CN110128918A - A kind of product of rubber and plastic flame protection coating and preparation method thereof - Google Patents
A kind of product of rubber and plastic flame protection coating and preparation method thereof Download PDFInfo
- Publication number
- CN110128918A CN110128918A CN201910454099.5A CN201910454099A CN110128918A CN 110128918 A CN110128918 A CN 110128918A CN 201910454099 A CN201910454099 A CN 201910454099A CN 110128918 A CN110128918 A CN 110128918A
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- CN
- China
- Prior art keywords
- mass parts
- protection coating
- flame protection
- flame
- retardant
- Prior art date
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- 238000000576 coating method Methods 0.000 title claims abstract description 88
- 239000011248 coating agent Substances 0.000 title claims abstract description 85
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- 239000005060 rubber Substances 0.000 title claims abstract description 33
- 229920003023 plastic Polymers 0.000 title claims abstract description 26
- 239000004033 plastic Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000003063 flame retardant Substances 0.000 claims abstract description 66
- 239000006185 dispersion Substances 0.000 claims abstract description 34
- 239000007788 liquid Substances 0.000 claims abstract description 33
- -1 polyphenol compound Chemical class 0.000 claims abstract description 22
- 239000000945 filler Substances 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 235000013824 polyphenols Nutrition 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 13
- 229920006112 polar polymer Polymers 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 230000004048 modification Effects 0.000 claims abstract description 7
- 238000012986 modification Methods 0.000 claims abstract description 7
- 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 class 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 claims description 30
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
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- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 13
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- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 claims description 4
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- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
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- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical group C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 4
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- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 4
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- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 2
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 2
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- 239000004640 Melamine resin Substances 0.000 claims description 2
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims description 2
- 229920000459 Nitrile rubber Polymers 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 2
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- QHWKHLYUUZGSCW-UHFFFAOYSA-N Tetrabromophthalic anhydride Chemical group BrC1=C(Br)C(Br)=C2C(=O)OC(=O)C2=C1Br QHWKHLYUUZGSCW-UHFFFAOYSA-N 0.000 claims description 2
- KYPYTERUKNKOLP-UHFFFAOYSA-N Tetrachlorobisphenol A Chemical compound C=1C(Cl)=C(O)C(Cl)=CC=1C(C)(C)C1=CC(Cl)=C(O)C(Cl)=C1 KYPYTERUKNKOLP-UHFFFAOYSA-N 0.000 claims description 2
- YMOONIIMQBGTDU-VOTSOKGWSA-N [(e)-2-bromoethenyl]benzene Chemical compound Br\C=C\C1=CC=CC=C1 YMOONIIMQBGTDU-VOTSOKGWSA-N 0.000 claims description 2
- DZHMRSPXDUUJER-UHFFFAOYSA-N [amino(hydroxy)methylidene]azanium;dihydrogen phosphate Chemical compound NC(N)=O.OP(O)(O)=O DZHMRSPXDUUJER-UHFFFAOYSA-N 0.000 claims description 2
- 150000008065 acid anhydrides Chemical class 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims description 2
- 229920000800 acrylic rubber Polymers 0.000 claims description 2
- 229910000410 antimony oxide Inorganic materials 0.000 claims description 2
- ZSTLPJLUQNQBDQ-UHFFFAOYSA-N azanylidyne(dihydroxy)-$l^{5}-phosphane Chemical compound OP(O)#N ZSTLPJLUQNQBDQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910021538 borax Inorganic materials 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- IUTYMBRQELGIRS-UHFFFAOYSA-N boric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OB(O)O.NC1=NC(N)=NC(N)=N1 IUTYMBRQELGIRS-UHFFFAOYSA-N 0.000 claims description 2
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- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 2
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- 229920002681 hypalon Polymers 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims description 2
- GVYLCNUFSHDAAW-UHFFFAOYSA-N mirex Chemical compound ClC12C(Cl)(Cl)C3(Cl)C4(Cl)C1(Cl)C1(Cl)C2(Cl)C3(Cl)C4(Cl)C1(Cl)Cl GVYLCNUFSHDAAW-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
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- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 150000008301 phosphite esters Chemical class 0.000 claims description 2
- XZTOTRSSGPPNTB-UHFFFAOYSA-N phosphono dihydrogen phosphate;1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(N)=N1.OP(O)(=O)OP(O)(O)=O XZTOTRSSGPPNTB-UHFFFAOYSA-N 0.000 claims description 2
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- VKFFEYLSKIYTSJ-UHFFFAOYSA-N tetraazanium;phosphonato phosphate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])(=O)OP([O-])([O-])=O VKFFEYLSKIYTSJ-UHFFFAOYSA-N 0.000 claims description 2
