CN113621178A - Nano metal hydroxide halogen-free flame retardant and preparation method of composite material thereof - Google Patents
Nano metal hydroxide halogen-free flame retardant and preparation method of composite material thereof Download PDFInfo
- Publication number
- CN113621178A CN113621178A CN202010387923.2A CN202010387923A CN113621178A CN 113621178 A CN113621178 A CN 113621178A CN 202010387923 A CN202010387923 A CN 202010387923A CN 113621178 A CN113621178 A CN 113621178A
- Authority
- CN
- China
- Prior art keywords
- metal hydroxide
- nano metal
- flame retardant
- halogen
- free flame
- 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.)
- Granted
Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 113
- 229910000000 metal hydroxide Inorganic materials 0.000 title claims abstract description 103
- 150000004692 metal hydroxides Chemical class 0.000 title claims abstract description 102
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 title claims abstract description 71
- 239000002131 composite material Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 26
- 239000011574 phosphorus Substances 0.000 claims abstract description 26
- 150000002391 heterocyclic compounds Chemical class 0.000 claims abstract description 23
- 239000002245 particle Substances 0.000 claims abstract description 15
- 239000000725 suspension Substances 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 claims abstract 6
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 71
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 71
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 59
- 239000000347 magnesium hydroxide Substances 0.000 claims description 57
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 57
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 15
- -1 methoxy, ethoxy, propoxy Chemical group 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 10
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 125000004104 aryloxy group Chemical group 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- FMGBDYLOANULLW-UHFFFAOYSA-N 3-isocyanatopropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCN=C=O FMGBDYLOANULLW-UHFFFAOYSA-N 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 3
- MBGQQKKTDDNCSG-UHFFFAOYSA-N ethenyl-diethoxy-methylsilane Chemical compound CCO[Si](C)(C=C)OCC MBGQQKKTDDNCSG-UHFFFAOYSA-N 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 3
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 238000002390 rotary evaporation Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 125000003944 tolyl group Chemical group 0.000 claims description 3
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 claims description 3
- LFRDHGNFBLIJIY-UHFFFAOYSA-N trimethoxy(prop-2-enyl)silane Chemical compound CO[Si](OC)(OC)CC=C LFRDHGNFBLIJIY-UHFFFAOYSA-N 0.000 claims description 3
- CWMFRHBXRUITQE-UHFFFAOYSA-N trimethylsilylacetylene Chemical compound C[Si](C)(C)C#C CWMFRHBXRUITQE-UHFFFAOYSA-N 0.000 claims description 3
- 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 abstract description 38
- 239000000463 material Substances 0.000 abstract description 12
- 238000002156 mixing Methods 0.000 description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 20
- 239000002002 slurry Substances 0.000 description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 239000010703 silicon Substances 0.000 description 10
- 229910052710 silicon Inorganic materials 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 125000000962 organic group Chemical group 0.000 description 9
- 239000012071 phase Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- 230000000670 limiting effect Effects 0.000 description 8
- 238000002485 combustion reaction Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000002048 multi walled nanotube Substances 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000000779 smoke Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- LJUXFZKADKLISH-UHFFFAOYSA-N benzo[f]phosphinoline Chemical group C1=CC=C2C3=CC=CC=C3C=CC2=P1 LJUXFZKADKLISH-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005297 material degradation process Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 238000002186 photoelectron spectrum Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
Classifications
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657172—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- 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
- C09C1/02—Compounds of alkaline earth metals or magnesium
- C09C1/028—Compounds containing only magnesium as metal
-
- 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
- C09C1/40—Compounds of aluminium
- C09C1/407—Aluminium oxides or hydroxides
-
- 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
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- 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
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a nano metal hydroxide halogen-free flame retardant and a preparation method of a composite material thereof, belongs to the technical field of high-molecular flame retardant materials, and solves the problems of low flame retardant efficiency and poor mechanical property of metal hydroxide halogen-free flame retardants in the prior art. A preparation method of a nano metal hydroxide halogen-free flame retardant comprises the following steps of 1: preparing a phosphorus-containing heterocyclic compound by using DOPO or derivatives thereof, a silane coupling agent and a catalyst as raw materials; step 2: adding the nano metal hydroxide particles into an organic solvent to prepare a nano metal hydroxide suspension; and step 3: and (2) dissolving the phosphorus-containing heterocyclic compound prepared in the step (1) in an organic solvent to form a solution, adding the formed solution into the nano metal hydroxide suspension obtained in the step (2), and carrying out nano metal hydroxide surface grafting to obtain the nano metal hydroxide halogen-free flame retardant. The invention prepares the halogen-free flame retardant composite material of nano metal hydroxide with excellent flame retardant property.
Description
Technical Field
The invention relates to the technical field of high-molecular flame retardant materials, in particular to a nano metal hydroxide halogen-free flame retardant and a preparation method of a composite material thereof.
Background
To control the flammability of the polymer, the most common method is to add a flame retardant. Among the flame retardants, the halogen-based flame retardants are most widely used. However, the use of halogen-based flame retardants is accompanied by the generation of corrosive, toxic fumes and other negative effects. In addition, new regulations, such as european directives on Waste of Electrical and Electronic Equipment (WEEE) and hazardous substances restriction (RoHS), limit the use of some halogen based flame retardants. Therefore, the development of halogen-free, non-toxic and smoke-inhibiting flame retardant is widely regarded. Common halogen-free flame retardants include Magnesium Hydroxide (MH), aluminum hydroxide (ATH), organic phosphorus compounds, nitrogen-containing compounds, organosilicon compounds, and the like. Researches show that the nano metal hydroxide fillers such as magnesium hydroxide, aluminum hydroxide and the like are excellent halogen-free flame retardants and can play a flame retardant role in both a condensed phase and a gas phase. Inert gas (H) generated during combustion of metal hydroxide2O) can be released into the gas phase, so that dilution is possibleThe concentration of the combustion gas and the suppression of combustion. In addition, the anhydrous magnesium oxide and aluminum oxide powder obtained by thermal decomposition has excellent fire resistance, and can play a role of a heat insulation layer when accumulated on the surface of the polymer to prevent heat from being transferred to the material from flame. However, when the amount of the nano metal hydroxide is more than 60 wt%, the ideal flame retardant effect can be achieved, and the flame retardant efficiency is relatively low. In addition, the nano metal hydroxide has poor compatibility with the polymer and is unevenly dispersed in the polymer matrix, thereby influencing the mechanical property of the composite material. Therefore, it remains a challenge to balance the flame retardancy and mechanical properties (especially toughness) of polymeric materials.
