CN114573822A - Synthesis of vinyl polysilazane and application of vinyl polysilazane in anti-graffiti coating - Google Patents
Synthesis of vinyl polysilazane and application of vinyl polysilazane in anti-graffiti coating Download PDFInfo
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- CN114573822A CN114573822A CN202210235109.8A CN202210235109A CN114573822A CN 114573822 A CN114573822 A CN 114573822A CN 202210235109 A CN202210235109 A CN 202210235109A CN 114573822 A CN114573822 A CN 114573822A
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- polysilazane
- resin
- vinyl
- graffiti
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- 229920001709 polysilazane Polymers 0.000 title claims abstract description 56
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 title claims abstract description 44
- 229920002554 vinyl polymer Polymers 0.000 title claims abstract description 44
- 238000000576 coating method Methods 0.000 title claims abstract description 24
- 239000011248 coating agent Substances 0.000 title claims abstract description 21
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 15
- 238000003786 synthesis reaction Methods 0.000 title abstract description 4
- 229920005989 resin Polymers 0.000 claims abstract description 35
- 239000011347 resin Substances 0.000 claims abstract description 35
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229920000642 polymer Polymers 0.000 claims abstract description 18
- 230000000694 effects Effects 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 10
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 7
- CFDHLFKYBUQNSE-UHFFFAOYSA-N 1-ethenyl-1-methylsilinane Chemical compound C=C[Si]1(C)CCCCC1 CFDHLFKYBUQNSE-UHFFFAOYSA-N 0.000 claims abstract description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 6
- YLJJAVFOBDSYAN-UHFFFAOYSA-N dichloro-ethenyl-methylsilane Chemical compound C[Si](Cl)(Cl)C=C YLJJAVFOBDSYAN-UHFFFAOYSA-N 0.000 claims abstract description 6
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000004821 distillation Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 238000001704 evaporation Methods 0.000 claims abstract description 4
- 238000007098 aminolysis reaction Methods 0.000 claims abstract 2
- 238000000016 photochemical curing Methods 0.000 claims description 19
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 10
- 229910001220 stainless steel Inorganic materials 0.000 claims description 10
- 239000010935 stainless steel Substances 0.000 claims description 10
- 238000004321 preservation Methods 0.000 claims description 9
- -1 alkyl benzophenones Chemical class 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 4
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 4
- 239000012965 benzophenone Substances 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 229910000077 silane Inorganic materials 0.000 claims description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 244000028419 Styrax benzoin Species 0.000 claims description 2
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 150000001343 alkyl silanes Chemical class 0.000 claims description 2
- 125000005376 alkyl siloxane group Chemical group 0.000 claims description 2
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical compound C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 claims description 2
- 229960002130 benzoin Drugs 0.000 claims description 2
- 150000008366 benzophenones Chemical class 0.000 claims description 2
- 239000012952 cationic photoinitiator Substances 0.000 claims description 2
- 239000007822 coupling agent Substances 0.000 claims description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 2
- 235000019382 gum benzoic Nutrition 0.000 claims description 2
- CPJRRXSHAYUTGL-UHFFFAOYSA-N isopentenyl alcohol Chemical group CC(=C)CCO CPJRRXSHAYUTGL-UHFFFAOYSA-N 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910001392 phosphorus oxide Inorganic materials 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims description 2
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 2
- 229920006305 unsaturated polyester Polymers 0.000 claims description 2
- 238000003828 vacuum filtration Methods 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 abstract description 9
- 238000001723 curing Methods 0.000 abstract description 6
- 238000005507 spraying Methods 0.000 abstract description 3
- 230000003373 anti-fouling effect Effects 0.000 abstract 2