- NSBGJRFJIJFMGW-UHFFFAOYSA-N trisodium;stiborate Chemical compound [Na+].[Na+].[Na+].[O-][Sb]([O-])([O-])=O NSBGJRFJIJFMGW-UHFFFAOYSA-N 0.000 claims description 2
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims description 2
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 claims description 2
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- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 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
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/04—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C09D127/06—Homopolymers or copolymers of vinyl chloride
-
- 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
-
- 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
- C09D163/04—Epoxynovolacs
-
- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
-
- 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
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K2003/026—Phosphorus
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention discloses a kind of product of rubber and plastic flame protection coatings and preparation method thereof, its composition is: 100 mass parts of polar polymer, 0.5~20 mass parts of two-dimensional nano filler, 5~50 mass parts of fire retardant, 0.01~10 mass parts of aminated compounds, 1~50 mass parts of polyphenol compound, 0.01~10 mass parts of multivalent metal salt.The preparation method of the flame protection coating is: first, two-dimensional nano filler, fire retardant, aminated compounds, polyphenol compound and multivalent metal salt are added in solvent A, it reacts under certain conditions, coating modification is carried out to two-dimensional nano filler and fire retardant, obtains dispersion liquid A；Polar polymer is dispersed in solvent B under certain conditions and obtains dispersion liquid B, solvent A is identical with solvent B or can dissolve each other；Then, dispersion liquid A and B are mixed under certain condition, obtains flame protection coating.The flame protection coating, which can be brushed, forms flame protection coating on surfaces such as expanded polystyrene (EPS) insulating foam, static rubber products.
Description
Technical field
The invention belongs to flame retardance of polymer technical fields, and in particular to a kind of product of rubber and plastic flame protection coating and its preparation
Method.
Background technique
Product of rubber and plastic is ubiquitous in the life of the mankind, inflammable while bringing great convenience to people's lives
Property to the production and living of the mankind bring serious security risk, therefore, exploitation flame-proofed polymer material becomes polymer arts
An important topic.
Currently, most common flame retardance of polymer technological means is to add fire retardant in a polymer matrix.Due to absolutely mostly
Number fire retardant is all highly polar, and most polymers are the compatibilities that nonpolarity or low pole lead to it with polymeric matrix
It is poor, the problems such as dispersion uneven, surface migration can occur in use process；And most fire retardants are effective to play
Flame retardant effect, loading is often larger, leads to the performances degradation such as mechanics, aging, rheology of polymer [Chemical
Engineering Journal,2018,334,108-122].In contrast, coating uniformly applies on product of rubber and plastic surface
One layer of flame protection coating is covered or sprays, it can be on the basis of not changing original product of rubber and plastic formula, processing technology and performance
Realize the highly effective flame-retardant [ACS Appl.Mater.Interfaces, 2017,9,40782-40791] of product of rubber and plastic.In addition, by
It is relatively thin in flame protection coating, so the dosage of fire retardant is less, the available effective control of the cost of product of rubber and plastic.
It is necessary to meet following condition is just able to satisfy actual requirement for flame protection coating: 1) fire retardant and filler uniformly point
It dissipates.The dispersing uniformity of fire retardant and filler in flame protection coating will affect the uniformity of coating, and then influence coating
Flame retardant property and mechanical property.In order to realize the evenly dispersed of fire retardant and filler, in traditional flame protection coating formula,
Often use of surfactants as dispersing agent, and the water solubility of surfactant make its be easy to be leached by media such as water and
Reduce the weatherability of flame protection coating.2) low migration of fire retardant.Fire retardant is often Polar low molecular weight compound,
It is easy to that migration occurs in the flame protection coating of thinner thickness or is leached by media such as water, and reduce flame protection coating
Flame-retarded efficiency.3) high adhesion force of flame protection coating.In traditional flame protection coating, flame protection coating and rubber and plastic system
The adhesive force on product surface only leans in flame protection coating polar polymer to realize, as filler, fire retardant, dispersing agent etc. are various
The addition of auxiliary agent seriously can reduce the adhesive force between coating and product of rubber and plastic surface and delamination is caused to be cracked.To sum up, above three
Problem is that design prepares efficient, weather-proof and high adhesion force flame protection coating important guiding.