In order to improve the compatibility of the nano metal hydroxide and the polymer matrix, the surface modification of the metal magnesium hydroxide is carried out to improve the compatibility of the metal magnesium hydroxide and the ethylene-vinyl acetate copolymer, and the method is an important method at present. In the prior art, the modified magnesium hydroxide has better dispersibility in resin and improves the flame retardant property of the material. But the elongation at break of the material does not exceed 60%.
The ethylene-vinyl acetate copolymer (EVA) has good elasticity and physical properties, and is widely applied to the fields of household appliances, building industry, decorative materials, wires and cables and the like. In practical application, the EVA has the problems of easy flammability and easy dripping, large smoke generation amount in the combustion process and easy generation of toxic and harmful gases, which seriously limits the application of the EVA. Many attempts have been made to improve the flame retardant properties of EVA. In the prior art, a proper amount of multi-walled carbon nanotubes (MWNTs) and Magnesium Hydroxide (MH) are added into an EVA/MH/MWNT nano composite material for synergistic action. The LOI value of EVA was 34% at 50 wt% MH addition. In the EVA/MH/MWNT composite material, 2 wt% MWNTs replaces MH, and the LOI value can be improved to 39%. The LOI value decreased to 37% with increasing amounts of MWNTs up to 4 wt%.
The 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) has the characteristics of high flame retardant efficiency and low smoke toxicity, and is widely concerned in the field of flame retardance. In the thermosetting polymer materials such as epoxy resin and the like, because DOPO can react with an epoxy group, good carbon forming and flame retardant effects can be achieved. However, because of the relatively low decomposition temperature, DOPO is difficult to be directly applied to many thermoplastic polymer materials with high processing temperature. The DOPO is chemically grafted to the surface of the inorganic nano metal hydroxide halogen-free flame retardant, so that the halogen-free flame retardant is prepared, on one hand, the good synergistic flame retardant effect can be exerted, on the other hand, the interfacial interaction between the inorganic flame retardant and a high polymer material can be effectively improved, and the method is a method for effectively improving the flame retardant efficiency and the dispersibility of the halogen-free flame retardant.
Disclosure of Invention
In view of the above analysis, the embodiments of the present invention are directed to providing a method for preparing a high-efficiency halogen-free nano metal hydroxide flame retardant and a composite material thereof, so as to solve the problems of low flame retardant efficiency and poor mechanical properties of the existing halogen-free flame retardant.
The invention is realized by the following technical scheme:
a preparation method of a nano metal hydroxide halogen-free flame retardant comprises the following steps:
step 1: preparing a phosphorus-containing heterocyclic compound by using DOPO or derivatives thereof, a silane coupling agent and a catalyst as raw materials;
step 2: adding the nano metal hydroxide particles into an organic solvent to prepare a nano metal hydroxide suspension;
and step 3: and (2) dissolving the phosphorus-containing heterocyclic compound prepared in the step (1) in an organic solvent to form a solution, adding the formed solution into the nano metal hydroxide suspension obtained in the step (2), and carrying out surface grafting on the nano metal hydroxide to prepare the nano metal hydroxide halogen-free flame retardant.
Further, in the step 1, 10-150 parts by weight of DOPO or a derivative thereof, 5-150 parts by weight of a silane coupling agent and 0.1-10 parts by weight of a catalyst are subjected to high-temperature reaction under the protection of nitrogen, and after the reaction is finished, the phosphorus-containing heterocyclic compound is obtained by rotary evaporation, washing and drying.
Further, in the step 2, 100 parts by weight of nano metal hydroxide particles are added into an organic solvent and stirred to form a first solution, and the pH of the first solution is adjusted to 10-11 to prepare the nano metal hydroxide suspension.
Further, in the step 3, 10-50 parts by weight of the phosphorus-containing heterocyclic compound obtained in the step 1 is dissolved in an organic solvent to form a second solution, the pH value of the second solution is adjusted to 10-11, the second solution is added into the nano metal hydroxide suspension obtained in the step 2, stirring and reacting are carried out, and after the reaction is finished, filtering, washing and drying are carried out to prepare the nano metal hydroxide halogen-free flame retardant.
Further, DOPO or a derivative thereof in step 1 has a P — H bond; DOPO or derivatives thereof have the structural formula I:
further, in the formula I, R1-R8One selected from hydrogen atom, alkyl, nitro, alkoxy, aryl and aryloxy; the alkyl is one of methyl, ethyl, propyl, butyl and pentyl; the alkoxy is one of methoxy, ethoxy, propoxy and butoxy; the aryl is one of phenyl, methylphenyl, dimethylphenyl, benzyl and benzyl ethyl; aryloxy is phenoxy.
Further, the silane coupling agent is one of vinyltriethoxysilane, vinyltrimethoxysilane, methylvinyldiethoxysilane, allyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, ethynyltrimethylsilane, 3-isocyanatopropyltrimethoxysilane and 3-isocyanatopropyltriethoxysilane.
Further, the nano metal hydroxide is one of aluminum hydroxide and magnesium hydroxide.
Furthermore, in the halogen-free flame retardant of the nano metal hydroxide, the chemical grafting amount of DOPO or the derivative thereof on the nano metal hydroxide is 0.1 to 8 weight percent.
The invention also provides a preparation method of the nano metal hydroxide halogen-free flame retardant composite material, and the nano metal hydroxide halogen-free flame retardant composite material is obtained by blending the nano metal hydroxide halogen-free flame retardant and the ethylene-vinyl acetate copolymer.
Compared with the prior art, the invention can realize at least one of the following beneficial effects:
1. the invention takes silane coupling agent as bridging, chemically grafts the phosphorus-containing flame retardant DOPO or the derivative thereof to the surface of magnesium hydroxide or aluminum hydroxide, and the introduction of organic groups changes the surface property of the nano hydroxide, so that the surface of the nano hydroxide becomes oleophilic and hydrophobic, the compatibility of the hydroxide nano particles and the EVA matrix is improved, and the mechanical property of the composite material is improved.
