CN108384403B - Preparation method of core-shell structure nano silicon dioxide/zinc stannate flame-retardant epoxy acrylate coating - Google Patents
Preparation method of core-shell structure nano silicon dioxide/zinc stannate flame-retardant epoxy acrylate coating Download PDFInfo
- Publication number
- CN108384403B CN108384403B CN201810146113.0A CN201810146113A CN108384403B CN 108384403 B CN108384403 B CN 108384403B CN 201810146113 A CN201810146113 A CN 201810146113A CN 108384403 B CN108384403 B CN 108384403B
- Authority
- CN
- China
- Prior art keywords
- sno
- nano
- coating
- epoxy acrylate
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 200
- 238000000576 coating method Methods 0.000 title claims abstract description 154
- 239000011248 coating agent Substances 0.000 title claims abstract description 146
- 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 title claims abstract description 45
- 239000003063 flame retardant Substances 0.000 title claims abstract description 45
- 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 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 239000011258 core-shell material Substances 0.000 title claims abstract description 23
- BNEMLSQAJOPTGK-UHFFFAOYSA-N zinc;dioxido(oxo)tin Chemical compound [Zn+2].[O-][Sn]([O-])=O BNEMLSQAJOPTGK-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 235000012239 silicon dioxide Nutrition 0.000 title abstract description 6
- 239000005543 nano-size silicon particle Substances 0.000 title abstract description 5
- 229910003107 Zn2SnO4 Inorganic materials 0.000 claims abstract description 125
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 107
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 99
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 99
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 99
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 99
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 14
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 13
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims abstract description 7
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims abstract description 7
- -1 zinc stannate compound Chemical class 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 29
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 28
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 19
- 239000007787 solid Substances 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 16
- 239000002244 precipitate Substances 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 12
- 239000011347 resin Substances 0.000 claims description 10
- 229920005989 resin Polymers 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000001723 curing Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 5
- 229910052753 mercury Inorganic materials 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 230000010355 oscillation Effects 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 229910001432 tin ion Inorganic materials 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 2
- 238000005286 illumination Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 59
- 229910052799 carbon Inorganic materials 0.000 abstract description 35
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 abstract description 15
- 239000001301 oxygen Substances 0.000 abstract description 15
- 239000002105 nanoparticle Substances 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 10
- 238000002834 transmittance Methods 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000007423 decrease Effects 0.000 abstract description 2
- 239000011592 zinc chloride Substances 0.000 abstract description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 36
- 239000010410 layer Substances 0.000 description 26
- 230000015556 catabolic process Effects 0.000 description 21
- 238000006731 degradation reaction Methods 0.000 description 21
- 238000010521 absorption reaction Methods 0.000 description 19
- 238000005452 bending Methods 0.000 description 14
- 238000002329 infrared spectrum Methods 0.000 description 13
- 239000011701 zinc Substances 0.000 description 13
- 238000004458 analytical method Methods 0.000 description 10
- 238000002441 X-ray diffraction Methods 0.000 description 9
- 239000011148 porous material Substances 0.000 description 9
- 238000005259 measurement Methods 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 238000002485 combustion reaction Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229910002808 Si–O–Si Inorganic materials 0.000 description 6
- 238000009413 insulation Methods 0.000 description 6
- 239000002861 polymer material Substances 0.000 description 6
- 229910018557 Si O Inorganic materials 0.000 description 5
- 229910020923 Sn-O Inorganic materials 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000002076 thermal analysis method Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 229910007542 Zn OH Inorganic materials 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 238000001757 thermogravimetry curve Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000000707 layer-by-layer assembly Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000009828 non-uniform distribution Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 229940071182 stannate Drugs 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C09D163/10—Epoxy resins modified by unsaturated compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
- C09D5/185—Intumescent paints
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/88—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by thermal analysis data, e.g. TGA, DTA, DSC
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Inorganic Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a preparation method of a core-shell structure nano silicon dioxide/zinc stannate flame-retardant epoxy acrylate coating. With ZnCl2And SnCl4·5H2O is used as a raw material to synthesize zinc stannate, CTAB and TEOS are used as raw materials to synthesize nano mesoporous silica, and the nano mesoporous silica and the TEOS are self-assembled to form a nano silica/zinc stannate compound with a core-shell structure. It is added to EA and UV cured to a coating. The structure, thermal stability, flame retardance and the like of the sample are represented by ultraviolet, infrared, DSC, oxygen index measuring instruments and the like. The results show that: the self-assembled core-shell structure nano particles have good flame retardant effect; when the content of the carbon is 0.6g, the highest carbon residue rate of the coating is 17.32% at 500 ℃ of a muffle furnace, and the limiting oxygen index reaches 30; the light transmittance of the coating decreases with the increase of the content thereof. Nano mesoporous SiO2/Zn2SnO4Can improve the high temperature resistance of the coating and can maintain the coating at higher hardness.
Description
Technical Field
The invention relates to the technical field of flame-retardant materials, in particular to a preparation method of a core-shell structure nano silicon dioxide/zinc stannate flame-retardant epoxy acrylate coating.
Background
With the development of polymer technology, polymer materials are applied in different fields, and have been integrated into the aspects of people's life. However, most of high polymer materials are not high temperature resistant and easy to burn, which causes harm to lives and properties of people, and the pollution caused by burning has serious influence on the environment. Therefore, the temperature resistance of the high polymer material is improved, and great help is brought to the reduction of fire. At present, a common method for improving the temperature resistance of polymer materials is to add a flame retardant in the preparation process of the polymer materials to enhance the flame resistance; wherein the nanometer materialThe material can effectively slow down the heat release rate of the polymer. Nano mesoporous SiO2Compared with the traditional nano SiO2The polymer has a special mesoporous structure and therefore has a large specific surface area, and has been applied to polymer materials, especially to coatings, but the flame retardant effect of the polymer added alone is poor, so the polymer is less used for flame retardant. Therefore, it is required to be compounded with other substances.
The zinc stannate is used as an inorganic substance, is important to be applied to metallurgical coking wastewater treatment, is often used in a composite way with other materials, has good compatibility in the composite way with nano materials, and the current research report on the zinc stannate also focuses on the flame retardance of the materials; for example, the application of the calcium carbonate coated with zinc stannate in the polyvinyl chloride cable material, the synthesis and the application of the zinc stannate coated on the surface of the nano inorganic flame retardant and the like have good flame retardant effect.
Disclosure of Invention
The invention aims to provide a preparation method of a core-shell structure nano silicon dioxide/zinc stannate flame-retardant epoxy acrylate coating with strong flame retardant property and good thermal stability.