Summary of the invention
The purpose of the present invention is to provide a kind of product of rubber and plastic flame protection coatings and preparation method thereof.It is provided by the present invention
Product of rubber and plastic flame protection coating be prepared by following: 100 mass parts of polar polymer, two-dimensional nano filler 0.5~20
Mass parts, 5~50 mass parts of fire retardant, 0.01~10 mass parts of aminated compounds, 1~50 mass parts of polyphenol compound are more
0.01~10 mass parts of valence metal salt.
Polar polymer of the present invention are as follows: phenolic resin, Lauxite, melamine resin, epoxy resin, phenolic aldehyde
Epoxy resin, polyurethane, polyureas, polyvinyl chloride, haloflex, chlorosulfonated polyethylene, neoprene, brombutyl,
Nitrile rubber, silicon rubber, polyacrylic acid, polymethylacrylic acid, polyvinyl acetate, acrylic rubber, fluorubber and they
One of derivative or a variety of mixtures.
Two-dimensional nano filler of the present invention are as follows: clay, graphite, boron nitride, black phosphorus, the lamella metal of the number of plies≤20 layer
One of compound and their derivative or a variety of mixtures.
Fire retardant of the present invention are as follows: halogenated flame retardant, phosphorus flame retardant, expansion type flame retardant, silicon-series five-retardant and
The mixture of one or more of inorganic fire retardants.Wherein, halogenated flame retardant include polybrominated diphenyl ethers, bromophenol,
Tetrabromophthalic anhydride, tetrabromo-phthalate, tetrabromobisphenol A, bromostyrene and its polymer, deca-BDE,
2,4,6- tribromphenol, clone, chlorinated paraffin, haloflex, tetrachlorobisphenol A, tetrachlorophthalic tetrachlorophthalic anhydrid, the special acid in sea
Acid anhydride, hexacholorocyclopentadiene, mirex；Phosphorus flame retardant includes phosphate, phosphonate ester, phosphite ester, phytic acid, phosphinic acids
Salt, phosphine oxide, phosphonium salt；Expansion type flame retardant include ammonium polyphosphate, melamine, boric acid melamine, polyphosphoric acid melamine,
Melamine pyrophosphate, melamine cyanurate, orthophosphoric acid melamine, urea phosphate, dicyandiamide and its derivative, guanidine and guanidine
Salt, ammonium pyrophosphate, trbasic zinc phosphate, phosphonitrile, pyrrolotriazine derivatives；Silicon-series five-retardant include ceramic precursor polymer, glass powder with low melting point,
Low melting point ceramic powder；Inorganic fire retardants includes antimony oxide, antimony pentoxide, sodium antimonate, magnesium hydroxide, aluminium hydroxide, gold
Belong to nanoparticle, red phosphorus, ardealite, zinc borate, boric acid, borax, molybdenum trioxide, ammonium octamolybdate, the close ammonium of eight molybdic acids.
Aminated compounds of the present invention are as follows: one or more mixing of the compound in structure containing primary amine groups
Object, for example, ethylenediamine, polyethyleneimine.
Polyphenol compound of the present invention are as follows: the one or more of the compound of phenolic hydroxyl group quantity >=2 mix in structure
Object is closed, for example, tannic acid, myrica extract, valonea extract, WK tannin extract.
Multivalent metal salt of the present invention are as follows: containing valence state >=metal salts of 2 metal ions it is one or more mixed
Object is closed, for example, ferric trichloride, copper chloride, cobalt chloride.
