CN114805930B - Flame retardant, and preparation method and application thereof - Google Patents
Flame retardant, and preparation method and application thereof Download PDFInfo
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- CN114805930B CN114805930B CN202210392798.3A CN202210392798A CN114805930B CN 114805930 B CN114805930 B CN 114805930B CN 202210392798 A CN202210392798 A CN 202210392798A CN 114805930 B CN114805930 B CN 114805930B
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 133
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 75
- 229920002379 silicone rubber Polymers 0.000 claims abstract description 50
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 46
- 239000004945 silicone rubber Substances 0.000 claims abstract description 40
- 239000002253 acid Substances 0.000 claims abstract description 36
- 230000032050 esterification Effects 0.000 claims abstract description 32
- 238000005886 esterification reaction Methods 0.000 claims abstract description 32
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 24
- XZAXQWXHBDKYJI-UHFFFAOYSA-N 2-[(6-oxobenzo[c][2,1]benzoxaphosphinin-6-yl)methyl]butanedioic acid Chemical compound C1=CC=C2P(CC(CC(=O)O)C(O)=O)(=O)OC3=CC=CC=C3C2=C1 XZAXQWXHBDKYJI-UHFFFAOYSA-N 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 38
- 239000010439 graphite Substances 0.000 claims description 29
- 229910002804 graphite Inorganic materials 0.000 claims description 29
- BWVAOONFBYYRHY-UHFFFAOYSA-N [4-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=C(CO)C=C1 BWVAOONFBYYRHY-UHFFFAOYSA-N 0.000 claims description 27
- 239000003054 catalyst Substances 0.000 claims description 24
- 229920000877 Melamine resin Polymers 0.000 claims description 19
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 19
- 229920001661 Chitosan Polymers 0.000 claims description 18
- 239000003963 antioxidant agent Substances 0.000 claims description 11
- 230000003078 antioxidant effect Effects 0.000 claims description 11
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 10
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 10
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 239000002048 multi walled nanotube Substances 0.000 claims description 9
- 239000011159 matrix material Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 claims description 6
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 5
- BXGYYDRIMBPOMN-UHFFFAOYSA-N 2-(hydroxymethoxy)ethoxymethanol Chemical compound OCOCCOCO BXGYYDRIMBPOMN-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000000498 ball milling Methods 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229920002101 Chitin Polymers 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- WSXIMVDZMNWNRF-UHFFFAOYSA-N antimony;ethane-1,2-diol Chemical compound [Sb].OCCO WSXIMVDZMNWNRF-UHFFFAOYSA-N 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 2
- 150000002009 diols Chemical class 0.000 claims 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 239000000779 smoke Substances 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 14
- 230000007246 mechanism Effects 0.000 abstract description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 7
- 239000011574 phosphorus Substances 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 4
- 238000007711 solidification Methods 0.000 abstract description 4
- 230000008023 solidification Effects 0.000 abstract description 4
- 239000007787 solid Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000007789 gas Substances 0.000 description 12
- -1 alkyl phosphate Chemical compound 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- 229920001296 polysiloxane Polymers 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 3
- 239000000347 magnesium hydroxide Substances 0.000 description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000004254 Ammonium phosphate Substances 0.000 description 2
- 229920002261 Corn starch Polymers 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 2
- 235000019289 ammonium phosphates Nutrition 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000008120 corn starch Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical group OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000007480 spreading Effects 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 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 description 1
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- 229920001276 ammonium polyphosphate Polymers 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
-
- 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
- C08K3/04—Carbon
-
- 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
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/21—Urea; Derivatives thereof, e.g. biuret
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34922—Melamine; Derivatives thereof
-
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/02—Cellulose; Modified cellulose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
- C08L3/02—Starch; Degradation products thereof, e.g. dextrin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
- C08L5/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of 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; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- 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
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Abstract
The invention belongs to the technical field of preparation of flame retardant materials, and particularly relates to a flame retardant, a preparation method and application thereof. The raw materials of the flame retardant comprise an acid source, a carbon source and an air source, wherein the acid source is an esterification product of dihydric alcohol containing benzene ring and [ (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] succinic acid; the flame retardant can reduce the smoke release amount and the heat release rate and improve the flame retardant property. The acid source in the flame retardant has both a phosphorus gas phase flame retardant mechanism and a solidification phase flame retardant mechanism, and the benzene ring content in the acid source is high, so that the compactness of the carbon layer can be improved. When the flame retardant is used for silicone rubber, the smoke release amount and the heat release rate can be reduced, and the flame retardant effect is improved.