2. The invention relates to a preparation method of a nano metal hydroxide halogen-free flame retardant and a composite material thereof, which utilizes the synergistic effect of a phosphorus-containing flame retardant DOPO and derivatives thereof and a gas phase and a solid phase of a nano metal hydroxide: the nanometer hydroxide is heated and decomposed to generate solid oxide and water vapor, the solid oxide can form a protective layer on the surface of a combustion material to prevent the further combustion of the material, and the solid flame retardant effect is achieved; the water vapor can dilute the oxygen of the combustible gas and play a role in gas phase flame retardance, so that the flame retardance of the EVA is improved from the gas phase and the solid phase simultaneously, and the flame retardance efficiency of the metal hydroxide is effectively improved.
3. Compared with the prior art, the nano metal hydroxide halogen-free flame retardant prepared by the invention is an organic-inorganic hybrid nano metal hydroxide halogen-free flame retardant, the nano hydroxide is subjected to surface modification, the phosphorus-containing heterocyclic compound is grafted to the surface of the hydroxide, the active sites on the surface of the nano hydroxide are increased, the specific surface area of the nano hydroxide is increased, and after the nano hydroxide halogen-free flame retardant is formed and prepared into a composite material with EVA, the nano hydroxide halogen-free flame retardant has good flame retardant property and mechanical property and good fluidity, and can meet the industrial requirements of EVA products.
In the invention, the technical schemes can be combined with each other to realize more preferable combination schemes. Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and drawings.
Drawings
The drawings are only for purposes of illustrating particular embodiments and are not to be construed as limiting the invention, wherein like reference numerals are used to designate like parts throughout.
FIG. 1 is an infrared spectrum of magnesium hydroxide particles surface-grafted with DOPO of example 1;
FIG. 2 is a transmission electron micrograph of a magnesium hydroxide starting material;
FIG. 3 is a transmission electron micrograph of magnesium hydroxide particles with DOPO grafted on the surface;
FIG. 4 is an X-ray photoelectron spectrum of the magnesium hydroxide particles of example 1 and magnesium hydroxide particles having DOPO grafted on the surface thereof;
FIG. 5 is a scanning electron microscope photograph of a liquid nitrogen quenched section of the ethylene-vinyl acetate copolymer/magnesium hydroxide composite of comparative example 2;
FIG. 6 is a scanning electron microscope photograph of a liquid nitrogen quenched section of the ethylene-vinyl acetate copolymer/magnesium hydroxide composite with surface grafted DOPO of example 1;
FIG. 7 is a scanning electron microscope photograph of a liquid nitrogen quenched section of an ethylene-vinyl acetate copolymer/magnesium hydroxide/silicon-containing organic group DOPO derivative composite material of comparative example 1;
FIG. 8 is a graph of the thermal weight loss for four different samples under an air atmosphere;
wherein: a: ethylene-vinyl acetate copolymer raw material;
b: comparative example 2 the mass ratio of ethylene-vinyl acetate copolymer to magnesium hydroxide was 50 wt%: 50 wt% of ethylene-vinyl acetate copolymer/magnesium hydroxide composite material;
c: example 1 mass ratio of ethylene-vinyl acetate copolymer to magnesium hydroxide surface-grafted with DOPO 48.6 wt%: 51.4 wt% of ethylene-vinyl acetate copolymer/magnesium hydroxide composite material with DOPO grafted on the surface;
d: comparative example 1 the mass ratio of the ethylene-vinyl acetate copolymer to the magnesium hydroxide and the silicon-containing organic group-containing DOPO derivative was 48.6 wt%: 50 wt%: 1.4 wt% of ethylene-vinyl acetate copolymer/magnesium hydroxide/DOPO derivative composite material containing silicon organic group;
FIG. 9 shows the limiting oxygen index test results for four different samples;
e0: ethylene-vinyl acetate copolymer raw material;
E/M: comparative example 2 the mass ratio of ethylene-vinyl acetate copolymer to magnesium hydroxide was 50 wt% to 50 wt% of the ethylene-vinyl acetate copolymer/magnesium hydroxide composite;
E/MDW: example 1 mass ratio of ethylene-vinyl acetate copolymer to magnesium hydroxide with DOPO grafted on surface 48.6 wt% 51.4 wt% ethylene-vinyl acetate copolymer/magnesium hydroxide with DOPO grafted on surface composite;
E/M/DW: comparative example 1 the mass ratio of ethylene-vinyl acetate copolymer to magnesium hydroxide and silicon-containing organic group DOPO derivative was 48.6 wt% to 50 wt% to 1.4 wt% of ethylene-vinyl acetate copolymer/magnesium hydroxide/silicon-containing organic group DOPO derivative composite material.
FIG. 10 is a graph of tensile strength test results for four different samples;
e0: ethylene-vinyl acetate copolymer raw material;
E/M: comparative example 2 the mass ratio of ethylene-vinyl acetate copolymer to magnesium hydroxide was 50 wt% to 50 wt% of the ethylene-vinyl acetate copolymer/magnesium hydroxide composite;
E/MDW: example 1 mass ratio of ethylene-vinyl acetate copolymer to magnesium hydroxide with DOPO grafted on surface 48.6 wt% 51.4 wt% ethylene-vinyl acetate copolymer/magnesium hydroxide with DOPO grafted on surface composite;
E/M/DW: comparative example 1 the mass ratio of ethylene-vinyl acetate copolymer to magnesium hydroxide and silicon-containing organic group DOPO derivative was 48.6 wt% to 50 wt% to 1.4 wt% of ethylene-vinyl acetate copolymer/magnesium hydroxide/silicon-containing organic group DOPO derivative composite material.
