, 0.1mol (11.83 g) of trimethylethoxysilane as a blocking agent were added, and the mixture was reacted at 50℃for 0.5 hours under nitrogen protection with stirring. Then 0.05mol (17 g) of hydroxyl-terminated polysiloxane is dripped into a four-necked flask for reaction, wherein the dripping time is 45min, and the reaction time is 3h.
(2) And (3) heating to 60 ℃, carrying out reduced pressure distillation for 30min, removing byproducts, and carrying out reduced pressure distillation to obtain the oligosiloxane with primary amine at two ends, wherein the reduced pressure vacuum degree is-0.095 MPa. Taking out the oligosiloxane with primary amine, placing the oligosiloxane into a dropping funnel, adding a uniform mixed solution of 0.2mol (59.66 g) pentaerythritol triacrylate and 20wt% (28 g) butyl acetate into a four-mouth bottle under the condition of drying and ventilation, gradually dripping the oligosiloxane with primary amine into the four-mouth bottle for continuous reaction for 1h, continuously reacting for 2h after dripping, reacting at 50 ℃, then continuously reacting for 3h after the reaction temperature is raised to 60 ℃, reacting for 6h in total, and cooling to obtain the tertiary amine polysiloxane-poly-acrylic resin.
(3) Taking 10g of tertiary amine type oligosiloxane polyacrylic resin obtained in the step (2), dissolving 0.7g of photoinitiator 4-acryloyloxy benzophenone in 3g of butyl acetate, uniformly mixing the three materials, adding 5.0g of 5wt% alkoxy (methyl) acryloyloxy titanium (RO) mTi(OOCC(R`)＝CH2)n solution, uniformly mixing the three materials again, taking 1.0g of the mixture to coat on tin, coating the tin with the thickness of 30 mu m, and using an ultraviolet curing machine to carry out photo-curing after the solvent volatilizes, wherein the wavelength of ultraviolet light is 365nm, the power is 2kW, and the illumination time is 40s, so as to obtain the titanium reinforced tertiary amine type polysiloxane polyacrylic resin coating after photo-curing. The coating was subjected to pencil hardness, hydrophobic angle test, and stability observation was performed on the tertiary amine type polysiloxane-polyacrylate resin component obtained in step (2). The results obtained are as follows: the pencil hardness was 4H, the water contact angle was 92.72 °, the sample did not solidify within three months, and the viscosity did not change significantly.
Comparative example 5
A tertiary amine polysiloxane polyacrylate resin without the addition of the end-capping agent trimethylethoxysilane was prepared again as in example 3 steps (1) - (2). 10g of the prepared tertiary amine polysiloxane-polyacrylate resin is taken, 0.7g of the photoinitiator 4-acryloxybenzophenone is dissolved in 3g of butyl acetate, after the three materials are uniformly mixed, 1.0g of the tertiary amine polysiloxane-polyacrylate resin is coated on tin, after the solvent volatilizes, an ultraviolet curing machine is used for photo-curing, the wavelength of the ultraviolet light is 365nm, the power is 2kW, the illumination time is 40s, the thickness is 30 mu m, and the cured tertiary amine polysiloxane-polyacrylate resin coating is obtained. The coatings were tested for pencil hardness, hydrophobic angle, and stability observations were made for the tertiary amine polysiloxane-polyacrylate resin products that were re-made. The results obtained are as follows: the pencil hardness was 2H and the water contact angle was 88.32 °, the product solidified to a solid within 5 days.
Comparative example 6
The tertiary amine polysiloxane polyacrylate resin prepared in the steps (1) - (2) of example 3 was taken. Taking 10g of tertiary amine type polysiloxane polyacrylic resin, adding 5g of pure substance alkoxy (methyl) acryloxytitanium without solvent, uniformly mixing, dissolving 0.7g of photoinitiator 4-acryloxybenzophenone in 3g of butyl acetate, uniformly mixing, taking 1.0g of the mixture, coating on tin, and carrying out photo-curing by using an ultraviolet curing machine after the solvent volatilizes, wherein the wavelength of ultraviolet light is 365nm, the power is 2kW, the illumination time is 40s, and the thickness is 30 mu m, thus obtaining the cured tertiary amine type polysiloxane polyacrylic resin coating. The coatings were tested for pencil hardness and hydrophobic angle. The results obtained are as follows: the pencil hardness was 2H and the water contact angle was 93.26 °.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (10)
1. A preparation method of photo-curing tertiary amine polysiloxane polyacrylate resin is characterized by comprising the following steps:
(1) Uniformly mixing an aminosilane coupling agent containing primary amine groups and a blocking agent, reacting, adding hydroxyl-terminated silicone oil, continuously reacting, and distilling under reduced pressure to obtain primary amine-containing oligosiloxane;
(2) And (3) adding the primary amine-containing oligosiloxane obtained in the step (1) into an organic solvent and polyacrylate for reaction to obtain the photo-curing tertiary amine polysiloxane polyacrylate resin.