In order to achieve the purpose, the invention adopts the following technical scheme:
nano SiO with core-shell structure2/Zn2SnO4The preparation method of the flame-retardant epoxy acrylate coating comprises the following steps:
1) preparation of nano mesoporous SiO2
2) Preparation of zinc stannate Zn2SnO4
ZnCl is added according to the molar ratio of zinc ions to tin ions of 2:12And SnCl4·5H2Placing O in a container, adding water to adjust the pH value of the solution to be 8.8-9.2, stirring and reacting for 15-25min, then transferring the mixed solution into a hydrothermal kettle with a polytetrafluoroethylene lining, continuing to react for 10-14h at the temperature of 180 ℃ and 220 ℃, cooling to room temperature, centrifuging, collecting precipitate, washing and drying to obtain a product Zn2SnO4；
3) Preparation of nano mesoporous SiO2/Zn2SnO4
According to the mass ratio of 1: 0.8-1.2, the nano mesoporous SiO is mixed with the solution2And Zn2SnO4Adding into water, stirring, subjecting the mixture to ultrasonic treatment for 15-30min, centrifuging, collecting solid, washing with deionized water, and adding into 1.8-2.2g/L NaNO3Performing ultrasonic treatment in the solution for 15-30min, centrifuging to obtain precipitate, drying, and grinding to obtain nanometer mesoporous SiO2/Zn2SnO4；
4) Preparation of epoxy acrylate coatings
Mixing acrylic acid, acrylamide and nano-mesoporous SiO2/Zn2SnO4And epoxy acrylate are uniformly mixed to obtain a mixture, and the mixture comprises the following components in percentage by mass: acrylic acid and acrylamide 35%, nano mesoporous SiO2/Zn2SnO42-6% of epoxy acrylate, 59-63% of epoxy acrylate, adding a photoinitiator into the mixture to obtain mixed resin, uniformly coating the mixed resin on a coating carrier, and curing by illumination to obtain the flame-retardant epoxy acrylate coating.
In step 1), the nano mesoporous SiO2The preparation method comprises the following steps: placing deionized water, cetyl trimethyl ammonium bromide and 1.8-2.2mol/L NaOH solution into a round bottom flask, refluxing and stirring at 75-85 ℃, reacting for 25-35min, then adding tetraethoxysilane, wherein the dosage ratio of the deionized water, the cetyl trimethyl ammonium bromide, the NaOH solution and the tetraethoxysilane is 300 mL: 0.8-1.2 g: 3 mL: 4.5-5.5mL, continuing to react for 1.5-2.5h, then filtering white precipitate at the bottom of the flask and drying for 8h, extracting the dried product with anhydrous methanol, refluxing at 85-95 ℃, stirring for 18-24h, filtering to obtain white solid, repeatedly extracting the white solid for 2-3 times, and finally drying the solid to obtain nano mesoporous SiO22。
Furthermore, the dosage ratio of the deionized water, the hexadecyl trimethyl ammonium bromide, the NaOH solution and the ethyl orthosilicate is 300 mL: 1 g: 3 mL: 5 mL.
In the step 2), the precipitate is alternately washed 3-4 times by deionized water and absolute ethyl alcohol.
In step 3), the nano mediumSiO pore2And Zn2SnO4The mass ratio of (A) to (B) is 1: 1.
In the step 4), the mass percent of acrylic acid in the mixture is 18-20%, and the mass percent of acrylamide is 15-17%.
In the step 4), the mixture comprises the following components in percentage by mass: 20% of acrylic acid, 15% of acrylamide and nano mesoporous SiO2/Zn2SnO46 percent and 59 percent of epoxy acrylate.
In the step 4), the addition amount of the photoinitiator is 3-3.5% of the total amount of the mixture.
In the step 4), firstly, adding acrylic acid and acrylamide into a beaker, ultrasonically dispersing by using 0.8-12KW ultrasonic waves until the acrylic acid and the acrylamide are dissolved, and then adding nano mesoporous SiO2/Zn2SnO4And after uniformly stirring, carrying out ultrasonic oscillation for 40-60min, then adding epoxy acrylate and 1173 photoinitiator, and after uniformly stirring, carrying out ultrasonic oscillation for 20-40min to obtain the mixed resin.
In the step 4), the light curing is carried out by adopting 800-1200W/cm2The high-pressure mercury lamp of (1).
The invention adopts the technical scheme that ZnCl is used2And SnCl4·5H2O is used as a raw material to synthesize zinc stannate, CTAB and TEOS are used as raw materials to synthesize nano mesoporous silica, the zinc stannate and the nano mesoporous silica are self-assembled to form a core-shell structure nano silica/zinc stannate compound, and then the core-shell structure nano silica/zinc stannate compound is added into EA to be cured into a coating through UV. The sample structure, the thermal stability, the flame retardance and the like are characterized by an ultraviolet, infrared, DSC, oxygen index tester and the like, and the result shows that the self-assembled core-shell structure nano particles have a good flame retardant effect, the high temperature resistance of the epoxy acrylate coating can be improved, and the coating can be maintained at a high hardness. In addition, the novel mesoporous SiO2The complex formulation of the flame retardant and the metal oxide improves the carbon residue of the polymer, and can convert toxic substances in smoke generated during combustion into harmless substances, thereby achieving the purposes of reducing the hazard of fire and lightening the environmental pollution.
Drawings
FIG. 1 is a drawing ofRice mesoporous SiO2XRD pattern of (a);
FIG. 2 shows Zn2SnO4XRD pattern of (a);
FIG. 3 is an infrared spectrum of the product, (a) Zn2SnO4(b) nano-mesoporous SiO2(c) nano-mesoporous SiO2/Zn2SnO4A complex;
FIG. 4 is a chart of the infrared spectrum of the coating of sample 1 of example 4;
FIG. 5 is a graph of the infrared spectrum of sample 4 of example 4;
FIG. 6 is a graph of the infrared spectrum of sample 5 in example 4;
FIG. 7 is a graph of the infrared spectrum of sample 7 in example 4;
FIG. 8 shows a nano-sized mesoporous SiO2/Zn2SnO4UV spectrogram of/EA;
FIG. 9 shows a nano-sized mesoporous SiO2/Zn2SnO4Thermogram of/EA;
FIG. 10 shows the nano-mesoporous SiO with different addition amounts2/Zn2SnO4The shape of the carbon residue of the coating (500 ℃).
Detailed Description
Nano SiO with core-shell structure2/Zn2SnO4The preparation method of the flame-retardant epoxy acrylate coating comprises the following steps:
1) preparation of nano mesoporous SiO2
In step 1), the nano mesoporous SiO2The preparation method comprises the following steps: placing deionized water, cetyl trimethyl ammonium bromide and 1.8-2.2mol/L NaOH solution into a round bottom flask, refluxing and stirring at 75-85 ℃, reacting for 25-35min, then adding tetraethoxysilane, wherein the dosage ratio of the deionized water, the cetyl trimethyl ammonium bromide, the NaOH solution and the tetraethoxysilane is 300 mL: 0.8-1.2 g: 3 mL: 4.5-5.5mL, continuing to react for 1.5-2.5h, then filtering white precipitate at the bottom of the flask and drying for 8h, extracting the dried product with anhydrous methanol, refluxing at 85-95 ℃, stirring for 18-24h, filtering to obtain white solid, repeatedly extracting the white solid for 2-3 times, and finally drying the solid to obtain the white solidNano mesoporous SiO2。
Preferably, the dosage ratio of the deionized water, the hexadecyl trimethyl ammonium bromide, the NaOH solution and the ethyl orthosilicate is 300 mL: 1 g: 3 mL: 5 mL.