FIG. 11 is a graph of elongation at break test results for four different samples;
e0: ethylene-vinyl acetate copolymer raw material;
E/M: comparative example 2 the mass ratio of ethylene-vinyl acetate copolymer to magnesium hydroxide was 50 wt% to 50 wt% of the ethylene-vinyl acetate copolymer/magnesium hydroxide composite;
E/MDW: example 1 mass ratio of ethylene-vinyl acetate copolymer to magnesium hydroxide with DOPO grafted on surface 48.6 wt% 51.4 wt% ethylene-vinyl acetate copolymer/magnesium hydroxide with DOPO grafted on surface composite;
E/M/DW: comparative example 1 the mass ratio of ethylene-vinyl acetate copolymer to magnesium hydroxide and silicon-containing organic group DOPO derivative was 48.6 wt% to 50 wt% to 1.4 wt% of ethylene-vinyl acetate copolymer/magnesium hydroxide/silicon-containing organic group DOPO derivative composite;
FIG. 12 is a schematic diagram of a process for producing three phosphorus-containing heterocyclic compounds;
FIG. 13 is a schematic view of a process for preparing a nano metal hydroxide halogen-free flame retardant by a nano hydroxide surface grafting reaction.
Detailed Description
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate preferred embodiments of the invention and together with the description, serve to explain the principles of the invention and not to limit the scope of the invention.
The invention provides a preparation method of a nano metal hydroxide halogen-free flame retardant, which comprises the following steps as shown in figures 1-8:
step 1: reacting DOPO or a derivative thereof with a silane coupling agent to prepare a phosphorus-containing heterocyclic compound;
under the protection of nitrogen, 10-150 parts by weight of DOPO or derivatives thereof, 5-150 parts by weight of silane coupling agent and 0.1-10 parts by weight of catalyst react for more than 24 hours at 130-140 ℃ under an anaerobic condition, and after the reaction is finished, the mixture is subjected to rotary evaporation, washed by detergent and dried to obtain the phosphorus-containing heterocyclic compound.
The catalyst is selected from one of triethylamine and azodiisobutyronitrile.
The purpose of washing is to wash away unreacted DOPO or a derivative thereof; the detergent is selected from one or more of cyclohexane, n-hexane and ethanol.
Specifically, DOPO or its derivatives need to have a P-H bond structure, i.e., a structure represented by structural formula I:
in the structural formula I, R1-R8Can be independently selected from one of hydrogen atom, alkyl, nitro, alkoxy, aryl and aryloxy. R1-R8The alkyl in (A) can be independently selected from one of methyl, ethyl, propyl, butyl and pentyl; the alkoxy can be independently selected from one of methoxy, ethoxy, propoxy and butoxy; the aryl group can be independently selected from one of phenyl, methylphenyl, dimethylphenyl, benzyl and benzyl ethyl; the aryloxy group may be selected from phenoxy.
In particular, when R in formula I1-R8When all the groups are hydrogen atoms, the DOPO is obtained: 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, the structure of which is shown in formula II:
the silane coupling agent can be one selected from the group consisting of vinyltriethoxysilane, vinyltrimethoxysilane, methylvinyldiethoxysilane, allyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, ethynyltrimethylsilane, 3-isocyanatopropyltrimethoxysilane, and 3-isocyanatopropyltriethoxysilane.
Illustratively, in the presence of Azobisisobutyronitrile (AIBN) as a catalyst, DOPO and Vinyltriethoxysilane (VTES) react to form three phosphorus-containing heterocyclic compounds, as shown in fig. 12.
Step 2: preparing a nano metal hydroxide suspension;
adding 100 parts by weight of nano metal hydroxide particles of raw materials into an organic solvent, stirring to form a first solution, and adjusting the pH of the first solution to 10-11 to form a nano metal hydroxide suspension.
The hydrolysis speed of the silane can be accelerated by adjusting the pH value of the first solution to be acidic or alkaline, and the product in the step (1) is adjusted to be alkaline by ammonia water before the reaction because the experimental raw material hydroxide suspension is alkaline. By optimizing experimental parameters, the grafting ratio of the phosphorus-containing heterocyclic compound on the surface of the magnesium hydroxide is preferably 2.4% when the pH of the first solution is adjusted to 10.5.
The nano metal hydroxide is one or a mixture of magnesium hydroxide and aluminum hydroxide.
And step 3: carrying out grafting reaction on the surface of the nano metal hydroxide to prepare the nano metal hydroxide halogen-free flame retardant;
dissolving 10-50 parts by weight of the phosphorus-containing heterocyclic compound in the step (1) in an organic solvent to form a second solution, adjusting the pH of the second solution to 10-11, adding the second solution into the suspension obtained in the step (2), and reacting for 6 hours at the temperature of 60-70 ℃ and the rotating speed of 200-300 rpm, and stirring for reaction. And after the reaction is finished, filtering, washing with a washing solvent, and drying to prepare the nano metal hydroxide halogen-free flame retardant.
The organic solvent in the steps 2 and 3 is one selected from benzene, toluene, xylene, N-dimethylformamide, N-dimethylacetamide, dichloromethane, chloroform, ethanol and acetone.
Illustratively, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and gamma-methacryloxypropyltrimethoxysilane (WD70) are used as raw materials to perform grafting reaction on the surface of the nano hydroxide to prepare the nano metal hydroxide halogen-free flame retardant, and the process is shown in FIG. 13.
The chemical grafting amount of DOPO or the derivative thereof on the nano metal hydroxide in the nano metal hydroxide compound is 0.1 to 8 weight percent.
In the prior art, the dispersibility of a metal hydroxide flame retardant in a matrix is improved through surface modification, or the flame retardant efficiency of the metal hydroxide is improved through simple synergistic compounding.
In the heating process of the DOPO-containing halogen-free flame retardant, more non-volatile molecular fragments can be generated by material degradation, including the sub-fragments of the phosphaphenanthrene group, aryl phosphoric acid, phosphorous acid compounds and the like, and the compounds are beneficial to carbon formation and can play a condensed phase flame retardant role on polymers; from the gas phase perspective, the phosphaphenanthrene group can generate P-C fracture at high temperature to form benzofuran, phosphorus oxygen free radical and the like, and the phosphorus oxygen free radical can quench alkane free radical, hydroxyl free radical and the like generated in the combustion process to stop chain reaction and play a role in gas phase flame retardance.
The invention provides a preparation method of a nano metal hydroxide halogen-free flame retardant composite material.