Description
Technical Field
The invention belongs to the technical field of preparation of flame retardant materials, and particularly relates to a flame retardant, a preparation method and application thereof.
Background
The flame retardant is an auxiliary agent for endowing the material with flame resistance or incombustibility, and is mainly designed for high polymer materials. Flame retardants are of many types and can be broadly classified as phosphorus-based, nitrogen-based, halogen-based, silicon-based, inorganic, intumescent, and other types of flame retardants. Among them, halogen flame retardants have been prohibited because they produce substances that are toxic to the human body and the surrounding environment when burned. Intumescent flame retardants are novel composite flame retardants which are widely focused in the field of flame retardance in China in recent years. The flame retardant has unique flame retardant mechanism and the characteristics of no halogen, low smoke and low toxicity, and is an important way for no halogenation of the flame retardant.
The intumescent flame retardant mainly comprises three components of an acid source, a carbon source and an air source, wherein the porous intumescent carbon layer is formed to play a flame retardant role in a condensed phase, and the formed carbon layer can prevent further degradation of an inner layer high polymer and release of combustible substances to the surface, and can prevent the heat source from transmitting to the high polymer and isolate the oxygen source, so that flame is prevented from spreading and spreading. The intumescent flame retardant has excellent flame retardant property, has the advantages of no halogen, low smoke, low toxicity, molten drop prevention and no corrosive gas, accords with the development direction of the future flame retardant, and has very broad development prospect.
The silicon rubber is used as one of high molecular materials, has the advantages of chemical inertia, stability and the like, and is widely applied to the automobile industry, electronic and electric appliances and medical appliances. Flame retardant modification of silicone rubber is one of the main directions of silicone rubber application research. The early-stage flame retardant for the silicone rubber is mainly halogen flame retardants such as decabromodiphenyl ether, tetrabromobisphenol A, poly-2, 6-dibromophenyl ether, chlorinated paraffin and the like, and the flame retardants have good flame retardant effect on the silicone rubber, but release harmful gases during combustion and have great harm to the environment, so that the application of the flame retardants is limited. The common flame retardants are inorganic flame retardants such as magnesium hydroxide and aluminum hydroxide, no harmful gas is released during combustion, combustion residues cannot pollute the environment, but the magnesium hydroxide and the aluminum hydroxide have obvious flame retardant effect only when the consumption is large, and a large amount of magnesium hydroxide is filled to cause great damage to the physical properties and the like of the silicone rubber. At present, the intumescent flame retardant is used as a direction of non-halogenated development, and has less research reports on the influence on the flame retardant property of the silicone rubber.
Chinese patent document CN111205511a discloses an intumescent flame retardant composition, the raw materials of which comprise an acid source, a carbon source and a gas source, wherein the acid source component comprises melamine phosphate and at least one of ammonium phosphate, ammonium sulfate, ammonium polyphosphate, tricresyl phosphate and alkyl phosphate, the mass percentage of melamine phosphate in the acid source component is 40-65%, the carbon source is pentaerythritol or a mixture of pentaerythritol and sorbitol, and the gas source is melamine or a mixture of melamine and dicyandiamide. When the flame retardant prepared by taking melamine phosphate, ammonium phosphate, tricresyl phosphate and the like as acid sources is applied to silicone rubber, problems of large smoke release amount, large heat release rate and the like can occur.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defects of large smoke release amount, large heat release rate, poor flame retardance and the like when the flame retardant in the prior art is applied to the silicone rubber, so as to provide the flame retardant, and the preparation method and the application thereof.