2) Preparation of zinc stannate Zn2SnO4
ZnCl is added in a molar ratio of zinc to tin ions of 2:1 (preferably 1:1)2And SnCl4·5H2Placing O in a container, adding water to adjust the pH value of the solution to 8.8-9.2, stirring and reacting for 15-25min, then transferring the mixed solution into a hydrothermal kettle with a polytetrafluoroethylene lining, continuing to react for 10-14h at the temperature of 180 ℃ and 220 ℃, cooling to room temperature, centrifuging, collecting precipitate, alternately washing for 3-4 times by using deionized water and absolute ethyl alcohol, and drying to obtain a product Zn2SnO4；
3) Preparation of nano mesoporous SiO2/Zn2SnO4
According to the mass ratio of 1: 0.8-1.2, the nano mesoporous SiO is mixed with the solution2And Zn2SnO4Adding into water, stirring, subjecting the mixture to ultrasonic treatment for 15-30min, centrifuging, collecting solid, washing with deionized water, and adding into 1.8-2.2g/L NaNO3Performing ultrasonic treatment in the solution for 15-30min, centrifuging to obtain precipitate, drying, and grinding to obtain nanometer mesoporous SiO2/Zn2SnO4；
4) Preparation of epoxy acrylate coatings
Firstly, adding acrylic acid and acrylamide into a beaker, ultrasonically dispersing by 0.8-1.2KW of ultrasonic wave until the acrylic acid and the acrylamide are dissolved, and then adding nano mesoporous SiO2/Zn2SnO4Uniformly stirring, then ultrasonically oscillating for 40-60min, then adding epoxy acrylate and 1173 photoinitiator, uniformly stirring, then ultrasonically oscillating for 20-40min to obtain mixed resin, then uniformly coating the mixed resin on a coating carrier by adopting 800-1200W/cm2Irradiating and curing by a high-pressure mercury lamp to obtain a flame-retardant epoxy acrylate coating;
wherein the mixed resin comprises the following components in percentage by mass: 18-20% of acrylic acid, 15-17% of acrylamide and nano mesoporous SiO2/Zn2SnO42-6 percent of epoxy acrylate, 59-63 percent of epoxy acrylate and 3-3.5 percent of photoinitiator.
The present invention is further illustrated in detail with reference to the following specific examples:
example 1
Nano mesoporous SiO2Preparation of
300mL of deionized water, 1.0g of hexadecyl trimethyl ammonium bromide, 3mL of 2mol/L NaOH solution are added into a 500mL round bottom flask, and the mixture is refluxed, stirred and reacted for 30min at 80 ℃. Then adding 5mL of ethyl orthosilicate for continuous reaction for 2h, filtering the white precipitate at the bottom of the flask, drying for 8h, putting the dried solid into a 250mL single-neck flask, adding 150mL of anhydrous methanol for extraction, refluxing at 90 ℃, stirring for 24h, filtering to obtain a white solid, repeatedly extracting the white solid for three times, and finally drying the white solid to obtain the nano mesoporous SiO2。
Example 2
Zinc stannate Zn2SnO4Preparation of
Collecting 1.363g ZnCl2、1.753g SnCl4·5H2Adding 20mL of water into a beaker with O (the molar ratio of zinc to tin ions is 2:1), adjusting the pH of the solution to 9, reacting for 20min at normal temperature (magnetic stirring), transferring the mixed solution into a hydrothermal kettle with a polytetrafluoroethylene lining, continuing to react for 12h at 200 ℃, and naturally cooling to room temperature. Centrifuging the precipitate, washing the centrifuged matter with deionized water and anhydrous ethanol for 3 times, and drying to obtain Zn product2SnO4 [5]。
Example 3
Layer-by-layer assembly method for preparing nano mesoporous SiO2/Zn2SnO4
Adding nano mesoporous SiO into a 50mL beaker2And Zn2SnO4(mass ratio 1:1) and 10mL of water. After stirring well, sonication for 20min, the mixture was centrifuged and the solid particles were washed with deionized water. Then the solid particles are placed in 10mL of NaNO of 2g/L3In solution[6]And (5) performing ultrasonic treatment for 20 min. Centrifuging to obtain white precipitate, drying, and grinding to obtain nanometer mediumSiO pore2/Zn2SnO4。
Example 4
1. Preparation of core-shell structure nano SiO2/Zn2SnO4 flame-retardant epoxy acrylate coating
The UV curable coating was prepared according to the formulation in Table 1 in a total amount of 10g, and an appropriate amount of 1173 photoinitiator was added. Firstly, adding acrylic acid and acrylamide into a 30mL beaker, ultrasonically dispersing for 10min by using 1KW ultrasonic wave until the acrylic acid and the acrylamide are dissolved, and then adding a proper amount of nano mesoporous SiO in the formula2/Zn2SnO4Uniformly stirring by using a glass rod, then ultrasonically oscillating for 50min to uniformly disperse, then adding a proper amount of EA and 1173 photoinitiator of 0.3g, uniformly stirring by using the glass rod, and then ultrasonically oscillating for 30min to uniformly disperse without bubbles. The coating was prepared by applying a coating to a glass plate using a 100 μm wet film maker at a coating thickness of 100 μm and then using a 1000W/cm2The high-pressure mercury lamp (2) is irradiated for 3 to 5 seconds to cure the material into a film. The strips were prepared by pouring the coating onto bars of dimensions 100X 6.5X 3mm3The mold was filled with the resin, and then cured into a strand by irradiating with a high-pressure mercury lamp for 30 to 50 seconds.
TABLE 1 nanometer mesoporous SiO2/Zn2SnO4Formula of EA ultraviolet curing flame-retardant coating liquid
2. Testing and characterization
(1) X-ray diffraction (XRD) measurement
An X-ray diffractometer is adopted, the parameter 2 theta is set to be 10-80 degrees, and the scanning speed is 4.0000 deg/min. Determination of nano mesoporous SiO2And Zn2SnO4XRD pattern of (a).
(2) Fourier Infrared (IR) spectroscopy
Setting the wave number range to 4000-500 cm by using a Fourier infrared spectrometer-1And measuring the infrared spectrums of the product and the flame-retardant EA system.
(3) Ultraviolet/visible Spectrophotometer (UV-Vis) measurements
Setting the wave number range to be 200 nm-800nm by adopting an ultraviolet/visible spectrophotometer, then placing the flame-retardant EA system coating film into a detection tank, and measuring the light transmittance of the film.
(4) Thermal analysis (DSC) measurement
A thermal analyzer is adopted, the initial temperature is set to be 25 ℃, the stopping temperature is set to be 750 ℃, and the sampling interval is 10 ℃/min. The thermal stability of the flame retardant EA system was determined.
(5) Water absorption measurement
The water absorption (W) is calculated by the formula:
in the formula: w1For film quality before immersion, W2Is the film quality after soaking.
(6) Measurement of hardness
Fixing a film which is cured on a glass plate in advance in a measuring instrument by adopting a pencil scratch hardness instrument, then placing pencils with different hardness on a propeller at an angle of 45 degrees, rotating an operating rod, propelling the pencils at a certain speed to leave scratches on the film, and if the scratches cannot break the flame-retardant film, the hardness of the pencils is the hardness of the coating.
(7) Determination of carbon residue rate
Carbon residue rate of sample calcined at 500 DEG CThe calculation formula is as follows:
in the formula: m1For pre-fired sample mass, M2Is the sample mass after firing.
(8) Determination of limiting oxygen index
The coating samples were mounted vertically on the top of the instrument using a HC-2 limit oxygen index instrument and fired and passed astm d2863-77 standard to obtain the LOI value of the coating.
(9) Vertical combustion measurement
Nano mesoporous SiO2/Zn2SnO4The vertical burning performance of the/EA flame-retardant coating is measured by a YCCT6022 type vertical burning tester.