The preparation method of flame protection coating provided by the present invention, includes the following steps:
1) coating modification of two-dimensional nano filler and fire retardant: by two-dimensional nano filler, fire retardant, aminated compounds, more
Phenolic compound and multivalent metal salt are added in solvent A, under certain conditions, pass through aminated compounds, Polyphenols chemical combination
Object and the triangular reaction of multivalent metal salt carry out coating modification to two-dimensional nano filler and fire retardant, obtain dispersion liquid A；
2) dissolution of polar polymer: polar polymer is dispersed in solvent B obtains dispersion liquid under certain conditions
B, solvent A is identical with solvent B or can dissolve each other；
3) preparation of flame protection coating: dispersion liquid A and B are mixed under certain condition, obtain flame protection coating.
Compared with prior art, the present invention the present invention is added by the Michael between polyphenol compound-aminated compounds
At reaction and the polygamy position complex reaction between schiff base reaction and polyphenol compound-polyvalent metal ion, formed three-dimensional
Reticular structure carries out coating decoration to two-dimensional nano filler and fire retardant, improve two-dimensional nano filler and fire retardant dispersibility,
While reducing fire retardant migration and leachability, the class mussel foot protein/poly-dopamine increasing stick system constructed out is also
Flame protection coating can be improved to the adhesive force of product of rubber and plastic.The present invention passes through polyphenol compound, aminated compounds and multivalence
The simple combination of metal salt synchronizes the migration and leaching of the dispersibility, fire retardant that solve two-dimensional nano filler and fire retardant
Property, flame protection coating stick three critical issues to product of rubber and plastic.The fire-retardant effect of flame protection coating not only can be improved
Energy and service life, and can simplify the formula of flame protection coating and reduce cost.
Detailed description of the invention:
Fig. 1 is the stereoscan photograph of 1 product of rubber and plastic flame protection coating of comparative example.
Fig. 2 is the stereoscan photograph of 1 product of rubber and plastic flame protection coating of embodiment.
Specific embodiment
With reference to the accompanying drawing and by specific embodiment come present invention be described in more detail.It should be understood that following embodiments
It is to limit its protection scope for illustrating rather than.
Comparative example 1:
A kind of product of rubber and plastic flame protection coating, is prepared from the following components: 100 mass parts of novolac epoxy resin,
3 mass parts of graphene oxide, 30 mass parts of ammonium polyphosphate, 5 mass parts of tannic acid, 1 mass parts of ethylenediamine, the flame protection coating
It is prepared using following steps:
1) graphene oxide, ammonium polyphosphate, tannic acid, ethylenediamine are added in the water of 50 mass parts, in 300r/min,
3h is stirred under the conditions of 60 DEG C, obtains dispersion liquid A；
2) novolac epoxy resin is added in the ethyl alcohol of 200 mass parts, 6000r/min stirring 10min makes it dissolve, and obtains
To dispersion liquid B；
3) dispersion liquid A and B are mixed, 600r/min stirs 10min, obtains flame protection coating.
Flame protection coating is coated on expanded polystyrene foam plate, tests its fire-retardant, weather-proof, adhesion after dry
It can (table 1) and microstructure (Fig. 1).
Comparative example 2:
A kind of product of rubber and plastic flame protection coating, is prepared from the following components: 100 mass parts of novolac epoxy resin,
3 mass parts of graphene oxide, 30 mass parts of ammonium polyphosphate, 1 mass parts of ethylenediamine, 1 mass parts of cobalt chloride.The flame protection coating
It is prepared using following steps:
1) graphene oxide, ammonium polyphosphate, ethylenediamine and cobalt chloride are added in the water of 50 mass parts, in 300r/
Min stirs 3h under the conditions of 60 DEG C, obtains dispersion liquid A；
2) novolac epoxy resin is added in the ethyl alcohol of 200 mass parts, 6000r/min stirring 10min makes it dissolve, and obtains
To dispersion liquid B；
3) dispersion liquid A and B are mixed, 600r/min stirs 10min, obtains flame protection coating.
Flame protection coating is coated on expanded polystyrene foam plate, tests its fire-retardant, weather-proof, adhesion after dry
Energy (table 1).