- 238000004140 cleaning Methods 0.000 abstract 1
- 230000001678 irradiating effect Effects 0.000 abstract 1
- 239000003973 paint Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 9
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 8
- 238000007664 blowing Methods 0.000 description 4
- 230000001186 cumulative effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- FXIVKZGDYRLHKF-UHFFFAOYSA-N C(C)OP(OC(C1=C(C=C(C=C1C)C)C)=O)(=O)C1=CC=CC=C1 Chemical compound C(C)OP(OC(C1=C(C=C(C=C1C)C)C)=O)(=O)C1=CC=CC=C1 FXIVKZGDYRLHKF-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- PMQIWLWDLURJOE-UHFFFAOYSA-N triethoxy(1,1,2,2,3,3,4,4,5,5,6,6,7,7,10,10,10-heptadecafluorodecyl)silane Chemical compound CCO[Si](OCC)(OCC)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCC(F)(F)F PMQIWLWDLURJOE-UHFFFAOYSA-N 0.000 description 2
- QLNOVKKVHFRGMA-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical group [CH2]CC[Si](OC)(OC)OC QLNOVKKVHFRGMA-UHFFFAOYSA-N 0.000 description 2
- VSTXCZGEEVFJES-UHFFFAOYSA-N 1-cycloundecyl-1,5-diazacycloundec-5-ene Chemical compound C1CCCCCC(CCCC1)N1CCCCCC=NCCC1 VSTXCZGEEVFJES-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- UPGGKUQISSWRJJ-XLTUSUNSSA-N Thiocoraline Chemical compound O=C([C@H]1CSSC[C@@H](N(C(=O)CNC2=O)C)C(=O)N(C)[C@@H](C(SC[C@@H](C(=O)NCC(=O)N1C)NC(=O)C=1C(=CC3=CC=CC=C3N=1)O)=O)CSC)N(C)[C@H](CSC)C(=O)SC[C@@H]2NC(=O)C1=NC2=CC=CC=C2C=C1O UPGGKUQISSWRJJ-XLTUSUNSSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005915 ammonolysis reaction Methods 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 239000012700 ceramic precursor Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000003670 easy-to-clean Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- UPGGKUQISSWRJJ-UHFFFAOYSA-N thiocoraline Natural products CN1C(=O)CNC(=O)C(NC(=O)C=2C(=CC3=CC=CC=C3N=2)O)CSC(=O)C(CSC)N(C)C(=O)C(N(C(=O)CNC2=O)C)CSSCC1C(=O)N(C)C(CSC)C(=O)SCC2NC(=O)C1=NC2=CC=CC=C2C=C1O UPGGKUQISSWRJJ-UHFFFAOYSA-N 0.000 description 1
- 108010062880 thiocoraline Proteins 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/60—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/62—Nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/16—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which all the silicon atoms are connected by linkages other than oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
Abstract
The synthesis of vinyl polysilazane and its application in anti-graffiti paint includes 1) stirring in benzene solution of methyl vinyl dichlorosilane, introducing ammonia gas, reacting at 300 deg.C for more than 4 hr, filtering, and vacuum suction filtering to obtain micromolecular methyl vinyl silazane; 2) aminolysis of dimethyldichlorosilane and methyldichloro hydrosilane to obtain an intermediate, heating slowly to 300 ℃ under the protection of nitrogen, keeping the temperature for reaction for more than or equal to 4 hours, and removing low-molecular polymer through reduced pressure distillation to obtain polysilazane polymer; 3) mixing the products of 1) and 2) according to a mass ratio of 5: 1-10, evaporating the solvent under the protection of nitrogen, and reacting for 24 hours at 200 ℃ to obtain vinyl polysilazane. Coating: uniformly mixing vinyl polysilazane, high-activity UV resin, a cross-linking agent, a catalyst, a photoinitiator, a solvent and an anti-fouling auxiliary agent, spraying, and irradiating and curing by ultraviolet rays. The invention has safe reaction temperature and high repeatability, and can prepare the fast-curing anti-fouling easy-cleaning vinyl polysilazane coating.
Description
Technical Field
The invention belongs to the technical field of chemical coatings, and relates to preparation of a photocureable coating.
Background
The polysilazane resin as a high-performance organic silicon resin type ceramic precursor has outstanding application prospects in various fields, for example, the polysilazane resin can be used for preparing a super-high temperature resistant coating in the national defense field, and can be used for preparing anti-graffiti, hydrophobic, wear-resistant and anti-corrosion coatings in the civil field. At present, the curing of the polysilazane coating mainly takes normal-temperature self-drying and high-temperature curing as main materials, and the research on the photocuring method is less. The vinyl polysilazane has low vinyl activity and cannot be directly initiated by an initiator to prepare a photocuring coating.