3. Results and analysis
(1) XRD analysis
A. Nano mesoporous SiO2XRD analysis
FIG. 1 shows a nano-sized mesoporous SiO2The XRD pattern of (A) is shown in FIG. 1: the obtained nano mesoporous SiO2Has characteristic crystal planes of (100), (110), and (200) and SiO2Standard cards (JCPDS N.O 29-0085) fit. Shows that the synthesized nano mesoporous SiO2MCM-41 with typical one-dimensional straight pore channel and hexagonal close packing[8]Mesoporous SiO2Structure, consistent with the results of muirateron; the two crystal planes at (110) and (200) are not very obvious, and it is likely that the prepared product contains a mesoporous structure to mask the characteristic crystal planes at the two positions.
B、Zn2SnO4XRD analysis
FIG. 2 is Zn2SnO4The XRD pattern of (A) is shown in FIG. 2: each crystal plane in the figure is consistent with a standard card (JCPDS 74-2184), and the position of the crystal plane can be seen to be the synthesized Zn2SnO4Is of inverse spinel phase structure.
(2) Infrared analysis
A. Product infrared analysis
FIG. 3 shows the product (i.e., nano SiO after self-assembly)2/Zn2SnO4) The infrared spectrum of (2) can be seen from FIG. 3: FIG. 3(a) line is Zn2SnO4In the infrared spectrum of 3429cm-1Is an antisymmetric stretching vibration peak of-OH; at 2980cm-1Is of the formula-CH3A stretching vibration peak of the key; at 1634cm-1Is the H-OH bending vibration peak of water; at 1470cm-1Is the bending vibration peak of the silicate. FIG. 3(b) line shows a nano-sized mesoporous SiO2In the infrared spectrum of 1225cm-1The position is the antisymmetric stretching vibration of the Si-O-Si bond; at 966cm-1And 800cm-1Is a Si-O stretching vibration peak; FIG. 3(C) is a self-assembled nano-mesoporous SiO2/Zn2SnO4Infrared spectrum of the compound, 1385cm-1And 1080cm-1All are affected by Sn-O bonds[9](ii) a At 3500cm-1-1250cm-1Characteristic absorption peaks within the range are the same as in fig. 3 (b); at 725cm-1、654cm-1The characteristic peak at (a) is the same as that of FIG. 3; from this, Zn can be confirmed2SnO4Successfully attached to core-shell structure nano SiO2The above. B. Nano mesoporous SiO2/Zn2SnO4EA Infrared analysis
FIG. 4 is a graph of the infrared spectrum of the coating of sample 1 (without the addition of acrylic acid and acrylamide), as can be seen from FIG. 4: at a temperature of between 100 and 500 ℃ and at 3433cm-1Is the-OH antisymmetric stretching vibration peak of water; at 2968cm-1Is represented by-CH3Peak of stretching vibration, 2959cm after 400 deg.C-1Shift and the intensity of the peak decreases; at 1734cm-1C ═ O stretching vibration peak, disappear after 400 ℃, at this time, carbonyl in EA is degraded; 1514cm-1The position is a stretching vibration peak of C-C bond, which gradually disappears along with the rise of temperature; 1618cm appeared at 500 deg.C-1The peak is the H-OH bending vibration absorption peak of water, which is caused by the absorption of water by the sample during the measurement; at 1454cm-1The part is a C-H bending vibration absorption peak, and the degradation disappears when the temperature is 400 ℃; at 1396cm-1And 1260cm-1The peak is a C-O-C symmetric stretching vibration peak which is generated by ester groups in the epoxy acrylate and disappears after 400 ℃, and the analysis shows that EA is mainly degraded between 150 ℃ and 400 ℃. At 1177cm-1C-O stretching vibration peak is formed, and disappears after 400 ℃; at 1101cm-1The peak is the stretching vibration peak of Si-O and disappears after 100 ℃; 1053cm-1The peak is the bending vibration peak of Sn-O, the intensity of the peak is gradually reduced between 100 ℃ and 400 ℃, and the peak is 1099cm-1Is an antisymmetric stretching vibration peak of a Si-O-Si bond; at 880cm-1The position is an in-plane bending and stretching vibration peak of Si-H, and the strength is reduced along with the rise of the temperature; 810cm-1And 744cm-1Where the Si-C bond vibrates telescopically. In conclusion, in the process of increasing the temperature from 100 ℃ to 500 ℃, because acrylic acid and acrylamide are not added, the coating layer is not expanded and can not form a heat insulation layer, and the nano mesoporous SiO2/Zn2SnO4At higher temperatures, degradation to char forms an oxygen barrier and, therefore, EA coatings cannot be effectively prevented from degradation.
FIG. 5 shows sample 4(0.3g of nano-mesoporous SiO)2/Zn2SnO4) The infrared spectrum of (2) is shown in FIG. 5: at 150-500 deg.C and 3439cm-1the-OH stretching vibration peak of water is formed, and the strength of the peak is weakened along with the rise of the temperature; at 2957cm-1Is represented by-CH3The stretching vibration peak of (A) almost disappears at 500 ℃; at 1717cm-1The peak is the C ═ O stretching vibration peak of acrylic acid and acrylamide, disappears after 250 ℃, and the coating begins to expand; at 1612cm-1When C ═ C is degraded; at 1510cm-1The vibration peak is an N-H stretching vibration peak of acrylamide, the degradation disappears after the temperature is 250 ℃, and the gas released by the degradation of the acrylic acid and the acrylamide expands the coating; at 1452cm-1The peak is the bending vibration peak of C-H, which disappears after 300 ℃. 1383cm-1The stretching vibration of Si-O bond is weakened continuously along with the temperature rise and disappears after 400 ℃. 1242cm-1The peak is the stretching vibration peak of C-O, and the degradation disappears after 350 ℃. 1173cm-1Is the stretching vibration peak of the compound Si-O-Si, and the degradation disappears after 300 ℃, at this time, part of the nano mesoporous SiO2/Zn2SnO4Is degraded; at 1042cm-1Is prepared from nano-mesoporous SiO2/Zn2SnO4The stretching vibration of the medium Si-O-Zn bond exists between 150 ℃ and 500 ℃. In conclusion, 0.3g of nano-mesoporous SiO is added2/Zn2SnO4When the coating expands, it forms a thermal barrier layer, which adheres to the SiO2Zinc stannate in the pore canal can catalyze organic matters to form carbon, and a thin and long air hole is formed, so that the oxygen is effectively delayed to enter; nano mesoporous SiO2/Zn2SnO4The degradation plays a role in heat insulation and oxygen insulation of the coating, so that the flame retardant property of the coating is improved.
FIG. 6 shows sample 5(0.4g of nano-mesoporous SiO)2/Zn2SnO4) The real-time infrared spectrogram of (1) can be known from FIG. 6: at 3433cm-1The position is a-OH stretching vibration peak in zinc stannate; at 1653cm-1Is the H-OH bending vibration absorption peak of water; in 1720cm-1The C ═ O bond is subjected to stretching vibration, and the degradation is completed after the temperature is 250 ℃; at 1593cm-1And 1605cm-1An N-H stretching vibration peak is formed, and the degradation is completed after the temperature is 350 ℃; at 2961cm-1Is of the formula-CH3The stretching vibration peak of (1); at 1504cm-1The part is a bending vibration peak of C-H, and the degradation is complete after the temperature is 250 ℃; at 1450cm-1The absorption peak is-CH stretching vibration peak, and the degradation is complete after 350 ℃. The degradation of the groups is generated by the degradation of acrylic acid and acrylamide, and the coating expands when heated; at 1383cm-1Where is the bending vibration of the Sn-O bond; at 1248cm-1Is of the formula-CH2Peak of stretching vibration at 1179cm-1The absorption peak is the bending vibration peak of Zn-OH[10](ii) a At 1097cm-1Is the antisymmetric stretching vibration peak of Si-O-Si; at 500 ℃, a strong absorption peak appears and is positioned at 1090cm-11030cm between-1Here, it is estimated that the peak of stretching vibration is a peak of both Si-O-Si and Sn-O. At 822cm-1The sample is subjected to Si-O symmetrical stretching vibration, the strength between 150 ℃ and 400 ℃ is weakened along with the temperature rise, a plurality of undegraded absorption peaks are still formed at 500 ℃, and the reason why the sample is not degraded is probably that the sample is attached to the nano mesoporous SiO2Zn in the pore canal2SnO4Is degraded with the rise of temperature and then forms a protective layer to make SiO2The degradation rate of the coating is reduced, and the sample under the formula has good heating performance and good thermal stability and has an enhancement effect on the high-temperature resistance of the coating.