For this purpose, the invention provides the following technical scheme.
The invention provides a flame retardant, which comprises an acid source, a carbon source and an air source;
the acid source is the esterification product of dihydric alcohol containing benzene ring and [ (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] succinic acid.
The flame retardant satisfying at least one of (1) to (2),
(1) The dihydric alcohol containing benzene ring is 1, 4-benzene dimethanol;
(2) The carbon source includes a first carbon source and a second carbon source;
preferably, the first carbon source is at least one of expandable graphite and multi-walled carbon nanotubes; the second carbon source is at least one of starch, chitosan, chitin and fiber.
The flame retardant satisfying at least one of (1) to (2),
(1) The initial expansion temperature of the expandable graphite is 100-200 ℃, and the expansion degree is 200-300;
(2) The number of layers of the multi-wall carbon nano tube is at least 2.
The flame retardant satisfying at least one of (1) to (3),
(1) The mass ratio of the first carbon source to the second carbon source is (0.5-1.5): 10-15;
(2) The mass ratio of the acid source to the carbon source to the gas source is (20-30) (10.5-16.5) (10-15);
(3) The air source is at least one of urea, melamine and polyamide.
The raw materials of the flame retardant comprise esterification products of 1, 4-benzenedimethanol and [ (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] succinic acid, expandable graphite, chitosan and melamine.
The preparation method of the flame retardant comprises the steps of mixing an acid source, a carbon source and a gas source and ball milling.
The preparation method of the acid source comprises the steps of sequentially carrying out a first reaction and a second reaction on dimethanol containing benzene ring and [ (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] succinic acid under the action of a first catalyst.
The preparation method satisfies at least one of (1) to (6),
(1) The temperature of the first reaction is 145-180 ℃ and the time is 4-6h;
(2) The temperature of the second reaction is 200-230 ℃, and the vacuum degree is minus 0.09MPa to minus 0.1MPa;
(3) The mass ratio of the dihydric alcohol containing benzene ring to [ (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] succinic acid is 1 (1.5-2.5);
(4) The first catalyst is at least one of antimony acetate, ethylene glycol antimony and antimony trioxide; preferably, the mass of the first catalyst is 2-4% of the mass of the dihydric alcohol containing benzene ring;
(5) The method further comprises the step of adding an antioxidant before the first reaction is carried out; preferably, the mass of the antioxidant is 0.1-0.5% of the dihydric alcohol containing benzene ring;
(6) The rotating speed of the ball milling is 100-300r/min.
When preparing an acid source, the mass of the first catalyst is 2-4% of that of dihydric alcohol containing benzene ring, and the mass of the antioxidant is 0.1-0.5% of that of dihydric alcohol containing benzene ring; wherein the antioxidant may be at least one of 1010, 1076 and 626.
The preparation method of the acid source comprises the steps of sequentially carrying out a first reaction and a second reaction on dimethanol containing benzene ring and [ (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] succinic acid under the action of a first catalyst; wherein, when the first reaction is carried out, 1, 4-benzenedimethanol and DDP ([ (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] succinic acid) are solid, the esterification product is liquid, the solid is reduced along with the progress of the reaction, the liquid is increased to a certain extent, and when the solid is converted into clear and transparent liquid, the first reaction is completed, and the time of the first reaction is generally about 4-6H.
And when the actual water yield reaches 90% -95% of the theoretical water yield, the second reaction is ended.
The invention also provides application of the flame retardant in the silicone rubber, and the specific steps of the application comprise mixing and curing the silicone rubber matrix, the flame retardant and the second catalyst.
The use satisfying at least one of (1) to (3),
(1) The mass ratio of the silicon rubber matrix to the flame retardant to the second catalyst is 100 (10-20) (1-3);
(2) The mass ratio of the second catalyst is (0.5-1): a mixture of ethyl orthosilicate and dibutyltin dilaurate of (1-2.5);
(3) The curing time is 12-24 hours.