Comparative example 3:
A kind of product of rubber and plastic flame protection coating, is prepared from the following components: 100 mass parts of novolac epoxy resin,
3 mass parts of graphene oxide, 30 mass parts of ammonium polyphosphate, 5 mass parts of tannic acid, 1 mass parts of cobalt chloride, the flame protection coating
It is prepared using following steps:
1) graphene oxide, ammonium polyphosphate, tannic acid, cobalt chloride are added in the water of 50 mass parts, in 300r/min,
3h is stirred under the conditions of 60 DEG C, obtains dispersion liquid A；
2) novolac epoxy resin is added in the ethyl alcohol of 200 mass parts, 6000r/min stirring 10min makes it dissolve, and obtains
To dispersion liquid B；
3) dispersion liquid A and B are mixed, 600r/min stirs 10min, obtains flame protection coating.
Flame protection coating is coated on expanded polystyrene foam plate, tests its fire-retardant, weather-proof, adhesion after dry
Energy (table 1).
Embodiment 1:
A kind of product of rubber and plastic flame protection coating, is prepared from the following components: 100 mass parts of novolac epoxy resin,
Graphene oxide (1-3 layers) 3 mass parts, 30 mass parts of ammonium polyphosphate, 1 mass parts of ethylenediamine, 5 mass parts of tannic acid, cobalt chloride 1
Mass parts.The flame protection coating is prepared using following steps:
1) graphene oxide, ammonium polyphosphate, ethylenediamine, tannic acid and cobalt chloride are added in the water of 50 mass parts,
300r/min reacts 3h under the conditions of 60 DEG C, obtains dispersion liquid A；
2) novolac epoxy resin is added in the ethyl alcohol of 200 mass parts, 6000r/min stirring 10min makes it dissolve, and obtains
To dispersion liquid B；
3) dispersion liquid A and B are mixed, 600r/min stirs 10min, obtains flame protection coating.
Flame protection coating is coated on expanded polystyrene foam plate, it is fire-retardant, weather-proof, glutinous that its is tested after dry solidification
Attached performance (table 1) and microstructure (Fig. 2).As shown in table 1, compared with comparative example 1, the flame retardant property of embodiment 1 is obviously obtained
Raising, weather resistance and Adhesion property and comparative example 1 are almost the same；It is the flame retardant property of embodiment 1, weather-proof compared with comparative example 2
Performance and Adhesion property are significantly improved；Compared with comparative example 3, the flame retardant property of embodiment 1 has obtained less amplitude
Raising, but weather resistance and Adhesion property are significantly improved.In addition, microstructure observing shows (Fig. 1 and figure
2), in the flame protection coating of comparative example 1, the agglomerated particle of graphene oxide and ammonium polyphosphate can be obviously observed, and
Apparent agglomeration is not observed then in the flame protection coating of embodiment 1, entire coating is highly uniform.Result above is said
Bright, the chemical reaction between tannic acid and ethylenediamine plays the weather resistance and Adhesion property that improve flame protection coating main
Effect；And the coordination between tannic acid and cobalt chloride plays main function to the flame retardant property for improving flame protection coating,
Inferred according to microstructure and macro property comparison, the raising of flame retardant property is mainly due to graphene oxide and ammonium polyphosphate point
The raising of property is dissipated, and tannic acid is swift in response with cobalt chloride, and the coating modification to filler and fire retardant is rapidly completed, thus to mentioning
High oxidation graphene and ammonium polyphosphate dispersibility play main function.
Fire-retardant, the weather-proof and Adhesion property of polystyrene foam plate compares in 1 embodiment 1 and comparative example 1-3 of table
Note: weather-proof, Adhesion property is adopted to be soaked in water and observes the complete and dropping situations of coating over 30 days and carry out qualitative evaluation.
Embodiment 2:
A kind of product of rubber and plastic flame protection coating, is prepared from the following components: 100 mass parts of polyvinyl chloride, organic
Clay (1-10 layers) 0.5 mass parts, 50 mass parts of red phosphorus, 10 mass parts of polyethyleneimine, 50 mass parts of WK tannin extract, ferric trichloride
10 mass parts.The flame protection coating is prepared using following steps:
1) organic clay, red phosphorus, polyethyleneimine, WK tannin extract and ferric trichloride are added in the water of 100 mass parts,
600r/min reacts 1h under the conditions of 80 DEG C, obtains dispersion liquid A；
2) polyvinyl chloride is added in the acetone of 500 mass parts, 3000r/min stirring 30min makes it dissolve, and is divided
Dispersion liquid B；
3) dispersion liquid A and B are mixed, 1000r/min stirs 30min, obtains flame protection coating.
Flame protection coating is coated on expanded polystyrene foam plate, its flame retardant property is tested after dry solidification, is hindered
Combustion performance is shown in Table 2.
The flame retardant property of polystyrene foam plate in 2 embodiment 2 of table
Embodiment 3:
A kind of product of rubber and plastic flame protection coating, is prepared from the following components: 100 mass parts of aqueous polyurethane, black
Phosphorus nanometer sheet (1-20 layers) 20 mass parts, 5 mass parts of deca-BDE, 0.5 mass parts of hexamethylene diamine, 4 mass parts of valonea extract, chlorine
Change copper 0.3.The flame protection coating is prepared using following steps:
1) black phosphorus nanometer sheet, deca-BDE, hexamethylene diamine, valonea extract and copper chloride are added to the water of 50 mass parts
In, 1h is reacted under the conditions of 600r/min, 80 DEG C, obtains dispersion liquid A；
2) aqueous polyurethane is added in the water of 100 mass parts, 1000r/min stirring 15min makes it dissolve, and is divided
Dispersion liquid B；
3) dispersion liquid A and B are mixed, 4500r/min stirs 10min, obtains flame protection coating.
Flame protection coating is coated on sheet rubber, its flame retardant property is tested after dry solidification, flame retardant property is shown in Table 3.
The flame retardant property of sheet rubber in 3 embodiment 3 of table
Embodiment 4:
A kind of product of rubber and plastic flame protection coating, is prepared from the following components: 100 mass parts of epoxy resin, nitridation
Boron (1-10 layers) 5 mass parts, 10 mass parts of tricresyl phosphate (β-chloroethyl) ester, 0.01 mass parts of polyethyleneimine, 1 matter of myrica extract
Measure part, 0.01 mass parts of ferric trichloride.The flame protection coating is prepared using following steps:
1) boron nitride, tricresyl phosphate (β-chloroethyl) ester, polyethyleneimine, myrica extract and ferric trichloride are added to 30 matter
In the water for measuring part, 1h is reacted under the conditions of 600r/min, 80 DEG C, obtains dispersion liquid A；
2) epoxy resin is added in the acetone of 200 mass parts, 300r/min stirring 15min makes it dissolve, and is divided
Dispersion liquid B；
3) dispersion liquid A and B are mixed, 4500r/min stirs 30min, obtains flame protection coating.
Flame protection coating is coated on sheet rubber, its flame retardant property is tested after dry solidification, flame retardant property is shown in Table 4.
The flame retardant property of sheet rubber in 4 embodiment 4 of table
Embodiment 5:
A kind of product of rubber and plastic flame protection coating, is prepared from the following components: 100 mass parts of silicon rubber, curing
Molybdenum (1-10 layers) 1 mass parts, 10 mass parts of tetrabromobisphenol A, 10 mass parts of glass powder with low melting point, 0.1 mass parts of ethylenediamine, tannin
Sour 3 mass parts, 0.1 mass parts of cobalt chloride.The flame protection coating is prepared using following steps:
1) molybdenum disulfide, tetrabromobisphenol A, glass powder with low melting point, ethylenediamine, tannic acid, myrica extract and cobalt chloride are added
Enter into the water of 100 mass parts, react 1h under the conditions of 600r/min, 80 DEG C, obtains dispersion liquid A；
2) silicon rubber is added in the tetrahydrofuran of 500 mass parts, 300r/min stirring 15min makes it dissolve, and obtains
Dispersion liquid B；
3) dispersion liquid A and B are mixed, 4500r/min stirs 30min, obtains flame protection coating.
Flame protection coating is coated on sheet rubber, its flame retardant property is tested after dry solidification, flame retardant property is shown in Table 5.
The flame retardant property of sheet rubber in 5 embodiment 5 of table
The above embodiments merely illustrate the technical concept and features of the present invention, and protection model of the invention can not be limited with this
It encloses.It is all any equivalent transformation or modification made according to the spirit of the present invention, should be covered by the scope of protection of the present invention.