FIG. 7 is sample 7(0.6g of nano-mesoporous SiO)2/Zn2SnO4) The EA coating of (2) can be seen from fig. 7: at 3431cm-1The part is a stretching vibration peak of-OH, and the intensity of an absorption peak is continuously weakened along with the rise of temperature; at 2974cm-1And 2872cm-1Is represented by-CH3Has a peak of stretching vibration of 2974cm-1The methyl peak of (A) gradually weakens after 300 ℃; at 2376cm-1、2218cm-1And 2365cm-1The absorption peak is impurity CO2Influence of (2)[11](ii) a At 1736cm-1Where C ═ O shows a peak of stretching vibration, gradually disappearing with the rise of temperature, and this is the partial degradation of acrylic acid(ii) a At 1645cm-1Is the N-H stretching vibration peak of acrylamide; shows that the acrylic acid and the acrylamide begin to degrade along with the temperature rise at the moment, an expansion layer is formed on the surface of the coating, and the degradation of the coating is protected to a certain extent at 1618cm-1Is of the formula-NH2An in-plane bending vibration peak which disappears when the temperature rises to 350 ℃; at 1518cm-1The peak is the bending vibration absorption peak of C-H, and the degradation disappears after 250 ℃. At 1448cm-1The strain is a-CH stretching vibration peak and is completely degraded after 350 ℃; 1389cm-1The part is a bending vibration peak of Sn-O, and the strength between 150 ℃ and 350 ℃ is continuously weakened along with the temperature; at 1175cm-1The position is the stretching vibration of Zn-OH, the temperature is continuously weakened between 150 ℃ and 250 ℃, and the nano mesoporous SiO is formed2/Zn2SnO4In the SiO layer2Zn in the pore canal2SnO4Is degraded; 1042cm-1The process is the stretching vibration of Si-O-Zn, and the Si-O-Zn is completely degraded after the temperature is 250 ℃; at 1092cm-1The peak is the stretching vibration of Si-O-Si, and the intensity of the peak is not obviously reduced due to the increase of the temperature; in summary, the nano-mesoporous SiO at high temperature2/Zn2SnO4The degradation rate is slow, and a flame-retardant carbon layer with good heat insulation is formed on the surface of the coating. Part of the substances are not completely degraded at 500 ℃, and the high-temperature resistance of the coating is good, which shows that the heat insulation of the expanded carbon layer and the nano mesoporous SiO are added2/Zn2SnO4The carbon layer with the accelerated degradation improves the flame retardant effect of the EA coating.
(3) Ultraviolet analysis
Nano mesoporous SiO2/Zn2SnO4EA UV analysis
FIG. 8 shows a nano-sized mesoporous SiO2/Zn2SnO4The UV spectrum of the/EA, as shown in FIG. 8, is as follows: adding nano mesoporous SiO2/Zn2SnO4The content (0g, 0.2g, 0.3g, 0.4g, 0.5g, 0.6g) of the nano-mesoporous SiO greatly affects the light transmittance of the coating, and the content of the nano-mesoporous SiO has great influence along with the change of the nano-mesoporous SiO2/Zn2SnO4The increase of the content obviously reduces the light transmittance of the coating because of Zn2SnO4And nano mesoporous SiO2All are white powders, self-assembled, Zn2SnO4Attached to nano mesoporous SiO2In the pore canal, compact white nano-particle powder is formed, which causes that the powder is difficult to dissolve when being added into acrylic acid and acrylamide solution and seriously shields light. Thereby making the scraped coating film opaque, which is a main cause of low measured light transmittance.
(4) Thermal analysis
A. Nano mesoporous SiO2/Zn2SnO4Thermal analysis of EA
FIG. 9 shows a nano-sized mesoporous SiO2/Zn2SnO4Thermal analysis of the/EA, in which the curves a-c in FIG. 9(A) are nano-mesoporous SiO2/Zn2SnO4The addition amount is 0g, 0.2g, 0.3g, and the curve d-f in FIG. 9(B) is the nano-mesoporous SiO2/Zn2SnO4The thermograms of the coatings at the addition levels of 0.4g, 0.5g, and 0.6g are shown in the graphs (A) and (B): the downward concave is the endothermic peak and the upward convex is the exothermic peak. With the rise of the temperature, the sample continuously absorbs heat, at the moment, the internal components of the coating begin to decompose, then the heat release gradually begins, cold crystallization begins after the exothermic peak temperature is reached, and the sample tends to be stable after complete decomposition; when the nano mesoporous SiO is not added2/Zn2SnO4(FIG. 9(A) Curve a), the exothermic peak temperature Tm of the coating is 436.2 deg.C, when the nano-mesoporous SiO is present2/Zn2SnO4When the content is increased to 0.6g (curve f in fig. 9 (B)), the exothermic peak temperature Tm of the coating is 559.6 ℃; to sum up, with the nano-mesoporous SiO2/Zn2SnO4The content is increased, and the heat absorption and release temperature of the coating is gradually increased, so that the thermal stability of the coating is improved.
(5) Nano mesoporous SiO2/Zn2SnO4Analysis of flame retardancy of EA coating
A. Nano mesoporous SiO2/Zn2SnO4EA coating limiting oxygen index and vertical burning results
Table 2 shows the nano-sized mesoporous SiO2/Zn2SnO4The limiting oxygen index of the EA coating and the results of the vertical burning, as can be seen from Table 2:
with nano mesoporous SiO2/Zn2SnO4With increasing amounts (0g, 0.2g, 0.3g, 0.4g, 0.5g, 0.6g), the coating changes from transparent to opaque. When the addition amount is 0g, the color of the coating is colorless and transparent; when the addition amount is 0.2g, the coating is light yellow and transparent; when the addition amount is 0.3g, 0.4g, 0.5g, 0.6g, the coating is white and opaque. The reason is that the nano mesoporous SiO2/Zn2SnO4Is white powder, can be dissolved when a small amount of EA is added into the nano mesoporous SiO2/Zn2SnO4Above 0.2g, it is difficult to dissolve in the EA coating system and after UV light curing, the coating is white and opaque.
LOI index of coating along with nano mesoporous SiO2/Zn2SnO4The content is increased without adding nano-mesoporous SiO2/Zn2SnO4In the process, the LOI of the coating is 18, and the UL-94 is V-1 level, so that the coating is easy to burn; 0.6g of nano-mesoporous SiO is added2/Zn2SnO4The LOI of the coating is 30, and the UL-94 reaches the V-0 level, so that the coating is not easy to burn. Thus, with nano-mesoporous SiO2/Zn2SnO4The flame retardant property of the coating is improved by increasing the content.