When the silicone rubber is prepared, the silicone rubber matrix and the flame retardant are mixed, stirred for 30-80min at the rotating speed of 800-1500r/min, then added with the second catalyst, stirred for 10-20s, and cured for 12-24h to obtain the silicone rubber.
The silicone rubber matrix is hydroxyl-terminated polysiloxane.
Flame retardant mechanisms of intumescent flame retardants include phosphorus-based gas phase flame retardant mechanisms and solid phase flame retardant mechanisms. Wherein, the phosphorus gas phase flame retardant mechanism: PO.generated by combustion is combined with high-energy free radicals in the flame, such as OH.and H.and the like, so that the concentration of the high-energy free radicals in the flame is reduced, and the temperature of the flame is further reduced. The mechanism of flame resistance of the solidification phase: the phosphoric acid generated by combustion is used as a dehydrating agent to remove water in the matrix polymer and form carbon.
The technical scheme of the invention has the following advantages:
1. the raw materials of the flame retardant provided by the invention comprise an acid source, a carbon source and an air source, wherein the acid source is an esterification product of dihydric alcohol containing benzene ring and [ (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] succinic acid; the flame retardant can reduce the smoke release amount and the heat release rate and improve the flame retardant property. The acid source in the flame retardant has both a phosphorus gas phase flame retardant mechanism and a solidification phase flame retardant mechanism, and the benzene ring content in the acid source is high, so that the compactness of the carbon layer can be improved. When the flame retardant is used for silicone rubber, the smoke release amount and the heat release rate can be reduced, and the flame retardant effect is improved.
The invention takes the esterification product of dihydric alcohol and [ (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] succinic acid as an acid source, the acid source has a plurality of benzene ring structures, and can improve the char formation and the compactness, and the heat resistance, thereby reducing the smoke release amount and the heat release rate, the acid source can promote the foaming expansion, form a porous carbon layer, play a role of heat insulation, and solve the problems of large smoke release amount and large heat release rate when the flame retardant prepared by taking micromolecules such as tricresyl phosphate and the like as the acid source in the prior art is applied to the silicon rubber.
The esterification product of dihydric alcohol and [ (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] succinic acid is taken as an acid source, the esterification product is matched with an air source and a carbon source, a phosphorus-containing structure in the acid source can exert a gas phase and solidification phase flame-retardant mechanism to form a carbon layer, a benzene ring structure can enhance the compactness of the carbon layer, the carbon source can increase the thickness of the carbon layer, the formation of the carbon layer is further promoted, nonflammable gas is generated after the air source is added for flame retardance, and the three are synergistic to enable the system to be rapidly foamed and expanded to form a porous carbon layer, so that the flame-retardant effect is improved.
2. The flame retardant provided by the invention takes an esterification product of 1, 4-benzenedimethanol and [ (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorinane-6-yl) methyl ] succinic acid as an acid source, the acid source has a large molecular weight, a plurality of benzene ring structures, the compactness of a carbon layer is enhanced, the flame retardant effect is improved, and compared with a micromolecular esterified substance, the acid source has better flame retardant effect.
The expandable graphite and/or the multi-wall carbon nano tube are used as a first carbon source, at least one of starch, chitosan, chitin and fiber is used as a second carbon source, and the two carbon sources are matched to accelerate the formation of a carbon layer and improve the char formation and heat resistance.
The expandable graphite under specific parameters can be rapidly expanded at low temperature, so that the heat insulation effect is achieved; the expandable graphite can accelerate the formation of the carbon layer, further reduce heat release, and has smoke suppression effect and heat insulation effect due to the expansion performance of the expandable graphite, thereby being beneficial to the flame retardant to achieve the optimal effect. The multi-wall carbon nano tube with the multi-layer structure has better smoke suppression effect.