2. The method for preparing a photo-curing tertiary amine polysiloxane-polyacrylate resin according to claim 1, wherein the aminosilane coupling agent containing primary amine groups in the step (1) is at least one of 3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyl methyldiethoxysilane and 3-aminopropyl methyldimethoxysilane;
The end capping agent in the step (1) is at least one of trimethylethoxysilane and methoxytrimethylsilane;
The hydroxyl-terminated silicone oil in the step (1) has an average molecular weight of 300-2000.
3. The method for preparing a photocurable tertiary amine polysiloxane polyacrylate resin as claimed in claim 1, wherein the molar ratio of said primary amine-containing aminosilane coupling agent to said capping agent in step (1) is 1:0.5 to 1;
The molar ratio of the hydroxyl-terminated silicone oil to the primary amine-containing aminosilane coupling agent in the step (1) is 1:1 to 2;
the reaction temperature in the step (1) is 40-55 ℃, the reaction time is 0.5-2 h, and the continuous reaction time is 2-4 h.
4. The method for preparing a photocurable tertiary amine polysiloxane polyacrylate resin according to claim 1, wherein the polyacrylate in the step (2) is at least one of trimethylolpropane triacrylate, pentaerythritol tetraacrylate and pentaerythritol triacrylate;
The organic solvent in the step (2) is at least one of ethyl acetate, propyl acetate, butyl acetate and benzotrifluoride.
5. The method for preparing a photo-curing tertiary amine polysiloxane-polyacrylate resin according to claim 1, wherein the reaction temperature in the step (2) is 50-60 ℃ and the reaction time is 1-6 h;
The temperature of the reduced pressure distillation in the step (1) is 50-60 ℃, and the vacuum degree is minus 0.08 to minus 0.095MPa;
The molar ratio of the polyacrylate in the step (2) to the aminosilane coupling agent containing primary amine groups in the step (1) is 1-2: 1, a step of;
the mass of the organic solvent in the step (2) is 10% -40% of the mass of the total reaction system, and the mass of the total reaction system is the mass sum of the amino silane coupling agent containing primary amine groups, the end capping agent, the hydroxyl-terminated silicone oil, the polyacrylate and the organic solvent.
6. A photocurable tertiary amine polysiloxane-polyacrylate resin prepared by the method of any one of claims 1-5.
7. A light-curable titanium reinforced tertiary amine polysiloxane polyacrylate resin coating comprising the light-curable tertiary amine polysiloxane polyacrylate resin of claim 6, comprising the following components:
Tertiary amine polysiloxane polyacrylate resin, alkoxy (methyl) acryloxytitanium, photoinitiator and organic solvent;
wherein the dosage of the photoinitiator is 2-9 wt% of the mass of the tertiary amine type polysiloxane acrylic resin, and the dosage of the alkoxy (methyl) acryloxytitanium is 1-25 wt% of the mass of the tertiary amine type polysiloxane acrylic resin.
8. The light-curable titanium reinforced tertiary amine polysiloxane polyacrylate resin coating of claim 7, wherein the alkoxy groups in the alkoxy (meth) acryloxytitanium (RO) mTi(OOCC(R`)＝CH2)n include isopropoxy and n-butoxy groups, and wherein 2 is greater than or equal to m is greater than or equal to 0; (meth) acryloyloxy includes methacryloyloxy and acryloyloxy, 4.gtoreq.n.gtoreq.2;
The alkoxy (methyl) acryloyloxy titanium is a product obtained by reacting isopropyl titanate and methacrylic acid according to a molar ratio of 1:2;
the photoinitiator is a type I photoinitiator or a type II photoinitiator;
The organic solvent is at least one of butyl acetate, propyl acetate, ethyl acetate and benzotrifluoride.
9. The method for preparing the photo-curing titanium reinforced tertiary amine type polysiloxane polyacrylate resin coating as claimed in claim 7 or 8, comprising the following steps:
Dissolving tertiary amine type polysiloxane polyacrylate resin and a photoinitiator in an organic solvent, adding alkoxy (methyl) acryloxytitanium, uniformly mixing, volatilizing the solvent, and performing photo-curing to obtain the photo-curing titanium reinforced tertiary amine type polysiloxane polyacrylate resin coating.
10. The method for preparing a photo-curing titanium reinforced tertiary amine polysiloxane-polyacrylate resin coating according to claim 9, wherein the ultraviolet light used for photo-curing has a wavelength of 365nm, a power of 2kW and an irradiation time of 30-50 s;
the photoinitiator is photoinitiator 754 or 4-acryloxybenzophenone 4-BPA.
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