The measurement result of the water absorption of the coating shows that only 0.4g of nano-mesoporous SiO is added2/Zn2SnO4When the coating absorbs water, the water absorption rate of the coating is 2 percent, and the rest coatings do not absorb water; all coatings reached a hardness of 5H.
In conclusion, when the nano-mesoporous SiO is used as the material2/Zn2SnO4When the content is 0.6g, the LOI of the EA coating reaches up to 30, and the UL-94 reaches the V-0 level, so that the coating is not easy to burn and has good thermal stability.
TABLE 2 nanometer mesoporous SiO2/Zn2SnO4EA coating limiting oxygen index and vertical burning results
B. Nano mesoporous SiO2/Zn2SnO4Analysis of residual carbon rate of EA coating
Table 3 shows the nano-sized mesoporous SiO2/Zn2SnO4The residual carbon rate of EA coating can be seen from Table 3: with nano mesoporous SiO2/Zn2SnO4The carbon residue rate of the coating is increased along with the increase of the content (0g, 0.2g, 0.3g, 0.4g, 0.5g and 0.6 g); wherein 0.6g of nano-mesoporous SiO is added2/Zn2SnO4The carbon residue rate of the coating is highest, the carbon residue rate of combustion under an alcohol lamp is 22.47%, and the carbon residue rate of combustion under a muffle furnace (500 ℃) is 17.32%; the reason for the higher carbon residue rate of the combustion coating under the alcohol lamp is as follows: when the alcohol burner burns, the coating is heated unevenly and burns incompletely; and the coating is burnt in a muffle furnace, so that the coating is uniformly heated and is fully burnt. Although the coating expands when heated to form a carbon layer on the surface for protection, the polymer in the carbon layer is degraded at high temperature, and the temperature at each position in the muffle furnace is different, so that the carbon residue rate of the coating is different, and the carbon residue rate is lower than that of an alcohol lamp.
In summary, after the coating is heated, the amino group and the acrylic acid in the acrylamide are degraded to release gas, so that the coating expands, and an expanded carbon layer is formed on the surface of the coating. Nano mesoporous SiO2/Zn2SnO4The carbon particles are degraded on the surface of the coating after being heated to form a tightly connected carbon particle structure, so that the carbon residue rate of the coating is improved.
TABLE 3 nanometer mesoporous SiO2/Zn2SnO4Residual carbon rate of EA coating
C. Nano mesoporous SiO2/Zn2SnO4EA carbon residue morphology analysis
Sample 1, the appearance of the combustion carbon residue without the addition of acrylic acid and acrylamide coating: the color of the coating changes from white to yellow along with the temperature rise between 100 ℃ and 300 ℃, because the EA yellowing resistance is not stable after being heated, so that the color of the coating is changed; the coating blackened but did not swell at 400-500 c because acrylic acid and acrylamide, which contained the acid source and gas source needed for swelling flame retardancy, were not added to the coating.
Sample 2, without the addition of nano-mesoporous SiO2/Zn2SnO4The morphology of EA coating carbon residue is as follows: the coating is heated stably at the temperature of 150 ℃ and 200 ℃ without obvious change; when the temperature is between 300 ℃ and 500 ℃; the carbon layer of the coating layer is in a collapsed state at 400 ℃ and 500 ℃ because the carbon layer has poor airtightness, is mainly composed of many fine carbon particles, and has a loose and porous structure. The carbon layer has poor heat insulation effect, and the porous structure can not prevent oxygen from entering the coating, so the flame retardant property of the coating is poor.
Sample 3, adding 0.2g of nano-mesoporous SiO2/Zn2SnO4The shape of the coating carbon residue-: the coating expands after 250 ℃, the shape of the carbon residue is good, and collapse does not occur; adding nano mesoporous SiO2/Zn2SnO4And then, the coating carbon layer has a good structure, a net-shaped compact carbon layer is formed, and the compact carbon layer can well insulate heat and isolate oxygen, so that the flame retardant effect is achieved.
Sample 4, adding 0.3g of nano-mesoporous SiO2/Zn2SnO4The shape of the carbon residue on the coating is as follows: the coating expands when heated at the temperature of 300 ℃ to 500 ℃, and the expanded appearance of the coating is better at the temperature of 300-400 ℃; the coating has small expansion at 500 ℃, but the carbon layer is dense because of the nano mesoporous SiO at high temperature2/Zn2SnO4The generated Si-O bond and Si-O-Zn bond are degraded and attached to the carbon layer, the expansion of the coating is inhibited, and the structure of the carbon layer is more compact, so that the heat resistance and the oxygen isolation of the carbon layer are improved, and the carbon residue rate of the coating is improved.
Sample 5, adding 0.4g of nano-mesoporous SiO2/Zn2SnO4The shape of the carbon residue on the coating is as follows: at the temperature of 300 ℃ and 400 ℃, the carbon residue of the coating has no cracks or collapse, the surface of the carbon layer is smooth, and the internal structure of the carbon layer is compact; the coating does not expand at 500 ℃, and a cavity appears in the middle of the coating because of the nano mesoporous SiO in the coating2/Zn2SnO4Non-uniform distribution.
Sample 6, adding 0.5g of nano-mesoporous SiO2/Zn2SnO4The shape of the coating carbon residue-: the surface of the coating begins to be carbonized at the temperature of 250 ℃ and 300 DEG C(ii) a The coating expands at the temperature of 350 ℃ and 400 ℃, and the shape of the carbon residue is good, which shows that the flame retardant effect of the coating is better in the temperature range.
Sample 7, 0.6g of nano-mesoporous SiO was added2/Zn2SnO4The shape of the carbon residue on the coating is as follows: the coating generates a charring layer at 250 ℃, and the coating begins to expand along with the increase of the temperature; the residual carbon of the coating at 500 ℃ has good appearance, the carbon layer has smooth appearance and compact internal carbon layer, prevents the oxygen in heat and air from spreading to the internal combustion area of the coating, and can effectively prevent the polymer pyrolysis component in an EA system from escaping, thereby playing a role in flame retardance[15]。
FIG. 10 shows the nano-mesoporous SiO with different addition amounts2/Zn2SnO4The morphology of the carbon residue of the coating (500 ℃) can be seen from FIG. 17: with nano mesoporous SiO2/Zn2SnO4The content is increased, the shape of the carbon residue of the coating basically shows a good trend, and especially 0.6g of nano mesoporous SiO is added2/Zn2SnO4And in addition, the carbon residue shape and the expansion multiple of the coating are good, the carbon layer is thick, the density is high, and the flame retardant property of the coating is improved.