According to the invention, the carbon source with a specific dosage is adopted, so that the rapid formation of the carbon layer can be promoted, and the flame retardant effect is improved.
3. The esterification product of the 1, 4-benzene dimethanol and [ (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] succinic acid, expandable graphite, chitosan and melamine can optimize the flame retardant effect of the flame retardant.
4. According to the preparation method of the flame retardant, provided by the invention, the dimethanol containing the benzene ring and [ (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] succinic acid sequentially perform a first reaction and a second reaction under the action of the catalyst, and the reaction conditions are controlled, so that the acid and the alcohol can be promoted to react as much as possible, the polymerization degree of an esterified substance is increased, the content of the benzene ring and phosphorus element is increased, and the char formation and flame retardance of a strong acid source are further improved.
5. The flame retardant provided by the invention is applied to the preparation of the silicone rubber, so that the problem of poor flame retardant effect of the silicone rubber in the prior art can be solved, the smoke release amount and the heat release amount are reduced, and the flame retardant effect of the silicone rubber is improved.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
Example 1
This example provides a flame retardant comprising, as raw materials, 20g of an esterification product of 1, 4-benzenedimethanol and DDP, 0.5g of expandable graphite, 10g of chitosan and 10g of melamine. Wherein the initial expansion temperature of the expandable graphite is 150 ℃ and the expansion degree is 300.
The embodiment also provides a preparation method of the flame retardant, which comprises the following steps,
the esterified product, the expandable graphite, the chitosan and the melamine are added into a ball mill according to the mass, and are stirred at the rotating speed of 100r/min, so as to obtain the flame retardant.
The preparation method of the esterification product of 1, 4-benzenedimethanol and DDP comprises the steps of adding 100g of 1, 4-benzenedimethanol, 150g of DDP, 2g of antimony acetate and 0.15g of 1010 antioxidant into a four-neck flask, heating to 150+/-3 ℃ for normal pressure reaction, and indicating that the first reaction is finished when all solids are converted into clear and transparent liquid, wherein the time of the first reaction is 4 hours, and nitrogen is not needed in the process; and then heating to 200 ℃ under the protection of nitrogen, vacuumizing to-0.09 MPa, and after the water yield reaches 90% of the theoretical water yield, finishing the reaction to obtain a light yellow solid, wherein the solid is an esterification product of 1, 4-benzenedimethanol and DDP, and the esterification product has a multi-benzene ring structure.
The embodiment also provides a preparation method of the silicon rubber, which comprises the following steps,
100g of hydroxyl-terminated polysiloxane (manufacturer is Jinan XingChi chemical Co., ltd., model XC-107) and 10g of the flame retardant are added into a stirring barrel, stirred at the speed of 800r/min for 30min, then 1g of catalyst (ethyl orthosilicate and dibutyltin dilaurate with the mass ratio of 0.5:1) is added, stirred for 10s, poured into a mold, and cured for 12h at room temperature to obtain the flame-retardant silicone rubber.
Example 2
This example provides a flame retardant comprising 25g of the esterification product of 1, 4-benzenedimethanol with DDP, 1g of expandable graphite, 13g of chitosan and 13g of melamine. Wherein the initial expansion temperature of the expandable graphite is 150 ℃ and the expansion degree is 300.
The embodiment also provides a preparation method of the flame retardant, which comprises the following steps,
the esterified product, the expandable graphite, the chitosan and the melamine are added into a ball mill according to the mass, and are stirred at the rotating speed of 200r/min, so as to obtain the flame retardant.
The preparation method of the esterification product of 1, 4-benzenedimethanol and DDP comprises the steps of adding 110g of 1, 4-benzenedimethanol, 220g of DDP, 3.3g of antimony acetate and 0.33g of 1010 antioxidant into a four-neck flask, heating to 167+/-3 ℃ for normal pressure reaction, and indicating that the first reaction is finished when all solids are converted into clear transparent liquid, wherein the time of the first reaction is 5 hours; then heating to 220 ℃ under the protection of nitrogen, vacuumizing to-0.095 MPa, and after the water yield reaches 92% of the theoretical water yield, finishing the reaction to obtain a light yellow solid, wherein the solid is an esterification product of 1, 4-benzenedimethanol and DDP, and the esterification product has a multi-benzene ring structure.