Disclosure of Invention
The invention aims to provide synthesis of vinyl polysilazane and application of vinyl polysilazane in anti-graffiti coatings. After the vinyl polysilazane is prepared, the vinyl polysilazane is matched with the high-activity UV resin, and the high-activity UV resin is initiated by an initiator, so that the vinyl in the vinyl polysilazane is further initiated, and the aim of preparing the vinyl polysilazane into the photocuring coating is fulfilled. Meanwhile, due to the fact that the doodling auxiliary agent is added in the scheme, the anti-doodling polysilazane photocureable coating can be prepared.
The invention relates to a method for synthesizing polysilazane, which comprises the following steps.
(1) Introducing dry high-purity ammonia gas into a benzene solution of methyl vinyl dichlorosilane under the condition of stirring, keeping the temperature of 300 ℃ in the reaction process for reacting for more than 4 hours, filtering out precipitates, and then carrying out vacuum filtration to obtain micromolecular methyl vinyl silazane Vi-PZ liquid.
(2) Preparing the polysilazane polymer PSZ. Carrying out ammonolysis on dimethyldichlorosilane and methyldichlorohydric silane according to the molar ratio of 1.5: 0.5-10 to prepare a low molecular intermediate, slowly heating to 300 ℃ at the heating rate of 5 ℃/min under the protection of nitrogen, carrying out heat preservation reaction for more than 4 hours, and carrying out reduced pressure distillation after the reaction is finished to remove a low molecular polymer PSZ and obtain a large molecular weight polysilazane polymer PSZ product.
(3) And (3) mixing the products obtained in the step (1) and the step (2) according to a mass ratio of 5: 1-10, evaporating the solvent under the protection of nitrogen, and then carrying out heat preservation reaction at 200 ℃ for 24 hours to obtain vinyl polysilazane Vi-PSZ.
The application of the vinyl polysilazane in the anti-doodling coating is characterized in that the anti-doodling coating is prepared from the following materials in percentage by mass:
vinyl polysilazane: 20 to 30 percent
High-activity UV resin: 15 to 25 percent
A crosslinking agent: 10 to 15 percent of
Catalyst: 0.5 to 1 percent
Photoinitiator (2): 2 to 5 percent
Anti-graffiti aids: 0.5 to 3 percent of
The balance being solvent.
The high-activity UV resin is one or more than two of polyacrylate UV resin, epoxy acrylate UV resin, polyurethane acrylate UV resin, polyester acrylate UV resin, unsaturated polyester acrylate UV resin, polyether acrylate UV resin or acrylated polyacrylic UV resin.
The crosslinking agent is one or more than two of amino silane coupling agent and titanate coupling agent.
The catalyst is one or more than two of 1, 8-diazabicycloundecene-7-ene, metal catalyst, 2-dimorpholinodiethyl ether, triethylene diamine, 2,4, 6-tri (dimethylaminomethyl) phenol or methyl hydroxyethyl ethylene diamine.
The photoinitiator refers to one or more of benzoin and derivatives, benzil, alkyl benzophenones, acyl phosphorus oxide, benzophenones, thioxanthones or cationic photoinitiators.
The anti-graffiti auxiliary agent is one or more than two of fluorine-containing silane coupling agent, fluorine-containing siloxane polymer, alkyl silane coupling agent, alkyl siloxane polymer and resin or oligomer with acrylate structure.
Mixing the above materials, spraying on the surface of stainless steel, blowing in oven at 50 deg.C for 1min to accumulate energy of 800-1200mj/cm2And (5) carrying out photocuring film formation through a UV machine.
According to the invention, the crosslinking agent, the catalyst, the photoinitiator and the anti-doodling functional auxiliary agent are compounded through crosslinking initiation of the high-activity UV resin, so that the difficulty that the ultraviolet curing coating cannot be prepared due to low vinyl activity in vinyl polysilazane is solved, and meanwhile, through reasonable blending of the formula, the fast-curing anti-doodling easy-to-clean polysilazane photocuring coating can be prepared, and the reaction temperature is safe and has high repeatability.
Detailed Description
The invention will be further illustrated by the following examples.
Example 1.
(1) And (3) synthesizing vinyl polysilazane.
1) Introducing dry high-purity ammonia gas into a benzene solution of methyl vinyl dichlorosilane under the condition of stirring, keeping the temperature of 300 ℃ in the reaction process for reacting for 4 hours, and filtering out precipitates to obtain micromolecular methyl vinyl silazane Vi-PZ liquid.
2) Preparation of polysilazane Polymer PSZ: performing coemmonolysis on dimethyldichlorosilane and methyldichlorohydric hydrosilane according to the molar ratio of 1.5:1 to prepare a low molecular intermediate, slowly heating to 300 ℃ at the heating rate of 5 ℃/min under the protection of nitrogen, performing heat preservation reaction for 4 hours, and performing reduced pressure distillation to remove the low molecular polymer PSZ after the reaction is finished.
3) And (3) products obtained in the steps 1) and 2) are mixed according to an instruction ratio of 5:1, under the protection of nitrogen, evaporating the solvent, and then carrying out heat preservation reaction at 200 ℃ for 24 hours to obtain vinyl polysilazane Vi-PSZ.
(2) And (2) preparing the photocuring anti-graffiti coating by using the vinyl polysilazane synthesized in the step (1).
26.07% vinyl polysilazane Vi-PSZ, 19.3% EBECRYL 8890 (good for new chemical engineering), 11.5% bis [3- (trimethoxysilyl) propyl ] in mass percent (%)]Amine, 0.5% of 1, 8-diazabicycloundecen-7-ene, 3.8% of photoinitiator 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, 1% of anti-graffiti auxiliary agent digaprotection 5000N, the balance being solvent propylene glycol methyl ether acetate, and mixingSpraying the mixture on the surface of stainless steel after uniform mixing, blowing for 1min at 50 ℃ in an oven, and accumulating energy of 800-1200mj/cm2And (5) carrying out photocuring film formation through a UV machine.
Example 2.
(1) And (3) synthesizing vinyl polysilazane.
1) Introducing dry high-purity ammonia gas into a benzene solution of methyl vinyl dichlorosilane while stirring, keeping the temperature of 300 ℃ in the reaction process for reacting for 4 hours, and filtering out precipitates to obtain micromolecular methyl vinyl silazane Vi-PZ liquid.
2) The preparation method of the polysilazane polymer PSZ comprises the steps of performing coemmonolysis on dimethyldichlorosilane and methyldichlorohydric silane according to a molar ratio of 1.5:0.5 to obtain a low-molecular intermediate, slowly heating to 300 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen, performing heat preservation reaction for 4 hours, and performing reduced pressure distillation to remove the low-molecular polymer PSZ after the reaction is finished.
3) And (3) products obtained in the steps 1) and 2) are mixed according to an instruction ratio of 5: 2, under the protection of nitrogen, the solvent is distilled off, and then the vinyl polysilazane Vi-PSZ can be obtained after the reaction for 24 hours at the temperature of 200 ℃.
(2) And (2) preparing the photocuring anti-graffiti coating by using the vinyl polysilazane synthesized in the step (1).
According to the mass percent (%), 22.07 percent of vinyl polysilazane, 24.3 percent of Gejieda UA-1117 UV resin in high-activity UV resin, 11.5 percent of cross-linking agent gamma-aminopropyltriethoxysilane, 0.5 percent of catalyst 1, 8-diazabicycloundecene-7-ene, 3.8 percent of photoinitiator 2-hydroxy-2-methyl-1-phenyl acetone, 1 percent of anti-graffiti auxiliary agent heptadecafluorodecyltriethoxysilane and the balance of solvent propylene glycol monomethyl ether acetate are evenly mixed and sprayed on the surface of stainless steel, air is blown for 1min at 50 ℃ in an oven, and the cumulative energy is 800 mj/cm2And (5) carrying out photocuring film formation through a UV machine.
Example 3.
(1) And (3) synthesizing vinyl polysilazane.
1) Introducing dry high-purity ammonia gas into a benzene solution of methyl vinyl dichlorosilane while stirring, keeping the temperature of 300 ℃ in the reaction process for reacting for 4 hours, and filtering out precipitates to obtain micromolecular methyl vinyl silazane Vi-PZ liquid.