Specifically, according to the following ethylene-vinyl acetate copolymer (EVA): adding the halogen-free flame retardant of the nano metal hydroxide into blending equipment according to the proportion of 1: 1-1: 1.5. Uniformly mixing EVA and the organic-inorganic hybrid nano metal hydroxide halogen-free flame retardant, adding the mixture into blending equipment, and banburying for 1.5-2 min. Banburying conditions are as follows: the temperature is 140-150 ℃, the feeding speed is 10-15 r/min, the rotating speed is 50-70 r/min, and the time is 5.5-7 min.
In addition, EVA can also be added in batches, firstly a part of ethylene-vinyl acetate copolymer is added, then the organic-inorganic hybrid nano metal hydroxide high-efficiency halogen-free flame retardant is added for continuously mixing uniformly, and then the rest ethylene-vinyl acetate copolymer is added for blending. And obtaining the composite material obtained by blending the organic-inorganic hybrid nano metal hydroxide high-efficiency halogen-free flame retardant and the ethylene-vinyl acetate after blending. When the EVA is added for multiple times, the nano particles and the EVA are mixed more uniformly, and the nano particles can be completely wrapped in the EVA.
Example 1
Preparation of phosphorus-containing hybridsA cyclic compound: 2.6mol of DOPO was added to a 250mL four-necked flask and N was allowed to flow through for 5min2And heated to 140 ℃. When DOPO was completely melted, 1mol of gamma-methacryloxypropyltrimethoxysilane (WD70) and 1mL of triethylamine were added to the four-necked flask, and N was continuously introduced2And reacting for 24 hours under the anaerobic condition to obtain the phosphorus-containing heterocyclic compound (DOPO-WD70) containing silicon organic groups.
78.0g of Magnesium Hydroxide (MH) powder was prepared into a slurry having a concentration of 0.1g/mL and placed in a 1L three-necked flask, the pH of the slurry was adjusted to 10.5, and the slurry was heated to 80 ℃. 20g of DOPO-WD70 was weighed out and dissolved in an appropriate amount of ethanol solvent (pH of the ethanol solvent was adjusted to 10.5), and added to the slurry. The reaction was carried out at 80 ℃ and 200rpm for 6 h. The reaction solution was filtered under positive pressure to obtain a product nano metal hydroxide complex (MH-WD70-DOPO), which MH-WD70-DOPO was washed 3 times with ethanol. MH-WD70-DOPO was dried overnight in a vacuum oven at 80 ℃ for use. FIG. 1 and FIGS. 3 to 4 show the IR spectrum, TEM image and photoelectron spectrum of MH-WD70-DOPO prepared in this example. In comparison with the transmission electron microscope image of magnesium hydroxide of FIG. 2, it can be seen from FIG. 1 that example 1 successfully produces surface-grafted magnesium hydroxide particles.
The preparation method of the nano metal hydroxide halogen-free flame retardant composite material comprises the following steps:
ethylene-vinyl acetate copolymer: 48.6 wt.%
Nano metal hydroxide halogen-free flame retardant (MH-WD 70-DOPO): 51.4 wt.%
Specifically, 31.8g of ethylene-vinyl acetate copolymer and 33.6g of MH-WD70-DOPO are weighed and added into an internal mixer in batches for melting and blending, wherein the internal mixing temperature is 135 ℃, the rotating speed is 50r/min, and the time is 7 min. After the blending is finished, the equilibrium torque of the obtained nano metal hydroxide halogen-free flame retardant composite material is 20.1 N.m, the melt index is 6.01%, the limiting oxygen index is 32.8%, the tensile strength is 11.48MPa, and the elongation at break is 209.13%.
Example 2
Preparing a phosphorus-containing heterocyclic compound: 2.6mol of DOPO was added to a 250mL four-necked flask and N was allowed to flow through for 5min2And heat upTo 140 ℃. When DOPO was completely melted, 1mol VTES and 1mL triethylamine were added to the four-necked flask, and N was continuously introduced2And reacting for 24 hours under the anaerobic condition to obtain the phosphorus-containing heterocyclic compound (DOPO-VTES).
78.0g of aluminum hydroxide (ATH) powder is prepared into slurry with the concentration of 0.1g/mL and placed in a 1L three-neck flask, the pH of the slurry is adjusted to 10.5, and the slurry is heated to 80 ℃. 20g of DOPO-WD70 was weighed out and dissolved in an appropriate amount of ethanol solvent (pH of the ethanol solvent was adjusted to 10.5), and added to the slurry. The reaction was carried out at 80 ℃ and 200rpm for 6 h. And (3) filtering the reaction liquid at positive pressure to obtain a product of the nano metal hydroxide halogen-free flame retardant (ATH-WD70-DOPO), and washing the ATH-WD70-DOPO with ethanol for 3 times. The ATH-WD70-DOPO was dried overnight in a vacuum oven at 80 ℃ for further use.
The preparation method of the nano metal hydroxide halogen-free flame retardant composite material comprises the following steps:
ethylene-vinyl acetate copolymer: 48.6 wt.%
Nanometer metal hydroxide halogen-free flame retardant (ATH-WD 70-DOPO): 51.4 wt.%
32.0g of ethylene-vinyl acetate copolymer and 33.8g of ATH-WD70-DOPO are weighed and added into an internal mixer in batches for melting and blending, the internal mixing temperature is 135 ℃, the rotating speed is 50r/min, and the time is 7 min. After the blending is finished, the equilibrium torque of the obtained nano metal hydroxide halogen-free flame retardant composite material is 10.2 N.m, the limiting oxygen index is 31.6%, the tensile strength is 12.13MPa, and the elongation at break is 170.57%.
Example 3
Preparing a phosphorus-containing heterocyclic compound: 2.6mol of DOPO was added to a 250mL four-necked flask and N was allowed to flow through for 5min2And heated to 140 ℃. When DOPO was completely melted, 1mol Vinyltriethoxysilane (VTES) and 1mL triethylamine were added to the four-necked flask, and N was continuously introduced2And reacting for 24h under the anaerobic condition to obtain the DOPO derivative (DOPO-VTES).