The embodiment also provides a preparation method of the silicon rubber, which comprises the following steps,
100g of hydroxyl-terminated polysiloxane (manufacturer is Jinan Xingchi chemical Co., ltd., model XC-107) and 15g of the flame retardant are added into a stirring barrel, stirred at the speed of 1000r/min for 50min, then 2g of catalyst (ethyl orthosilicate and dibutyl tin dilaurate with the mass ratio of 0.6:1.6) are added, stirred for 15s, poured into a mold, and cured for 18h at room temperature to obtain the flame retardant silicone rubber.
Example 3
This example provides a flame retardant comprising, as raw materials, 30g of an esterification product of 1, 4-benzenedimethanol and DDP, 1.5g of expandable graphite, 15g of chitosan and 15g of melamine. Wherein the initial expansion temperature of the expandable graphite is 150 ℃ and the expansion degree is 300.
The embodiment also provides a preparation method of the flame retardant, which comprises the following steps,
the esterified product, the expandable graphite, the chitosan and the melamine are added into a ball mill according to the mass, and are stirred at the rotating speed of 300r/min, so as to obtain the flame retardant.
The preparation method of the esterification product of 1, 4-benzenedimethanol and DDP comprises the steps of adding 120g of 1, 4-benzenedimethanol, 300g of DDP, 4.8g of antimony acetate and 0.6g of 1010 antioxidant into a four-neck flask, heating to 170+/-3 ℃ for normal pressure reaction, and indicating that the first reaction is finished when all solids are converted into clear transparent liquid, wherein the time of the first reaction is 6 hours; then heating to 230 ℃ under the protection of nitrogen, vacuumizing to-0.1 MPa, and after the water yield reaches 95% of the theoretical water yield, finishing the reaction to obtain a light yellow solid, wherein the solid is an esterification product of 1, 4-benzenedimethanol and DDP, and the esterification product has a multi-benzene ring structure.
The embodiment also provides a preparation method of the silicon rubber, which comprises the following steps,
100g of hydroxyl-terminated polysiloxane (manufacturer is Jinan XingChi chemical Co., ltd., model XC-107) and 20g of the flame retardant are added into a stirring barrel, stirring is carried out at a speed of 1500r/min for 80min, then 3g of catalyst (ethyl orthosilicate and dibutyltin dilaurate with a mass ratio of 1:2.1) is added, stirring is carried out for 20s, the mixture is poured into a mould, and the mixture is solidified for 24h at room temperature, thus obtaining the flame-retardant silicone rubber.
Example 4
This example provides a flame retardant comprising, as raw materials, 20g of an esterification product of 1, 4-benzenedimethanol and DDP, 0.5g of multi-walled carbon nanotubes, 10g of chitosan and 10g of melamine. Wherein the number of layers of the multi-wall carbon nano tube is 4.
The embodiment also provides a preparation method of the flame retardant, which comprises the following steps,
adding the esterified product, the multi-wall carbon nano tube, the chitosan and the melamine into a ball mill according to the mass, and stirring at the rotating speed of 100r/min to obtain the flame retardant.
The preparation method of the esterification product of 1, 4-benzenedimethanol and DDP comprises the steps of adding 100g of 1, 4-benzenedimethanol, 150g of DDP, 2g of antimony acetate and 0.15g of 1010 antioxidant into a four-neck flask, heating to 150+/-3 ℃ for normal pressure reaction, and indicating that the first reaction is finished when all solids are converted into clear and transparent liquid, wherein the time of the first reaction is 4 hours; and then heating to 200 ℃ under the protection of nitrogen, vacuumizing to-0.09 MPa, and after the water yield reaches 90% of the theoretical water yield, finishing the reaction to obtain a light yellow solid, wherein the solid is an esterification product of 1, 4-benzenedimethanol and DDP, and the esterification product has a multi-benzene ring structure.