2) The preparation method of the polysilazane polymer PSZ comprises the steps of performing coemmonolysis on dimethyldichlorosilane and methyldichlorohydric silane according to a molar ratio of 1:1 to obtain a low-molecular intermediate, slowly heating to 300 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen, performing heat preservation reaction for 4 hours, and performing reduced pressure distillation to remove the low-molecular polymer PSZ after the reaction is finished.
3) And (3) products obtained in the steps 1) and 2) are mixed according to an instruction ratio of 5: 1.5, distilling off the solvent under the protection of nitrogen after mixing, and then carrying out heat preservation reaction at 200 ℃ for 24 hours to obtain the vinyl polysilazane Vi-PSZ.
(2) And (2) preparing the photocuring anti-graffiti coating by using the vinyl polysilazane synthesized in the step (1).
According to mass percent, 23.07 percent of vinyl polysilazane, 24.8 percent of high-activity UV resin, namely, a thiocoraline L-6903UV resin, 10 percent of cross-linking agent tetrabutyl titanate, 0.5 percent of catalyst, 1, 8-diazabicycloundecen-7-ene, 3.8 percent of photoinitiator, 2,4, 6-trimethylbenzoyl ethyl phenylphosphonate, 1 percent of anti-graffiti auxiliary agent Dow Corning PMX-200 and the balance of solvent, namely propylene glycol monomethyl ether acetate are uniformly mixed and sprayed on the surface of stainless steel, air is blown in an oven for 1min at 50 ℃, and the cumulative energy is 800-2And (5) carrying out photocuring film formation through a UV machine.
Comparative examples were compared using the usual photocurable coating formulation and other protocols.
Comparative example 1.
According to the mass percent, 57.1 percent of high-activity UV resin is made into novel chemical EBECRYL 8890, 3.8 percent of photoinitiator 2,4, 6-trimethyl benzoyl phenyl ethyl phosphonate, 1 percent of doodle-resistant additive Digao Protect 5000N, and the balance is solvent propylene glycol monomethyl ether acetate, the mixture is uniformly mixed and sprayed on the surface of stainless steel, air blowing is carried out in an oven at 50 ℃ for 1min, and the accumulated energy is 800 mj/cm-2And (5) carrying out photocuring film formation through a UV machine.
Comparative example 2.
46.1% of the vinyl polysilazane prepared in example 2, 10.5% of a crosslinking agent, gamma-aminopropyltriethoxysilane, 0.5% of a catalyst 1 were mixed in mass percent (%)8-diazabicycloundecen-7-ene, 3.8% of 2,4, 6-trimethylbenzoyl phenyl ethyl phosphonate as a photoinitiator, 1% of an anti-graffiti auxiliary agent heptadecafluorodecyl triethoxysilane and the balance of a solvent propylene glycol methyl ether acetate, uniformly mixing, spraying on the surface of stainless steel, blowing in an oven at 50 ℃ for 1min, and accumulating energy of 800-2And (5) carrying out photocuring film formation by a UV machine.
Comparative example 3.
According to the mass percent (%), 57.6 percent of vinyl polysilazane prepared in example 3, 4.3 percent of 2,4, 6-trimethyl benzoyl phenyl ethyl phosphonate as a photoinitiator, 1 percent of doodle-resisting auxiliary agent PMX-200 and the balance of propylene glycol methyl ether acetate are uniformly mixed and sprayed on the surface of stainless steel, air is blown in an oven at 50 ℃ for 1min, and the cumulative energy is 800-1200mj/cm2And (5) carrying out photocuring film formation through a UV machine.
Comparative example 4.
According to the mass percent (%), 57.6 percent of commercial Merck vinyl polysilazane (trademark Durazane 1800), 4.3 percent of photoinitiator 1-hydroxycyclohexyl phenyl ketone, 1 percent of Dow Corning PMX-200 and the balance of solvent propylene glycol methyl ether acetate are evenly mixed and sprayed on the surface of stainless steel, air is blown in an oven at 50 ℃ for 1min, and the cumulative energy is 800-2And (5) carrying out photocuring film formation through a UV machine.
Comparative example 5.