78.0g of Magnesium Hydroxide (MH) powder was prepared into a slurry having a concentration of 0.1g/mL and placed in a 1L three-necked flask, the pH of the slurry was adjusted to 10.5, and the slurry was heated to 80 ℃. 20g of DOPO-VTES was weighed out and dissolved in an appropriate amount of ethanol solvent (pH of the ethanol solvent was adjusted to 10.5), and added to the slurry. The reaction was carried out at 80 ℃ and 200rpm for 6 h. And filtering the reaction liquid under positive pressure to obtain a nano metal hydroxide halogen-free flame retardant (MH-VTES-DOPO), and washing the MH-VTES-DOPO with ethanol for 3 times. MH-WD70-DOPO was dried overnight in a vacuum oven at 80 ℃ for use.
The preparation method of the nano metal hydroxide halogen-free flame retardant composite material comprises the following steps:
ethylene-vinyl acetate copolymer: 48.6 wt.%
Nano metal hydroxide halogen-free flame retardant (MH-VTES-DOPO): 51.4 wt.%
31.8g of ethylene-vinyl acetate copolymer and 33.6g of MH-VTES-DOPO particles are weighed and added into an internal mixer in batches for melt blending, the internal mixing temperature is 135 ℃, the rotating speed is 50r/min, and the time is 7 min. After the blending is finished, the equilibrium torque of the obtained nano metal hydroxide halogen-free flame retardant composite material is 20.1 N.m, the limiting oxygen index is 32.5%, the tensile strength is 11.48MPa, and the elongation at break is 209.13%.
Comparative example 1
Preparing a phosphorus-containing heterocyclic compound: 2.6mol of DOPO was added to a 250mL four-necked flask and N was allowed to flow through for 5min2And heated to 140 ℃. When DOPO was completely melted, 1mol VTES and 1mL triethylamine were added to the four-necked flask, and N was continuously introduced2And reacting for 24 hours under the anaerobic condition to obtain the phosphorus-containing heterocyclic compound (DOPO-VTES).
78.0g of magnesium hydroxide powder is taken to prepare slurry with the concentration of 0.1g/mL and placed in a 1L three-neck flask, the pH of the slurry is adjusted to 10.5, and the slurry is heated to 80 ℃. 20g of DOPO-VTES was weighed out, dissolved in an appropriate amount of ethanol solvent (pH of the ethanol solvent was adjusted to 10.5), and added to the slurry. The reaction was carried out at 80 ℃ and 200rpm for 6 h. The reaction liquid is filtered under positive pressure to obtain a product of the nano metal hydroxide halogen-free flame retardant (MH-VTES-DOPO), and the product is washed for 3 times by ethanol. The product was dried overnight in a vacuum oven at 80 ℃ until use.
The preparation method of the nano metal hydroxide halogen-free flame retardant composite material comprises the following steps:
ethylene-vinyl acetate copolymer: 48.6 wt.%
Aluminum hydroxide: 50 wt.%
Nano metal hydroxide halogen-free flame retardant (MH-VTES-DOPO): 1.4 wt.%
32.0g of ethylene-vinyl acetate copolymer, 32.9g of MH-VTES-DOPO and 1.0g of DOPO derivative are weighed and added into an internal mixer in batches for melting and blending, the internal mixing temperature is 135 ℃, the rotating speed is 50r/min, and the time is 7 min. After the blending is finished, the equilibrium torque of the obtained nano metal hydroxide halogen-free flame retardant composite material is 19.2 N.m, the limiting oxygen index is 30.5%, the tensile strength is 7.78MPa, and the elongation at break is 138.70%.
Comparative example 2
The flame retardant composite material comprises the following components in percentage by weight:
ethylene-vinyl acetate copolymer: 50 wt.%
Magnesium hydroxide: 50 wt.%
32.7g of ethylene-vinyl acetate copolymer and 32.7g of magnesium hydroxide particles are weighed and added into an internal mixer in batches for melt blending, the internal mixing temperature is 135 ℃, the rotating speed is 50r/min, and the time is 7 min. After blending, a composite material was prepared as shown in fig. 5. The composite material obtained had an equilibrium torque of 31.09 N.m, a melt index of 1.57g/min, a limiting oxygen index of 28.2%, a tensile strength of 8.18MPa and an elongation at break of 127.58%.
Comparative example 3
The flame retardant composite material comprises the following components in percentage by weight:
ethylene-vinyl acetate copolymer: 50 wt.%
Aluminum hydroxide: 50 wt.%
32.9g of ethylene-vinyl acetate copolymer and 32.9g of aluminum hydroxide particles are weighed and added into an internal mixer in batches for melt blending, the internal mixing temperature is 135 ℃, the rotating speed is 50r/min, and the time is 7 min. After the blending, the balance torque of the obtained composite material is 32.1 N.m, the limiting oxygen index is 28.8%, the tensile strength is 11.59MPa, and the elongation at break is 148.75%.
Comparing with fig. 5-7, it can be seen that in the prior art, the nano metal hydroxide halogen-free flame retardant composite material prepared by directly mixing the ethylene-vinyl acetate copolymer and the hydroxide has large granularity and rough particles, and the composite material prepared by mixing the nano hydroxide with the ethylene-vinyl acetate copolymer after surface modification has small granularity and smooth surface.
The smaller the equilibrium torque of the flame retardant, the better the flowability of the flame retardant material, the better its processability and the better its mechanical properties. Examples 1 to 3 and comparative examples 1 to 3, the equilibrium torque of the nano metal hydroxide halogen-free flame retardant composite material prepared in examples 1 to 3 is lower than that of the flame retardant in comparative examples 1 to 3, and the tensile strength and the elongation at break of the flame retardant in examples 1 to 3 are higher than those of comparative examples 1 to 3. As shown in FIGS. 10 to 11, the tensile strength and elongation at break of example 1 are superior to those of comparative examples 1 and 2. The mechanical property of the nano metal hydroxide halogen-free flame retardant composite material prepared by the invention is superior to that of the flame retardant composite material prepared by the prior art.