The embodiment also provides a preparation method of the silicon rubber, which comprises the following steps,
100g of hydroxyl-terminated polysiloxane (manufacturer is Jinan XingChi chemical Co., ltd., model XC-107) and 10g of the flame retardant are added into a stirring barrel, stirred at the speed of 800r/min for 30min, then 1g of catalyst (ethyl orthosilicate and dibutyltin dilaurate with the mass ratio of 0.5:1) is added, stirred for 10s, poured into a mold, and cured for 12h at room temperature to obtain the flame-retardant silicone rubber.
Example 5
This example provides a flame retardant comprising, as raw materials, 20g of an esterification product of 1, 4-benzenedimethanol and DDP, 0.5g of expandable graphite, 5g of cellulose, 5g of corn starch, and 10g of urea. Wherein the initial expansion temperature of the expandable graphite is 120 ℃ and the expansion degree is 240.
The embodiment also provides a preparation method of the flame retardant, which comprises the following steps,
the esterified product, the expandable graphite, the cellulose, the corn starch and the urea are added into a ball mill according to the mass, and are stirred at the rotating speed of 100r/min, so as to obtain the flame retardant.
The preparation method of the esterification product of 1, 4-benzenedimethanol and DDP comprises the steps of adding 100g of 1, 4-benzenedimethanol, 150g of DDP, 2g of ethylene glycol antimony and 0.15g of 1076 antioxidant into a four-neck flask, heating to 150+/-3 ℃ for normal pressure reaction, and indicating that the first reaction is finished when all solids are converted into clear transparent liquid, wherein the time of the first reaction is 4 hours; then heating to 200 ℃ under the protection of nitrogen, vacuumizing to-0.09 MPa, and after the water yield reaches more than 90% of the theoretical water yield, finishing the reaction to obtain a light yellow solid, wherein the solid is an esterification product of 1, 4-benzenedimethanol and DDP, and the esterification product has a multi-benzene ring structure.
The embodiment also provides a preparation method of the silicon rubber, which comprises the following steps,
100g of hydroxyl-terminated polysiloxane (manufacturer is Jinan XingChi chemical Co., ltd., model XC-107) and 10g of the flame retardant are added into a stirring barrel, stirred at the speed of 800r/min for 30min, then 1g of catalyst (ethyl orthosilicate and dibutyltin dilaurate with the mass ratio of 0.5:1) is added, stirred for 10s, poured into a mold, and cured for 12h at room temperature to obtain the flame-retardant silicone rubber.
Comparative example 1
The comparative example provides a method for preparing silicone rubber, comprising the following steps,
100g of silicone rubber (model XC-107 from Jinan Xinchi chemical Co., ltd.) was added to the beaker, stirred for 60 minutes in a 1000r/min disperser, after stirring uniformly, 2g of catalyst (mass ratio of ethyl orthosilicate to dibutyltin dilaurate: 1:2) was added, stirring was continued for 20 seconds, poured into a mold, and cured at room temperature for 24 hours.
Comparative example 2
This comparative example provides a flame retardant comprising raw materials of 20g tricresyl phosphate, 0.5g expandable graphite, 10g chitosan and 10g melamine. Wherein the initial expansion temperature of the expandable graphite is 150 ℃ and the expansion degree is 300.
The comparative example also provides a preparation method of the flame retardant, which comprises the following steps,
adding tricresyl phosphate, expandable graphite, chitosan and melamine into a ball mill according to the mass, and stirring at a rotating speed of 100r/min to obtain the flame retardant.
The comparative example also provides a method for preparing silicone rubber, comprising the following steps,
100g of hydroxyl-terminated polysiloxane (manufacturer is Jinan XingChi chemical Co., ltd., model XC-107) and 10g of the flame retardant are added into a stirring barrel, stirred at the speed of 800r/min for 30min, then 1g of catalyst (ethyl orthosilicate and dibutyltin dilaurate with the mass ratio of 0.5:1) is added, stirred for 10s, poured into a mold, and cured for 12h at room temperature to obtain the flame-retardant silicone rubber.