From the above results, it can be seen that (1) the present example synthesizes nano-mesoporous SiO with cetyl trimethyl ammonium bromide and ethyl orthosilicate as reactants2(ii) a Zn is prepared by taking zinc chloride and stannic chloride as reactants2SnO4The synthesized zinc stannate is characterized to be inverse spinel phase positive Zn by XRD2SnO4(ii) a Synthetic nano SiO2Is SiO with a pore passage2Successfully self-assemble the nano mesoporous SiO2/Zn2SnO4. (2) Nano mesoporous SiO2/Zn2SnO4The infrared spectrum of the flame-retardant system of EA shows that when nano-mesoporous SiO2/Zn2SnO4When the content of the (B) is 0.6g, the flame retardant effect is optimal, the degradation is not completed under the real-time infrared display at 500 ℃, and the carbon residue rate at 500 ℃ of the muffle furnace reaches 17.32%. (3) Increase the nano mesoporous SiO2/Zn2SnO4The content has great influence on the transparency of the coating, and when the content is 0.6g in the visible light region between 500nm and 800nm, the light transmittance is lower than 25 percent, and the optimal light transmittance is nano dielectric constantSiO pore2/Zn2SnO4When the addition amount is 0.2g, 85% is reached, and the rest is between 40% and 60%. (4) When nano-mesoporous SiO2/Zn2SnO4When the addition amount is 0g, the thermal stability is poor, a plurality of heat absorption and release peaks appear, and the heat absorption and release peaks are along with the nano mesoporous SiO2/Zn2SnO4The content increase of the thermal stability is improved. The thermal stability was best when the amount of 0.6g was added. (5) When nano-mesoporous SiO2/Zn2SnO4When the content is 0.6g, the LOI of the EA coating reaches up to 30, and the UL-94 reaches the V-0 level, so that the coating is not easy to burn and has good thermal stability.
Claims (9)
1. Nano SiO with core-shell structure2/Zn2SnO4The preparation method of the flame-retardant epoxy acrylate coating is characterized by comprising the following steps: which comprises the following steps:
1) preparation of nano mesoporous SiO2
Placing deionized water, hexadecyl trimethyl ammonium bromide and 1.8-2.2mol/L NaOH solution into a flask, refluxing and stirring at 75-85 ℃, reacting for 25-35min, then adding tetraethoxysilane, wherein the dosage ratio of the deionized water, the hexadecyl trimethyl ammonium bromide, the NaOH solution and the tetraethoxysilane is 300 mL: 0.8-1.2 g: 3 mL: 4.5-5.5mL, continuously reacting for 1.5-2.5h, then filtering and drying the precipitate at the bottom of the flask, extracting the dried product with anhydrous methanol, refluxing at 85-95 ℃, stirring for 18-24h, filtering to obtain solid, repeatedly extracting the solid for 2-3 times, and finally drying the solid to obtain the nano mesoporous SiO2；
2) Preparation of zinc stannate Zn2SnO4
ZnCl is added according to the molar ratio of zinc ions to tin ions of 2:12And SnCl4·5H2Placing O in a container, adding water to adjust the pH =8.8-9.2, stirring and reacting for 15-25min, then transferring the mixed solution into a hydrothermal kettle with a polytetrafluoroethylene lining, continuing to react for 10-14h at the temperature of 180 ℃ and 220 ℃, cooling to room temperature, centrifuging, collecting precipitate, washing and drying to obtain a product Zn2SnO4；
3) Preparation of nano mesoporous SiO2/Zn2SnO4
According to the mass ratio of 1: 0.8-1.2, the nano mesoporous SiO is mixed with the solution2And Zn2SnO4Adding into water, stirring, subjecting the obtained mixture to ultrasonic treatment for 15-30min, centrifuging, collecting solid, washing with deionized water, and adding the solid into 1.8-2.2g/L NaNO3Performing ultrasonic treatment in the solution for 15-30min, centrifuging to obtain precipitate, drying, and grinding to obtain nanometer mesoporous SiO2/Zn2SnO4；
4) Preparation of epoxy acrylate coatings
Mixing acrylic acid, acrylamide and nano-mesoporous SiO2/Zn2SnO4And epoxy acrylate are uniformly mixed to obtain a mixture, and the mixture comprises the following components in percentage by mass: acrylic acid and acrylamide 35%, nano mesoporous SiO2/Zn2SnO4 2-6% of epoxy acrylate, 59-63% of epoxy acrylate, adding a photoinitiator into the mixture to obtain mixed resin, uniformly coating the mixed resin on a coating carrier, and curing by illumination to obtain the flame-retardant epoxy acrylate coating.
2. The core-shell structure nano SiO of claim 12/Zn2SnO4The preparation method of the flame-retardant epoxy acrylate coating is characterized by comprising the following steps: the dosage ratio of the deionized water, the hexadecyl trimethyl ammonium bromide, the NaOH solution and the ethyl orthosilicate is 300 mL: 1 g: 3 mL: 5 mL.
3. The core-shell structure nano SiO of claim 12/Zn2SnO4The preparation method of the flame-retardant epoxy acrylate coating is characterized by comprising the following steps: in the step 2), the precipitate is alternately washed 3-4 times by deionized water and absolute ethyl alcohol.
4. The core-shell structure nano SiO of claim 12/Zn2SnO4The preparation method of the flame-retardant epoxy acrylate coating is characterized by comprising the following steps: step (ii) of3) In (b), the nano mesoporous SiO2And Zn2SnO4The mass ratio of (A) to (B) is 1: 1.
5. The core-shell structure nano SiO of claim 12/Zn2SnO4The preparation method of the flame-retardant epoxy acrylate coating is characterized by comprising the following steps: in the step 4), the mass percent of acrylic acid in the mixture is 18-20%, and the mass percent of acrylamide is 15-17%.
6. The core-shell structure nano SiO of claim 52/Zn2SnO4The preparation method of the flame-retardant epoxy acrylate coating is characterized by comprising the following steps: in the step 4), the mixture comprises the following components in percentage by mass: 20% of acrylic acid, 15% of acrylamide and nano mesoporous SiO2/Zn2SnO4 6 percent and 59 percent of epoxy acrylate.
7. The core-shell structure nano SiO of claim 12/Zn2SnO4The preparation method of the flame-retardant epoxy acrylate coating is characterized by comprising the following steps: in the step 4), the addition amount of the photoinitiator is 3-3.5% of the total amount of the mixture.
8. The core-shell structure nano SiO of claim 12/Zn2SnO4The preparation method of the flame-retardant epoxy acrylate coating is characterized by comprising the following steps: in the step 4), firstly, adding acrylic acid and acrylamide into a beaker, ultrasonically dispersing by using 0.8-1.2KW ultrasonic waves until the acrylic acid and the acrylamide are dissolved, and then adding nano mesoporous SiO2/Zn2SnO4And after uniformly stirring, carrying out ultrasonic oscillation for 40-60min, then adding epoxy acrylate and 1173 photoinitiator, and after uniformly stirring, carrying out ultrasonic oscillation for 20-40min to obtain the mixed resin.
9. The core-shell structure nano SiO of claim 12/Zn2SnO4A preparation method of a flame-retardant epoxy acrylate coating,the method is characterized in that: in the step 4), the light curing is carried out by adopting 800-1200W/cm2The high-pressure mercury lamp of (1).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810146113.0A CN108384403B (en) | 2018-02-12 | 2018-02-12 | Preparation method of core-shell structure nano silicon dioxide/zinc stannate flame-retardant epoxy acrylate coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810146113.0A CN108384403B (en) | 2018-02-12 | 2018-02-12 | Preparation method of core-shell structure nano silicon dioxide/zinc stannate flame-retardant epoxy acrylate coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108384403A CN108384403A (en) | 2018-08-10 |
| CN108384403B true CN108384403B (en) | 2019-12-31 |
Family
ID=63068881
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810146113.0A Active CN108384403B (en) | 2018-02-12 | 2018-02-12 | Preparation method of core-shell structure nano silicon dioxide/zinc stannate flame-retardant epoxy acrylate coating |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108384403B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110628085B (en) * | 2019-09-02 | 2020-10-09 | 厦门大学 | Mesoporous silicon resin flame retardant, preparation method and flame-retardant composite material thereof |
| CN111300567A (en) * | 2019-11-29 | 2020-06-19 | 安徽智晟通讯科技有限公司 | Preparation method of efficient composite wood fire retardant |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6528552B1 (en) * | 2000-11-14 | 2003-03-04 | Mitsubishi Gas Chemical Company, Inc. | Resist composition excellent in flame resistance |
| WO2004041930A1 (en) * | 2002-11-05 | 2004-05-21 | Mitsubishi Plastics, Inc. | Flame-resistant vinyl chloride based resin composition and formed product therefrom |
| CN105198404A (en) * | 2015-09-29 | 2015-12-30 | 河南科技大学 | SnO2-Zn2SnO4 pressure sensitive and capacitive difunctional ceramic material and preparation method thereof |
| CN107674548A (en) * | 2017-11-01 | 2018-02-09 | 青岛农业大学 | A kind of preparation method based on magnetic gradient self-healing corrosion-inhibiting coating |
-
2018
- 2018-02-12 CN CN201810146113.0A patent/CN108384403B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6528552B1 (en) * | 2000-11-14 | 2003-03-04 | Mitsubishi Gas Chemical Company, Inc. | Resist composition excellent in flame resistance |
| WO2004041930A1 (en) * | 2002-11-05 | 2004-05-21 | Mitsubishi Plastics, Inc. | Flame-resistant vinyl chloride based resin composition and formed product therefrom |
| CN105198404A (en) * | 2015-09-29 | 2015-12-30 | 河南科技大学 | SnO2-Zn2SnO4 pressure sensitive and capacitive difunctional ceramic material and preparation method thereof |
| CN107674548A (en) * | 2017-11-01 | 2018-02-09 | 青岛农业大学 | A kind of preparation method based on magnetic gradient self-healing corrosion-inhibiting coating |
Non-Patent Citations (3)
| Title |
|---|
| "Oxide-catalyzed growth of Ag2O/Zn2SnO4 hybrid nanowires and their reversible catalytic ambient ethanol/oxygen detection";Wenjie Cai. etc;《Journal of Materials Chemistry》;20100511;第5265-5270页 * |
| "偏锡酸锌纳米微粒的水热法制备及其对甲基橙降解的光催化性能";张晓丹等;《化学研究》;20121130;第23卷(第6期);第86-89页 * |
| "贵金属催化剂对锡酸锌气敏特性的影响";徐甲强等;《云南大学学报（自然科学版）》;19971231;第79-82页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108384403A (en) | 2018-08-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Xu et al. | Zeolitic imidazolate framework-8 was coated with silica and investigated as a flame retardant to improve the flame retardancy and smoke suppression of epoxy resin | |
| Zhang et al. | Design of h-BN@ boronate polymer core-shell nanoplates to simultaneously enhance the flame retardancy and mechanical properties of epoxy resin through the interficial regulation | |
| CN108384403B (en) | Preparation method of core-shell structure nano silicon dioxide/zinc stannate flame-retardant epoxy acrylate coating | |
| CN102850905B (en) | Aqueous expansion-type steel structure fireproof paint and preparation method thereof | |
| Jiao et al. | Synergistic effects of Fe2O3 with layered double hydroxides in EVA/LDH composites | |
| CN108384402B (en) | Nano zinc stannate flame retardant with core-shell structure and epoxy acrylate intumescent flame retardant coating with core-shell structure and phosphorus and nitrogen synergistic effect of nano zinc stannate flame retardant and phosphorus and nitrogen | |
| CN105038521B (en) | A kind of metal Ludox expandable flame retardant coating and preparation method thereof | |
| Xu et al. | The flame retardancy and smoke suppression effect of a hybrid containing dihydrogen phosphate anion modified reduced graphene oxide/layered double hydroxide on epoxy resin | |
| Xu et al. | Fabrication of organophosphate-grafted kaolinite and its effect on the fire-resistant and anti-ageing properties of amino transparent fire-retardant coatings | |
| CN111154233B (en) | Flame-retardant epoxy resin based on iron-containing nickel silicate and preparation method thereof | |
| JP3456956B2 (en) | Fiber coating material and coating liquid used for it | |
| CN110606990A (en) | Hyperbranched polysiloxane-coated ammonium polyphosphate flame retardant and preparation method thereof | |
| CN105189356B (en) | The manufacture method of heat-resisting aluminium hydroxide | |
| CN107641135B (en) | Organosilane compound, filler, resin composition and copper-clad plate | |
| Zhang et al. | Fabrication of phytic acid embellished kaolinite and its effect on the flame retardancy and thermal stability of ethylene vinyl acetate composites | |
| Zhang et al. | Double organic groups‐containing polyhedral oligomeric silsesquioxane filled epoxy with enhanced fire safety | |
| Li et al. | Functionalized magnesium hydroxide with zinc borate and 3‐aminopropyltriethoxysilane for enhanced flame retardant and smoke suppressant properties of epoxy resins | |
| CN108219140A (en) | A kind of metal hybrid POSS and its epoxy acrylate anti-flaming dope | |
| CN110628085B (en) | Mesoporous silicon resin flame retardant, preparation method and flame-retardant composite material thereof | |
| CN105131688B (en) | A kind of photocuring expandable flame retardant coating of stanniferous ionic liquid fire retardant and the application fire retardant | |
| CN111867974B (en) | Precipitated white carbon black and preparation method thereof | |
| JP2018177550A (en) | Zirconia powder for high refractive index material and method for manufacturing the same | |
| CN110218508B (en) | Epoxy acrylate flame-retardant material containing phosphate intercalation layered hydroxide of zinc, aluminum and tin and preparation method thereof | |
| CN112940614A (en) | Film forming material for high-temperature superheated steam resistant coating and preparation method of coating | |
| Hu et al. | UV‐Irradiation Cured Organic‐inorganic Hybrid Nanocomposite Initiated by Ethoxysilane‐modified Multifunctional Polymeric Photoinitiator through Sol‐gel Process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20180810 Assignee: Putian Dongsheng Coatings Co.,Ltd. Assignor: PUTIAN University Contract record no.: X2023350000209 Denomination of invention: Preparation method of core-shell structure nano silica/zinc stannate flame retardant epoxy acrylate coating Granted publication date: 20191231 License type: Common License Record date: 20230428 Application publication date: 20180810 Assignee: Putian City Hanjiang District Antai coating Co.,Ltd. Assignor: PUTIAN University Contract record no.: X2023350000213 Denomination of invention: Preparation method of core-shell structure nano silica/zinc stannate flame retardant epoxy acrylate coating Granted publication date: 20191231 License type: Common License Record date: 20230428 |
|
| EE01 | Entry into force of recordation of patent licensing contract | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20180810 Assignee: Fujian sankeshu New Material Co.,Ltd. Assignor: PUTIAN University Contract record no.: X2023350000239 Denomination of invention: Preparation method of core-shell structure nano silica/zinc stannate flame retardant epoxy acrylate coating Granted publication date: 20191231 License type: Common License Record date: 20230517 |
|
| EE01 | Entry into force of recordation of patent licensing contract | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20180810 Assignee: PUTIAN HANJIANG YD PCB Co.,Ltd. Assignor: PUTIAN University Contract record no.: X2023350000399 Denomination of invention: Preparation method of core-shell structure nano silica/zinc stannate flame retardant epoxy acrylate coating Granted publication date: 20191231 License type: Common License Record date: 20231024 |
|
| EE01 | Entry into force of recordation of patent licensing contract |