The higher the melt index and the limited oxygen index are, the better the flame retardant performance of the flame retardant is, as shown in fig. 9, the limited oxygen index of example 1 is higher than that of comparative examples 1-2. Therefore, the flame retardant prepared by the preparation method of the halogen-free flame retardant of nano metal hydroxide provided by the invention has better mechanical property and flame retardant property than the flame retardant in the prior art. As shown in fig. 8, the decomposition temperature of the flame retardant composite prepared by grafting the surface of the metal hydroxide in example 1 and comparative example 1 was higher than that of the flame retardant composite prepared by directly mixing the ethylene-vinyl acetate copolymer with magnesium hydroxide in comparative example 2.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
Claims (10)
1. A preparation method of a nano metal hydroxide halogen-free flame retardant is characterized by comprising the following steps:
step 1: preparing a phosphorus-containing heterocyclic compound by using DOPO or derivatives thereof, a silane coupling agent and a catalyst as raw materials;
step 2: adding the nano metal hydroxide particles into an organic solvent to prepare a nano metal hydroxide suspension;
and step 3: and (2) dissolving the phosphorus-containing heterocyclic compound prepared in the step (1) in an organic solvent to form a solution, adding the formed solution into the nano metal hydroxide suspension obtained in the step (2), and carrying out surface grafting on the nano metal hydroxide to prepare the nano metal hydroxide halogen-free flame retardant.
2. The preparation method of the halogen-free flame retardant of the nano metal hydroxide as claimed in claim 1, wherein in the step 1, 10-150 parts by weight of DOPO or the derivative thereof, 5-150 parts by weight of the silane coupling agent and 0.1-10 parts by weight of the catalyst are subjected to high-temperature reaction under the protection of nitrogen, and after the reaction is finished, the phosphorus-containing heterocyclic compound is prepared by rotary evaporation, washing and drying.
3. The method for preparing the nano metal hydroxide halogen-free flame retardant according to claim 2, wherein in the step 2, 100 parts by weight of nano metal hydroxide particles are added into an organic solvent and stirred to form a first solution, and the pH of the first solution is adjusted to 10-11 to prepare the nano metal hydroxide suspension.
4. The method for preparing the nano metal hydroxide halogen-free flame retardant according to claim 3, wherein in the step 3, 10 to 50 parts by weight of the phosphorus-containing heterocyclic compound obtained in the step 1 is dissolved in an organic solvent to form a second solution, the pH of the second solution is adjusted to 10 to 11, the second solution is added into the nano metal hydroxide suspension obtained in the step 2, the stirring reaction is carried out, and after the reaction is finished, the nano metal hydroxide halogen-free flame retardant is prepared by filtering, washing and drying.
6. the method for preparing the nano metal hydroxide halogen-free flame retardant according to claim 5, wherein R in the formula I1-R8One selected from hydrogen atom, alkyl, nitro, alkoxy, aryl and aryloxy;
the alkyl is one of methyl, ethyl, propyl, butyl and pentyl;
the alkoxy is one of methoxy, ethoxy, propoxy and butoxy;
the aryl is one of phenyl, methylphenyl, dimethylphenyl, benzyl and benzyl ethyl;
the aryloxy group is phenoxy.
7. The method for preparing the nano metal hydroxide halogen-free flame retardant according to claim 2, wherein the silane coupling agent is one of vinyltriethoxysilane, vinyltrimethoxysilane, methylvinyldiethoxysilane, allyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, ethynyltrimethylsilane, 3-isocyanatopropyltrimethoxysilane, and 3-isocyanatopropyltriethoxysilane.
8. The method for preparing the nano metal hydroxide halogen-free flame retardant according to claim 2, wherein the nano metal hydroxide is one of aluminum hydroxide and magnesium hydroxide.
9. The method for preparing the nano metal hydroxide halogen-free flame retardant according to claims 1-8, wherein the chemical grafting amount of DOPO or the derivative thereof on the nano metal hydroxide in the nano metal hydroxide halogen-free flame retardant is 0.1-8 wt%.
10. A preparation method of a nano metal hydroxide halogen-free flame retardant composite material is characterized in that the nano metal hydroxide halogen-free flame retardant disclosed by claim 1-9 is blended with an ethylene-vinyl acetate copolymer to obtain the nano metal hydroxide halogen-free flame retardant composite material.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010387923.2A CN113621178B (en) | 2020-05-09 | 2020-05-09 | Nano metal hydroxide halogen-free flame retardant and preparation method of composite material thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010387923.2A CN113621178B (en) | 2020-05-09 | 2020-05-09 | Nano metal hydroxide halogen-free flame retardant and preparation method of composite material thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN113621178A true CN113621178A (en) | 2021-11-09 |
CN113621178B CN113621178B (en) | 2022-08-23 |
Family
ID=78377510
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202010387923.2A Active CN113621178B (en) | 2020-05-09 | 2020-05-09 | Nano metal hydroxide halogen-free flame retardant and preparation method of composite material thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN113621178B (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115044223A (en) * | 2022-05-12 | 2022-09-13 | 广东安拓普聚合物科技有限公司 | Low-smoke halogen-free cable material and preparation method thereof |
CN116355346A (en) * | 2023-04-07 | 2023-06-30 | 广东安拓普聚合物科技有限公司 | Low-smoke halogen-free flame-retardant crosslinked polyolefin for energy storage |
CN117925053A (en) * | 2024-03-22 | 2024-04-26 | 江苏华光新材料科技有限公司 | Powder coating for goods shelf and preparation method thereof |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101117581A (en) * | 2007-09-04 | 2008-02-06 | 华南理工大学 | Method for preparing metal hydroxide combustion inhibitor |