Claims (6)
1. a kind of product of rubber and plastic flame protection coating, which is characterized in that it is prepared from the following components: polar polymer 100
Mass parts, 0.5~20 mass parts of two-dimensional nano filler, 5~50 mass parts of fire retardant, 0.01~10 mass parts of aminated compounds,
1~50 mass parts of polyphenol compound, 0.01~10 mass parts of multivalent metal salt, the aminated compounds are as follows: contain in structure
There are one or more mixtures of the compound of primary amine groups, the polyphenol compound are as follows: phenolic hydroxyl group quantity >=2 in structure
Compound one or more mixtures, the multivalent metal salt are as follows: containing valence state >=metal salts of 2 metal ions
One or more mixtures.
2. flame protection coating according to claim 1, which is characterized in that the polar polymer are as follows: phenolic resin,
Lauxite, melamine resin, epoxy resin, novolac epoxy resin, polyurethane, polyureas, polyvinyl chloride, haloflex,
Chlorosulfonated polyethylene, neoprene, brombutyl, nitrile rubber, silicon rubber, polyacrylic acid, polymethylacrylic acid, poly-vinegar
One of vinyl acetate, acrylic rubber, fluorubber and their derivative or a variety of mixtures.
3. flame protection coating according to claim 1, which is characterized in that the two-dimensional nano filler are as follows: the number of plies≤
One of 20 layers clay, graphite, boron nitride, black phosphorus, lamella metallic compound and their derivative or a variety of mixing
Object.
4. flame protection coating according to claim 1, it is characterised in that the fire retardant are as follows: halogenated flame retardant, phosphorus system
The mixture of one or more of fire retardant, expansion type flame retardant, silicon-series five-retardant and inorganic fire retardants.
5. flame protection coating according to claim 1, which is characterized in that halogenated flame retardant includes polybrominated diphenyl ethers, bromine
Substituting phenol, tetrabromophthalic anhydride, tetrabromo-phthalate, tetrabromobisphenol A, bromostyrene and its polymer, ten bromines
Diphenyl ether, 2,4,6- tribromphenol, clone, chlorinated paraffin, haloflex, tetrachlorobisphenol A, tetrachlorophthalic tetrachlorophthalic anhydrid,
Extra large spy acid anhydrides, hexacholorocyclopentadiene, mirex；Phosphorus flame retardant include phosphate, phosphonate ester, phosphite ester, phytic acid,
Phosphinates, phosphine oxide, phosphonium salt；Expansion type flame retardant includes ammonium polyphosphate, melamine, boric acid melamine, polyphosphoric acid three
Poly cyanamid, melamine pyrophosphate, melamine cyanurate, orthophosphoric acid melamine, urea phosphate, dicyandiamide and its derivative,
Guanidine and guanidine salt, ammonium pyrophosphate, trbasic zinc phosphate, phosphonitrile, pyrrolotriazine derivatives；Silicon-series five-retardant includes ceramic precursor polymer, low melting point
Glass powder, low melting point ceramic powder；Inorganic fire retardants includes antimony oxide, antimony pentoxide, sodium antimonate, magnesium hydroxide, hydrogen-oxygen
Change aluminium, metal nanoparticle, red phosphorus, ardealite, zinc borate, boric acid, borax, molybdenum trioxide, ammonium octamolybdate, the close ammonium of eight molybdic acids.
6. a kind of preparation method of the described in any item flame protection coatings of claim 1-5, which is characterized in that including walking as follows
It is rapid:
1) coating modification of two-dimensional nano filler and fire retardant: by two-dimensional nano filler, fire retardant, aminated compounds, Polyphenols
Compound and multivalent metal salt are added in solvent A, under certain conditions, by aminated compounds, polyphenol compound and
The triangular reaction of multivalent metal salt carries out coating modification to two-dimensional nano filler and fire retardant, obtains dispersion liquid A；
2) polar polymer: being dispersed in solvent B obtain dispersion liquid B under certain conditions by the dissolution of polar polymer, molten
Agent A is identical with solvent B or can dissolve each other；
3) preparation of flame protection coating: dispersion liquid A and B are mixed under certain condition, obtain flame protection coating.
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