26.07% of the vinyl polysilazane prepared in example 1, 19.3% of the high-activity UV resin, New chemical EBECRYL 8890, 11.5% of the crosslinking agent bis [3- (trimethoxysilyl) propyl ] propyl]Amine, 0.5 percent of catalyst 1, 8-diazabicycloundec-7-ene, 3.8 percent of photoinitiator 2,4, 6-trimethylbenzoyl ethyl phenylphosphonate and the balance of solvent propylene glycol methyl ether acetate are uniformly mixed and sprayed on the surface of stainless steel, air is blown for 1min at 50 ℃ in an oven, and the accumulated energy is 800-1200mj/cm2And (5) carrying out photocuring film formation through a UV machine.
The test results were as follows:
description of the drawings: 1. the vinyl polysilazane has poor vinyl photocuring activity, and if the comparative example 2/3/4 not matched with the active UV resin relies on a photoinitiator, neither the polysilazane made by us nor commercially available can obtain a good film-forming effect by photocuring, and the hardness and wear resistance of the coating are insufficient.
2. Although comparative example 1, in which polysilazane was not added, had a good film formation, the silicone-based anti-graffiti assistant and the UV resin did not chemically react, and thus the anti-graffiti property of the coating was remarkably poor.
3. Comparative example 5, with no added anti-graffiti aid, formed a good film, but the anti-graffiti was significantly less than example 1/2/3.
Claims (2)
1. A method for synthesizing vinyl polysilazane is characterized by comprising the following steps:
(1) introducing dry high-purity ammonia gas into a benzene solution of methyl vinyl dichlorosilane under the condition of stirring, keeping the temperature of 300 ℃ in the reaction process for reacting for more than or equal to 4 hours, filtering out precipitates, and then carrying out vacuum filtration to obtain micromolecular methyl vinyl silazane liquid;
(2) preparation of polysilazane Polymer: aminolysis is carried out on dimethyl dichlorosilane and methyl dichlorohydric silane according to the molar ratio of 1.5: 0.5-10 to prepare a low molecular intermediate, the temperature is raised to 300 ℃ at the speed of 5 ℃/min under the protection of nitrogen, the reaction is carried out for more than or equal to 4 hours under the condition of heat preservation, reduced pressure distillation is carried out after the reaction is finished to remove low molecular polymers, and the rest is high molecular weight polysilazane polymer products;
(3) and (3) mixing the products obtained in the step (1) and the step (2) according to a mass ratio of 5: 1-10, evaporating the solvent under the protection of nitrogen, and then carrying out heat preservation reaction at 200 ℃ for 24 hours to obtain vinyl polysilazane.
2. The application of the vinyl polysilazane of claim 1 in the anti-graffiti coating is characterized in that the anti-graffiti coating is prepared from the following materials in percentage by mass:
vinyl polysilazane: 20% -30%;
high-activity UV resin: 15% -25%;
a crosslinking agent: 10% -15%;
catalyst: 0.5% -1%;
photoinitiator (2): 2% -5%;
anti-graffiti aids: 0.5% -3%;
the balance being solvent;
the high-activity UV resin is one or more than two of polyacrylate UV resin, epoxy acrylate UV resin, polyurethane acrylate UV resin, polyester acrylate UV resin, unsaturated polyester acrylate UV resin, polyether acrylate UV resin or acrylated polyacrylic UV resin;
the crosslinking agent is one or more than two of amino silane coupling agent and titanate coupling agent;
the catalyst is one or more than two of 1, 8-diazabicycloundecene-7-ene, metal catalyst, 2-dimorpholinodiethyl ether, triethylene diamine, 2,4, 6-tri (dimethylaminomethyl) phenol or methyl hydroxyethyl ethylene diamine;
the photoinitiator refers to one or more of benzoin and derivatives, benzil, alkyl benzophenones, acyl phosphorus oxide, benzophenones, thioxanthones or cationic photoinitiators;
the anti-graffiti auxiliary agent is one or more than two of fluorine-containing silane coupling agent, fluorine-containing siloxane polymer, alkyl silane coupling agent, alkyl siloxane polymer and resin or oligomer with acrylate structure;
the materials are uniformly mixed and sprayed on the surface of stainless steel, air is blown in an oven for 1min at 50 ℃, and the accumulated energy is 800-2And (5) carrying out photocuring film formation through a UV machine.
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