CN101914237A (en) * | 2010-09-03 | 2010-12-15 | 东华大学 | Halogen-free phosphorus-free modified magnesium hydroxide flame retardant ethylene-vinyl acetate copolymer and preparation method thereof |
CN103304883A (en) * | 2012-03-14 | 2013-09-18 | 中国科学院化学研究所 | Composition of halogen-free flame-retardant ethylene/vinyl acetate copolymer of phosphorus-containing heterocyclic compound |
CN106957454A (en) * | 2017-04-18 | 2017-07-18 | 中国科学技术大学 | A kind of nano material coated fire retardant and preparation method thereof |
WO2018014443A1 (en) * | 2016-07-18 | 2018-01-25 | 江林(贵州)高科发展股份有限公司 | Halogen-free phosphorus-containing silicon flame retardant, flame retardant transparent polycarbonate material, and preparation and use thereof |
CN110194852A (en) * | 2018-02-27 | 2019-09-03 | 江苏艾特克阻燃材料有限公司 | A kind of modified magnesium hydroxide, surface modifying method and application |
-
2020
- 2020-05-09 CN CN202010387923.2A patent/CN113621178B/en active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101117581A (en) * | 2007-09-04 | 2008-02-06 | 华南理工大学 | Method for preparing metal hydroxide combustion inhibitor |
CN101914237A (en) * | 2010-09-03 | 2010-12-15 | 东华大学 | Halogen-free phosphorus-free modified magnesium hydroxide flame retardant ethylene-vinyl acetate copolymer and preparation method thereof |
CN103304883A (en) * | 2012-03-14 | 2013-09-18 | 中国科学院化学研究所 | Composition of halogen-free flame-retardant ethylene/vinyl acetate copolymer of phosphorus-containing heterocyclic compound |
WO2018014443A1 (en) * | 2016-07-18 | 2018-01-25 | 江林(贵州)高科发展股份有限公司 | Halogen-free phosphorus-containing silicon flame retardant, flame retardant transparent polycarbonate material, and preparation and use thereof |
CN106957454A (en) * | 2017-04-18 | 2017-07-18 | 中国科学技术大学 | A kind of nano material coated fire retardant and preparation method thereof |
CN110194852A (en) * | 2018-02-27 | 2019-09-03 | 江苏艾特克阻燃材料有限公司 | A kind of modified magnesium hydroxide, surface modifying method and application |
Non-Patent Citations (2)
Title |
---|
徐亚新,等: "无卤含磷阻燃剂协效氢氧化镁阻燃乙烯-醋酸乙烯酯共聚物的研究", 《绝缘材料》 * |
韩忆,等: "DOPO 接枝氢氧化镁阻燃聚丙烯研究", 《塑料工业》 * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115044223A (en) * | 2022-05-12 | 2022-09-13 | 广东安拓普聚合物科技有限公司 | Low-smoke halogen-free cable material and preparation method thereof |
CN116355346A (en) * | 2023-04-07 | 2023-06-30 | 广东安拓普聚合物科技有限公司 | Low-smoke halogen-free flame-retardant crosslinked polyolefin for energy storage |
CN116355346B (en) * | 2023-04-07 | 2023-11-24 | 广东安拓普聚合物科技股份有限公司 | Low-smoke halogen-free flame-retardant crosslinked polyolefin for energy storage |
CN117925053A (en) * | 2024-03-22 | 2024-04-26 | 江苏华光新材料科技有限公司 | Powder coating for goods shelf and preparation method thereof |
CN117925053B (en) * | 2024-03-22 | 2024-05-17 | 江苏华光新材料科技有限公司 | Powder coating for goods shelf and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
CN113621178B (en) | 2022-08-23 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN113621178B (en) | Nano metal hydroxide halogen-free flame retardant and preparation method of composite material thereof | |
CN109135189B (en) | P/N/Si-containing multi-element polyphosphazene silazane flame retardant for epoxy resin and preparation method thereof | |
Zhou et al. | Construction of anti-flame network structures in cotton fabrics with pentaerythritol phosphate urea salt and nano SiO2 | |
CN109912799B (en) | Phosphorus-containing organic silicon flame retardant and preparation and application thereof | |
CN111793090A (en) | DOPO silicon phosphorus synergistic flame retardant and preparation method and application thereof | |
CN109180952A (en) | A kind of nitrogen phosphorus silicon synergistic halogen-free flame retardants of graft grapheme and preparation method thereof | |
CN110804212B (en) | Preparation method and application of modified flame-retardant compound | |
CN114855298A (en) | Flame-retardant smoke-inhibiting polylactic acid fiber and preparation method thereof | |
CN114044907B (en) | Intumescent flame retardant functionalized POSS flame retardant and preparation method thereof | |
Zhang et al. | Ultra-high flame-retardant efficiency of phosphorous-silicon hybrid microsphere in poly (butylene adipate-co-terephthalate) | |
Yang et al. | A smart DOPO‐containing decoration armed on Salen‐polyphosphazene toward high‐efficient flame retardancy for epoxy thermoset | |
CN112094502A (en) | High-temperature-resistant mixed silicone rubber and preparation method thereof | |
CN112898666A (en) | Modified semi-siloxane synergistic intumescent flame-retardant low-density polyethylene and preparation method thereof | |
CN112759914A (en) | Compound halogen-free flame-retardant engineering resin and preparation method and application thereof | |
CN114736511B (en) | Low-modulus, anti-Gao Wenyou halogen, flame-retardant and reinforced high-temperature nylon material and preparation method thereof | |
CN116622190A (en) | Organophosphorus-nitrogen flame retardant @ halloysite nanotube hybrid/epoxy resin composite material, and preparation method and application thereof | |
CN113372471B (en) | Phosphorus-oxidized epoxy elastomer and flame-retardant composite material | |
CN113121882B (en) | Functionalized graphene oxide-aluminum hypophosphite flame retardant and preparation method and application thereof | |
CN105061760B (en) | A kind of phosphorous hydridization graphene oxide modified cyanic acid ester resin and preparation method thereof | |
CN115304636A (en) | Organic silicon flame retardant containing phosphorus and nitrogen, and preparation method and application thereof | |
CN110330724B (en) | High-impact-resistance flame-retardant polypropylene composite material and preparation method thereof | |
CN113234324A (en) | Flame-retardant ceramizable organic silicon material and preparation method thereof | |
CN114685937A (en) | Flame-retardant epoxy resin composite material and preparation method thereof | |
CN115304860B (en) | Flame-retardant polypropylene composite material and preparation method and application thereof | |
CN109879907B (en) | Three-source integrated intumescent flame retardant, hybrid intumescent flame retardant grafted by three-source integrated intumescent flame retardant, and preparation methods and applications of three-source integrated intumescent flame retardant and hybrid intumescent flame retardant |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |