CN116063866A - Vermiculite-based composite flame retardant and preparation method thereof - Google Patents
Vermiculite-based composite flame retardant and preparation method thereof Download PDFInfo
- Publication number
- CN116063866A CN116063866A CN202310032855.1A CN202310032855A CN116063866A CN 116063866 A CN116063866 A CN 116063866A CN 202310032855 A CN202310032855 A CN 202310032855A CN 116063866 A CN116063866 A CN 116063866A
- Authority
- CN
- China
- Prior art keywords
- vermiculite
- weight
- parts
- flame retardant
- based composite
- 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.)
- Pending
Links
- 239000010455 vermiculite Substances 0.000 title claims abstract description 112
- 229910052902 vermiculite Inorganic materials 0.000 title claims abstract description 112
- 235000019354 vermiculite Nutrition 0.000 title claims abstract description 112
- 239000003063 flame retardant Substances 0.000 title claims abstract description 77
- 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 56
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 claims abstract description 30
- 239000002245 particle Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 14
- 235000019832 sodium triphosphate Nutrition 0.000 claims abstract description 11
- 238000009830 intercalation Methods 0.000 claims description 36
- 230000002687 intercalation Effects 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 25
- 238000001914 filtration Methods 0.000 claims description 23
- 238000005406 washing Methods 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 13
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 239000006228 supernatant Substances 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 239000007822 coupling agent Substances 0.000 claims description 7
- 239000004576 sand Substances 0.000 claims description 7
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 230000008878 coupling Effects 0.000 claims description 5
- 238000010168 coupling process Methods 0.000 claims description 5
- 238000005859 coupling reaction Methods 0.000 claims description 5
- 239000002270 dispersing agent Substances 0.000 claims description 5
- 238000005188 flotation Methods 0.000 claims description 5
- PNGBYKXZVCIZRN-UHFFFAOYSA-M sodium;hexadecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCCCCCS([O-])(=O)=O PNGBYKXZVCIZRN-UHFFFAOYSA-M 0.000 claims description 5
- 239000012530 fluid Substances 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 3
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 3
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 3
- -1 aminosiloxane Chemical class 0.000 claims description 2
- 239000010410 layer Substances 0.000 abstract description 27
- 239000011229 interlayer Substances 0.000 abstract description 11
- 239000003973 paint Substances 0.000 abstract description 9
- 239000006087 Silane Coupling Agent Substances 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 125000003277 amino group Chemical group 0.000 abstract description 2
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 7
- 229920002379 silicone rubber Polymers 0.000 description 7
- 239000004945 silicone rubber Substances 0.000 description 7
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000779 smoke Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000002041 carbon nanotube Substances 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 239000012796 inorganic flame retardant Substances 0.000 description 3
- 230000020477 pH reduction Effects 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000000979 retarding effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- YZYDPPZYDIRSJT-UHFFFAOYSA-K boron phosphate Chemical compound [B+3].[O-]P([O-])([O-])=O YZYDPPZYDIRSJT-UHFFFAOYSA-K 0.000 description 1
- 229910000149 boron phosphate Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002120 nanofilm Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- CVNKFOIOZXAFBO-UHFFFAOYSA-J tin(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Sn+4] CVNKFOIOZXAFBO-UHFFFAOYSA-J 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 239000000080 wetting agent Substances 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
- 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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/28—Compounds of silicon
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
- C09C3/041—Grinding
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/06—Treatment with inorganic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/12—Treatment with organosilicon compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/32—Thermal properties
- C01P2006/37—Stability against thermal decomposition
Abstract
The invention discloses a vermiculite-based composite flame retardant and a preparation method thereof. According to the invention, the closely attached vermiculite layers are firstly spread by tetramethyl ammonium bromide to form a structure with interlayer space, then vermiculite particles with uniform particle size are obtained as much as possible by adopting a floatation method, and then the interior of the vermiculite sheets is aminated by adopting a silane coupling agent with amino groups, so that the subsequent flame retardant is ensured to enter the interlayer. According to the invention, the flame retardant such as sodium tripolyphosphate is intercalated between vermiculite layers, the sodium tripolyphosphate and the vermiculite are synergistic to realize flame retardance, and the composite flame retardant has excellent flame retardance, and has good compatibility with polymers, so that the prepared fireproof paint has the defects of high adhesive force and good thermal stability.
Description
Technical Field
The invention relates to the technical field of flame retardants, in particular to a vermiculite-based composite flame retardant and a preparation method thereof.
Background
The flame retardant is a functional auxiliary capable of imparting flame retardancy to flammable polymers, and can be classified into additive flame retardants and reactive flame retardants according to the method of use. In recent years, environmental protection consciousness of people is stronger, requirements on fire safety and flame retardance of products are higher, and halogen-free, low-smoke and low-toxicity environment-friendly flame retardants become pursued targets of people. Among them, inorganic flame retardants exhibit good environmental protection properties, but flame retardant properties are not excellent as organic flame retardants. Some organic flame retardants contain a halogen, in addition, the polymer such as plastic and resin has a small molecular weight, and migration and precipitation occur.
The halogen-free flame retardant which is studied at present mainly comprises calcium carbonate, aluminum hydroxide, magnesium hydroxide, layered silicate materials, inorganic phosphorus-based, boron-based, expanded graphite and other inorganic flame retardant materials, organic nitrogen-based and phosphorus-based flame retardants and the like. The halogen-free flame retardant has the advantages of environmental protection, low smoke and the like, but the single flame retardant component also has the defects of poor flame retardant effect, poor smoke suppression effect and the like.
The layers of vermiculite are single-molecule hydration layers, each layer of vermiculite is composed of silicon oxygen tetrahedra, and are connected in an interlayer hydrogen bond mode, and water molecules are connected with each layer of silicon oxygen tetrahedra in a hydrogen bond mode, so that the thixotropic property of the system is greatly increased. The melting point of vermiculite is 1370-1400 ℃, and the heat conductivity coefficient is extremely low by 0.046W/(M.K). The expansion between heated layers is 2-40 times when meeting fire, and has excellent flame retardant property.
Patent CN104804440B discloses a method for preparing a silicone rubber/vermiculite composite material, which is to react expanded vermiculite with diisocyanate: preparing an isocyanate modified expanded vermiculite, and generating a layer of isocyanate-reactive molecular film on the surface of the expanded vermiculite; then polymerizing the modified polymer with condensed silicone rubber to generate silicone rubber/expanded vermiculite prepolymer; and finally, adding a silane coupling agent into the silicone rubber/expanded vermiculite prepolymer for crosslinking to generate the silicone rubber/expanded composite elastomer material. After the expanded vermiculite is doped, the mechanical property, the heat preservation property and the flame retardant property of the silicone rubber are improved, but the effect of the organic flame retardant is far less than that of the silicone rubber.
Patent CN115160645a discloses a preparation method of a vermiculite compound flame retardant material, wherein the vermiculite compound flame retardant material comprises vermiculite, carbon nanotubes, boron phosphate and tin hydroxide. According to the preparation method, vermiculite is prepared by pretreatment of vermiculite, the vermiculite carbon nano tube composite material is prepared by crystallization treatment, the vermiculite flame retardant material is prepared by mixing with an organic plastic material, and a curing agent is added to prepare a plastic finished product with high flame retardant property, but the carbon nano tube has high cost and does not thoroughly solve the limitation of an inorganic flame retardant.
Disclosure of Invention
Aiming at the defects in the prior art, the technical problem to be solved by the invention is to provide the vermiculite-based composite flame retardant and the preparation method thereof, wherein the composite flame retardant is prepared by adopting different flame retardant components, and the synergistic effect and the intercalation effect of the composite flame retardant are utilized, so that the influence of direct dispersion of flame retardant molecules in materials on the material performance in the prior art is overcome, and the flame retardant smoke suppression effect of the flame retardant is improved together.
In order to solve the problems, the invention adopts the technical scheme that:
the invention provides a preparation method of a vermiculite-based composite flame retardant, which comprises the following steps:
(1) Acidizing intercalation
60 to 80 weight parts of nano vermiculite, 8 to 10 weight parts of tetramethyl ammonium bromide and 0.5 to 2 weight parts of 98 percent sulfuric acid are added into 500 weight parts of deionized water, and after stirring reaction is carried out for 4 to 8 hours at 80 ℃, the mixture is filtered, washed and dried to obtain the tetramethyl ammonium bromide intercalation modified vermiculite.
Before acidification intercalation, the layers of vermiculite are tightly attached, and the acidification intercalation is to support a tightly combined interlayer structure by using tetramethyl ammonium bromide in an acidic environment, otherwise, the intercalation of the flame retardant cannot be directly carried out.
(2) Particle size flotation
Taking 1-8 parts by weight of tetramethyl ammonium bromide intercalated modified vermiculite, adding 4-8 parts by weight of dispersing agent, sanding for 4-8 hours in a sand mill by using zirconia balls with the diameter of 2mm, adding 20-30 parts by weight of deionized water, settling for 12-24 hours, centrifuging, filtering, washing and drying supernatant fluid to obtain vermiculite with uniform particle size and tetramethyl ammonium bromide in the interlayer.
The excessively wide particle size range can lead to small-particle-size vermiculite or exfoliated monolithic vermiculite after acidification intercalation to be filled between large-particle-size layers, and influence the intercalation effect of the final flame retardant, so that the particle size range is between 1 and 100 mu m.
(3) Amino coupling
Adding 5-10 parts by weight of intercalation modified vermiculite treated in the step (2) and 10-15 parts by weight of toluene into a three-neck flask, introducing nitrogen, heating and stirring, adding 2-8 parts by weight of an aminosilane coupling agent when the temperature is raised to 80-100 ℃, and heating to 120 ℃ for reaction for 30min; and after the reaction is finished, filtering, washing and vacuum drying to obtain the amino vermiculite.
The amino silane coupling agent is added to aminate hydroxyl groups on the surface and between the vermiculite layers, and the H atom reaction activity of the amino groups is obviously higher than that of the H atoms on the silicon hydroxyl groups, so that the intercalation of the flame retardant is more easy to occur.
(4) Flame retardant intercalation
Adding 5-10 parts by weight of aminated vermiculite and 10-15 parts by weight of ethanol into a three-neck flask, introducing nitrogen, heating and stirring, adding 4-8 parts by weight of intercalation agent when the temperature is raised to 40-60 ℃, refluxing and stirring at 80 ℃ for reacting for 0.5-1 h, filtering, washing and vacuum drying to obtain the vermiculite-based organic-inorganic composite flame retardant.
Further, the dispersing agent is one or more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and sodium hexadecyl sulfonate.
Further, the intercalation agent is one or more of sodium tripolyphosphate, sodium hexametaphosphate and sodium borohydride.
Further, the aminosiloxane coupling agent is one or more of KH550, KH540, KH792 and KH 602.
The invention also provides a vermiculite-based composite flame retardant, which is prepared by the preparation method of the vermiculite-based composite flame retardant.
Thirdly, the vermiculite-based composite flame retardant provided by the invention is applied to fireproof materials.
According to the invention, the closely attached vermiculite layers are firstly spread by tetramethyl ammonium bromide to form a structure with interlayer space, then a floatation method is adopted to obtain vermiculite particles with uniform particle size as much as possible, so that the purposes of avoiding uneven dispersion possibly caused by uneven particle size and affecting the intercalation effect of a final flame retardant are achieved, and then an amino silane coupling agent is adopted to carry out amination on the inside of vermiculite sheets, so that the follow-up flame retardant is ensured to enter the interlayer, namely better compounding. The vermiculite layers are single molecular hydration layers, each layer of vermiculite is formed by silicon oxygen tetrahedrons, the vermiculite layers are connected in an interlayer hydrogen bond mode, water molecules are also connected with each layer of silicon oxygen tetrahedrons in a hydrogen bond mode, and the vermiculite has good dispersibility and compatibility in the fireproof coating. The vermiculite has excellent flame retardant property, and the high temperature can lead the interlayer of the vermiculite to continuously and rapidly expand in the flame retardant process of the vermiculite, so that flame retardants such as sodium tripolyphosphate and the like can be released, and the two materials are synergistic to realize flame retardance, so that the flame retardant has more excellent flame retardant performance.
Detailed Description
For a further understanding of the present invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are merely intended to illustrate further features and advantages of the invention, and are not limiting of the claims of the invention.
The reagents or apparatus used in the present invention are conventional products commercially available without identifying the manufacturer.
Example 1
(1) Acidizing intercalation
Adding 70 parts by weight of nano vermiculite, 8 parts by weight of tetramethyl ammonium bromide and 1 part by weight of 98% sulfuric acid into 500 parts by weight of deionized water, stirring at 80 ℃ for reaction for 6 hours, and then filtering, washing and drying to obtain tetramethyl ammonium bromide intercalation modified vermiculite;
(2) Particle size flotation
Taking 6 parts by weight of tetramethyl ammonium bromide intercalated modified vermiculite, adding 7 parts by weight of sodium hexadecyl sulfonate, sanding for 6 hours in a sand mill by using zirconia balls with the diameter of 2mm, adding 30 parts by weight of deionized water, settling for 24 hours, obtaining supernatant by adopting a decantation method, centrifuging, filtering, washing and drying the supernatant to obtain vermiculite with uniform particle size and tetramethyl ammonium bromide contained between layers;
(3) Amino coupling
Adding 10 parts by weight of intercalation modified vermiculite treated in the step (2) and 12 parts by weight of toluene into a three-neck flask, introducing nitrogen, heating and stirring, adding 6 parts by weight of an aminosilane coupling agent when the temperature is increased to 90 ℃, and heating to 120 ℃ for reaction for 30min; after the reaction is finished, filtering, washing and vacuum drying to obtain amino vermiculite;
(4) Flame retardant intercalation
Adding 8 parts by weight of amino vermiculite and 12 parts by weight of ethanol into a three-neck flask, introducing nitrogen, heating and stirring, adding 6 parts by weight of sodium tripolyphosphate when the temperature is raised to 50 ℃, refluxing and stirring for reaction for 1h at 80 ℃, filtering, washing and vacuum drying to obtain the vermiculite-based composite flame retardant.
Example 2
(1) Acidizing intercalation
Adding 80 parts by weight of nano vermiculite, 10 parts by weight of tetramethyl ammonium bromide and 2 parts by weight of 98% sulfuric acid into 500 parts by weight of deionized water, stirring at 80 ℃ for reaction for 8 hours, and then filtering, washing and drying to obtain tetramethyl ammonium bromide intercalation modified vermiculite;
(2) Particle size flotation
Taking 3 parts by weight of tetramethyl ammonium bromide intercalated modified vermiculite, adding 4 parts by weight of sodium dodecyl benzene sulfonate, sanding for 6 hours in a sand mill by using zirconia balls with the diameter of 2mm, adding 20 parts by weight of deionized water, settling for 16 hours, centrifuging, filtering, washing and drying supernatant fluid to obtain vermiculite with uniform particle size and tetramethyl ammonium bromide contained between layers;
(3) Amino coupling
Adding 5 parts by weight of intercalation modified vermiculite treated in the step (2) and 10 parts by weight of toluene into a three-neck flask, introducing nitrogen, heating and stirring, adding 2 parts by weight of an aminosilane coupling agent when the temperature is raised to 80 ℃, and heating to 120 ℃ for reaction for 30min; after the reaction is finished, filtering, washing and vacuum drying to obtain amino vermiculite;
(4) Flame retardant intercalation
Adding 5 parts by weight of amino vermiculite and 10 parts by weight of ethanol into a three-neck flask, introducing nitrogen, heating and stirring, adding 4 parts by weight of sodium hexametaphosphate when the temperature is raised to 50 ℃, carrying out reflux stirring reaction for 0.8h at 80 ℃, filtering, washing and drying in vacuum to obtain the vermiculite-based composite flame retardant.
Example 3
(1) Acidizing intercalation
Adding 60 parts by weight of nano vermiculite, 9 parts by weight of tetramethyl ammonium bromide and 0.8 part by weight of 98% sulfuric acid into 500 parts by weight of deionized water, stirring at 80 ℃ for reaction for 4 hours, and then filtering, washing and drying to obtain tetramethyl ammonium bromide intercalation modified vermiculite;
(2) Particle size flotation
8 parts by weight of tetramethyl ammonium bromide intercalated modified vermiculite is taken, 8 parts by weight of sodium dodecyl sulfate is added, zirconia balls with the diameter of 2mm are used for sanding for 8 hours in a sand mill, 30 parts by weight of deionized water is added, sedimentation is carried out for 20 hours, and supernatant fluid is centrifuged, filtered, washed and dried to obtain vermiculite with uniform particle size and tetramethyl ammonium bromide contained between layers;
(3) Amino coupling
Adding 5-10 parts by weight of intercalation modified vermiculite treated in the step (2) and 10-15 parts by weight of toluene into a three-neck flask, introducing nitrogen, heating and stirring, adding 2-8 parts by weight of an aminosilane coupling agent when the temperature is raised to 80-100 ℃, and heating to 120 ℃ for reaction for 30min; after the reaction is finished, filtering, washing and vacuum drying to obtain amino vermiculite;
(4) Flame retardant intercalation
Adding 10 parts by weight of amino vermiculite and 15 parts by weight of ethanol into a three-neck flask, introducing nitrogen, heating and stirring, adding 8 parts by weight of sodium borohydride when the temperature is raised to 60 ℃, refluxing and stirring for reaction for 1h at 80 ℃, filtering, washing and vacuum drying to obtain the vermiculite-based composite flame retardant.
Comparative example 1
(1) Adding 70 parts by weight of nano vermiculite, 8 parts by weight of tetramethyl ammonium bromide and 1 part by weight of 98% sulfuric acid into 500 parts by weight of deionized water, stirring at 80 ℃ for reaction for 6 hours, and then filtering, washing and drying to obtain tetramethyl ammonium bromide intercalation modified vermiculite;
(2) Taking 6 parts by weight of tetramethyl ammonium bromide intercalated modified vermiculite, adding 7 parts by weight of sodium hexadecyl sulfonate, sanding for 6 hours in a sand mill by using zirconia balls with the diameter of 2mm, adding 30 parts by weight of deionized water, settling for 24h, adopting a decanting method to obtain supernatant, centrifuging, filtering, washing and drying the supernatant to obtain vermiculite with uniform particle size and tetramethyl ammonium bromide in the interlayer;
(3) Adding 10 parts by weight of intercalation modified vermiculite treated in the step (2) and 12 parts by weight of ethanol into a three-neck flask, introducing nitrogen, heating and stirring, adding 6 parts by weight of sodium tripolyphosphate when the temperature is raised to 50 ℃, refluxing and stirring at 80 ℃ for reaction for 1h, filtering, washing and vacuum drying to obtain the vermiculite-based composite flame retardant.
Comparative example 2
(1) Adding 70 parts by weight of nano vermiculite, 8 parts by weight of tetramethyl ammonium bromide and 1 part by weight of 98% sulfuric acid into 500 parts by weight of deionized water, stirring at 80 ℃ for reaction for 6 hours, and then filtering, washing and drying to obtain tetramethyl ammonium bromide intercalation modified vermiculite;
(2) Taking 6 parts by weight of tetramethyl ammonium bromide intercalation modified vermiculite and 6 parts by weight of sodium tripolyphosphate, adding 7 parts by weight of sodium hexadecyl sulfonate, sanding for 6 hours in a sand mill by using zirconia balls with the diameter of 2mm, adding 30 parts by weight of deionized water, settling for 24 hours, obtaining supernatant by adopting a decanting method, centrifuging, filtering, washing and drying the supernatant, and obtaining the vermiculite-based composite flame retardant.
Comparative example 3
And (3) crushing the nano vermiculite and the sodium tripolyphosphate according to the weight ratio of 1:1 by a ball mill, and screening to 200 meshes to obtain the composite flame retardant.
Adding 50 parts by weight of water into a material tank of a high-speed dispersing machine, sequentially adding 0.4 part by weight of a dispersing agent 5040, 0.4 part by weight of a defoaming agent NXZ and 0.4 part by weight of a wetting agent OP-10 under the high-speed dispersing effect, slowly adding 100.0 parts by weight of expansion type examples 1-3 and comparative examples 1-3 respectively to prepare a composite flame retardant, dispersing at high speed for 2 hours, reducing the dispersing speed, adding 25.0 parts by weight of polyacrylate emulsion, a proper amount of polyacrylic acid type thickening agent, a pH value regulator AMP-95 and the like, and stirring and dispersing for more than 1 hour to obtain the fireproof paint.
The fire retardant coatings prepared by the composite fire retardants prepared in examples 1 to 3 and comparative examples 1 to 3 were tested and evaluated, and the test results are shown in Table 1.
(1) Flame retardant properties: vertical burn tests were performed on this according to UL94 standard.
(2) Limiting oxygen index: the test was performed according to GBT 2406.2 standard.
(3) Smoke density: the test was performed according to GB/T8323.2 standard.
(4) Adhesion test: refer to GB/T9286-1998.
(5) Constant temperature and humidity weather resistance test: solidifying the paint film on an IPC B25A comb-shaped electrode plate, controlling the dry film thickness to be 50 mu m, and placing the electrode plate in a constant temperature and humidity box at 85 ℃ and 85%RH for 720 hours; after the test is finished, whether appearance phenomena such as white shift, foaming, pinholes, cracks, fine cracks, wrinkling, falling off, separation, color change and the like exist in the appearance of the paint film or not is observed.
(6) Cold and hot impact test: the paint film is solidified on an IPC B25A comb-shaped electrode plate, the dry film thickness is controlled to be 50um, and the paint film is placed in an environment test box with the high temperature of 125 ℃ and the low temperature of 40 ℃ and the high temperature and the low temperature of 30 minutes respectively and the high temperature and the low temperature of 2 minutes respectively, and 700 cycles are performed.
(7) Salt spray resistance test: measuring the neutral salt spray resistance of GB/T1771 1991 colored paint and varnish; after the test is finished, observing whether the appearance of the paint film has the phenomena of foaming, rust stain, creep, blushing, blackening, falling, separating and the like.
TABLE 1
As can be seen from the data in Table 1, firstly, the fire retardants such as sodium tripolyphosphate are intercalated between vermiculite layers, the vermiculite itself has excellent fire retardant performance, and in the fire retarding process of the vermiculite, the high temperature can lead the vermiculite layers to continuously and rapidly expand, so that the fire retardants such as sodium tripolyphosphate can be released, and the fire retardants and the vermiculite cooperate to realize fire retardation, so that the fire retarding performance is more excellent. And secondly, the vermiculite layers are single-molecule hydration layers, each layer of vermiculite is formed by silicon oxygen tetrahedrons, the vermiculite layers are connected in an interlayer hydrogen bond mode, water molecules are also connected with each layer of silicon oxygen tetrahedrons in a hydrogen bond mode, and the vermiculite has good dispersibility and compatibility in the fireproof paint.
Those skilled in the art can also make appropriate changes and modifications to the above-described embodiments in light of the above disclosure. Therefore, the invention is not limited to the specific embodiments disclosed and described above, but some modifications and changes of the invention should be also included in the scope of the claims of the invention. In addition, although specific terms are used in the present specification, these terms are for convenience of description only and do not limit the present invention in any way.
Claims (6)
1. A preparation method of a vermiculite-based composite flame retardant is characterized by comprising the following steps: the method comprises the following steps:
(1) Acidizing intercalation
Adding 60-80 parts by weight of nano vermiculite, 8-10 parts by weight of tetramethyl ammonium bromide and 0.5-2 parts by weight of 98% sulfuric acid into 500 parts by weight of deionized water, stirring at 80 ℃ for reaction for 4-8 hours, and then filtering, washing and drying to obtain tetramethyl ammonium bromide intercalation modified vermiculite;
(2) Particle size flotation
Taking 1-8 parts by weight of tetramethyl ammonium bromide intercalated modified vermiculite, adding 4-8 parts by weight of dispersing agent, sanding for 4-8 hours in a sand mill by using zirconia balls with the diameter of 2mm, adding 20-30 parts by weight of deionized water, settling for 12-24 hours, centrifuging, filtering, washing and drying supernatant fluid to obtain vermiculite with uniform particle size and tetramethyl ammonium bromide contained between layers;
(3) Amino coupling
Adding 5-10 parts by weight of intercalation modified vermiculite treated in the step (2) and 10-15 parts by weight of toluene into a three-neck flask, introducing nitrogen, heating and stirring, adding 2-8 parts by weight of an aminosilane coupling agent when the temperature is raised to 80-100 ℃, and heating to 120 ℃ for reaction for 30min; after the reaction is finished, filtering, washing and vacuum drying to obtain amino vermiculite;
(4) Flame retardant intercalation
Adding 5-10 parts by weight of aminated vermiculite and 10-15 parts by weight of ethanol into a three-neck flask, introducing nitrogen, heating and stirring, adding 4-8 parts by weight of intercalation agent when the temperature is raised to 40-60 ℃, refluxing and stirring at 80 ℃ for reacting for 0.5-1 h, filtering, washing and vacuum drying to obtain the vermiculite-based composite flame retardant.
2. The method for preparing a vermiculite-based composite fire retardant according to claim 1, wherein: the dispersing agent is one or more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and sodium hexadecyl sulfonate.
3. The method for preparing a vermiculite-based composite fire retardant according to claim 1, wherein: the intercalation agent is one or more of sodium tripolyphosphate, sodium hexametaphosphate and sodium borohydride.
4. The method for preparing a vermiculite-based composite fire retardant according to claim 1, wherein: the aminosiloxane coupling agent is one or more of KH550, KH540, KH792 and KH 602.
5. A vermiculite-based composite flame retardant, characterized in that: a method of preparing a vermiculite-based composite fire retardant according to any one of claims 1 to 4.
6. The vermiculite-based composite fire retardant of claim 5, wherein: the composite flame retardant is applied to fireproof materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310032855.1A CN116063866A (en) | 2023-01-10 | 2023-01-10 | Vermiculite-based composite flame retardant and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310032855.1A CN116063866A (en) | 2023-01-10 | 2023-01-10 | Vermiculite-based composite flame retardant and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116063866A true CN116063866A (en) | 2023-05-05 |
Family
ID=86174462
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310032855.1A Pending CN116063866A (en) | 2023-01-10 | 2023-01-10 | Vermiculite-based composite flame retardant and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116063866A (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200610810A (en) * | 2004-09-21 | 2006-04-01 | Ind Tech Res Inst | A composite of flame retardant clay/silicon and its use |
| CN101307182A (en) * | 2008-06-26 | 2008-11-19 | 东华大学 | Method for preparing meso-scale flaky vermiculite and heat-resistant polymer heat insulation composite membrane |
| CN104072805A (en) * | 2014-07-02 | 2014-10-01 | 新疆奥吉立节能科技股份有限公司 | Vermiculite-based composite flame retardant and preparation method thereof |
| CN110183730A (en) * | 2019-05-24 | 2019-08-30 | 武汉工程大学 | Organic modified nano basic zirconium phosphate cladded type ammonium polyphosphate and preparation method thereof |
| CN110894369A (en) * | 2019-10-31 | 2020-03-20 | 武汉工程大学 | Flame retardant based on phosphaphenanthrene group modified zirconium phosphate and preparation method thereof |
| CN111607255A (en) * | 2020-06-09 | 2020-09-01 | 新疆大学 | Polylactic acid-modified vermiculite composite material, preparation method and application |
| CN112876740A (en) * | 2021-01-29 | 2021-06-01 | 武汉工程大学 | Phenylboronic acid grafted and modified zirconium phosphate-based flame retardant and preparation method thereof |
-
2023
- 2023-01-10 CN CN202310032855.1A patent/CN116063866A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200610810A (en) * | 2004-09-21 | 2006-04-01 | Ind Tech Res Inst | A composite of flame retardant clay/silicon and its use |
| CN101307182A (en) * | 2008-06-26 | 2008-11-19 | 东华大学 | Method for preparing meso-scale flaky vermiculite and heat-resistant polymer heat insulation composite membrane |
| CN104072805A (en) * | 2014-07-02 | 2014-10-01 | 新疆奥吉立节能科技股份有限公司 | Vermiculite-based composite flame retardant and preparation method thereof |
| CN110183730A (en) * | 2019-05-24 | 2019-08-30 | 武汉工程大学 | Organic modified nano basic zirconium phosphate cladded type ammonium polyphosphate and preparation method thereof |
| CN110894369A (en) * | 2019-10-31 | 2020-03-20 | 武汉工程大学 | Flame retardant based on phosphaphenanthrene group modified zirconium phosphate and preparation method thereof |
| CN111607255A (en) * | 2020-06-09 | 2020-09-01 | 新疆大学 | Polylactic acid-modified vermiculite composite material, preparation method and application |
| CN112876740A (en) * | 2021-01-29 | 2021-06-01 | 武汉工程大学 | Phenylboronic acid grafted and modified zirconium phosphate-based flame retardant and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 刘开平, 王尉和, 宫华, 李连生: "矿物材料及其纳米技术改造", 中国矿业, no. 02, 15 February 2005 (2005-02-15) * |
| 毛庆辉;叶早萍;陈春升;: "阻燃隔热蛭石水溶胶整理剂的制备及应用", 印染, no. 04, 15 February 2013 (2013-02-15) * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102653628B (en) | Preparation method and application of nano sol modified waterborne polyurethane emulsion | |
| CN105295645B (en) | A kind of heat resist modification epoxy-based lacquers and its preparation method and application | |
| CN112961528A (en) | Environment-friendly fireproof coating and preparation method thereof | |
| CN107142018B (en) | Water-based environment-friendly modified asphalt waterproof coiled material and manufacturing process thereof | |
| CN102850905A (en) | Aqueous expansion-type steel structure fireproof paint and preparation method thereof | |
| CN111269624B (en) | Wide-temperature-range heat-insulation water-based damping coating and preparation method thereof | |
| CN101892004B (en) | Ultraviolet-cured heat-resistant coating and preparation and application methods thereof | |
| CN105885582A (en) | Water-borne plastic paint and preparation method thereof | |
| Yang et al. | Flame retarded rigid polyurethane foam composites based on gel-silica microencapsulated ammonium polyphosphate | |
| Wang et al. | Study on novel flame retarded LDH-TDI-HEA-VTES-acrylate composites and their flame retardant mechanism | |
| CN110903689A (en) | Hydrophobic modified ternary intumescent flame retardant, preparation method thereof and water-based intumescent fire retardant coating | |
| CN113773735A (en) | Flame-retardant waterborne polyurethane material | |
| CN110396350B (en) | Anticorrosive paint and preparation method and application thereof | |
| CN113549388A (en) | Water-based single-component seal primer coating and preparation method thereof | |
| CN116063866A (en) | Vermiculite-based composite flame retardant and preparation method thereof | |
| CN115975467A (en) | High-adhesion nano anticorrosion and heat-insulation integrated coating and preparation method thereof | |
| CN105924781A (en) | Halogen-free and flame-retardant polypropylene cable material and preparation method thereof | |
| CN113773497B (en) | High-temperature-resistant modified silicone adhesive and application thereof in flexible mica plate | |
| CN112920687B (en) | Single-component flake type epoxy zinc-rich anti-corrosive primer and preparation method thereof | |
| CN108384410A (en) | A kind of environment-friendlyfireproof fireproof paint and preparation method thereof | |
| WO2019083136A1 (en) | Self-healing polyurea/sol-gel silica nanohybrid cured product, and preparation method therefor | |
| CN113717610A (en) | Nano titanium modified flaky zinc powder anticorrosive paint and preparation method thereof | |
| CN109694214B (en) | Novel bonding material for expanded perlite insulation board and preparation method and application thereof | |
| CN116355469B (en) | Intumescent fire retardant coating for railway vehicle and preparation method thereof | |
| CN105505052A (en) | Steel-structure super-thin intumescent fire-retardant coating and preparing method thereof |
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 |