Comparative example 3
This comparative example provides a flame retardant comprising 20g DDP, 0.5g expandable graphite, 10g chitosan and 10g melamine. Wherein the initial expansion temperature of the expandable graphite is 150 ℃ and the expansion degree is 300.
The comparative example also provides a preparation method of the flame retardant, which comprises the following steps,
adding DDP, expandable graphite, chitosan and melamine into a ball mill according to the mass, and stirring at a rotating speed of 100r/min to obtain the flame retardant.
The comparative example also provides a method for preparing silicone rubber, comprising the following steps,
100g of hydroxyl-terminated polysiloxane (manufacturer is Jinan XingChi chemical Co., ltd., model XC-107) and 10g of the flame retardant are added into a stirring barrel, stirred at the speed of 800r/min for 30min, then 1g of catalyst (ethyl orthosilicate and dibutyltin dilaurate with the mass ratio of 0.5:1) is added, stirred for 10s, poured into a mold, and cured for 12h at room temperature to obtain the flame-retardant silicone rubber.
Test examples
The test examples provide performance tests and test methods for the flame retardant silicone rubber prepared in each example and comparative example, and in particular,
the method for testing the limiting oxygen index of the flame-retardant silicone rubber comprises the following steps: reference is made to ISO 4589:1984, testing;
the method for testing the smoke release rate of the flame-retardant silicone rubber comprises the following steps: test with reference to ISO 5660-1;
the method for testing the tensile strength of the flame-retardant silicone rubber comprises the following steps: test with reference to GBT 16491-2008;
the test method of the breaking elongation of the flame-retardant silicone rubber comprises the following steps: the test was conducted with reference to JIS K6404-3-1999.
Table 1 results of performance testing of silicone rubbers of examples and comparative examples
| Limiting oxygen index | Rate of smoke release (m 2 /s) | Tensile Strength (MPa) | Elongation at break (%) | |
| Example 1 | 24.6 | 0.16 | 0.39 | 281 |
| Example 2 | 28.1 | 0.14 | 0.44 | 343 |
| Example 3 | 30.2 | 0.11 | 0.56 | 369 |
| Example 4 | 24.1 | 0.19 | 0.34 | 270 |
| Example 5 | 24.3 | 0.17 | 0.36 | 272 |
| Comparative example 1 | 20 | 0.3 | 0.2 | 105 |
| Comparative example 2 | 21.6 | 0.25 | 0.33 | 266 |
| Comparative example 3 | 22.2 | 0.22 | 0.35 | 269 |
According to the results shown in Table 1, when the flame retardant provided by the invention is used for preparing silicone rubber, the smoke release amount and the heat release rate can be reduced on the basis of ensuring mechanical properties such as tensile strength and the like of the silicone rubber; the limiting oxygen index is high, which is helpful for reducing the heat release rate and improving the flame retardance of the silicone rubber.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (10)
1. The flame retardant is characterized by comprising an acid source, a carbon source and an air source;
the acid source is an esterification product of dihydric alcohol containing benzene ring and [ (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] succinic acid;
the carbon source includes a first carbon source and a second carbon source; the first carbon source is at least one of expandable graphite and multi-wall carbon nano tubes; the second carbon source is at least one of starch, chitosan, chitin and fiber; the mass ratio of the first carbon source to the second carbon source is (0.5-1.5): 10-15;
the mass ratio of the acid source to the carbon source to the gas source is (20-30) (10.5-16.5) (10-15);
the air source is at least one of urea, melamine and polyamide;
the preparation method of the flame retardant comprises the following steps: mixing an acid source, a carbon source and a gas source, and ball milling.
2. The flame retardant of claim 1, wherein the benzene ring-containing glycol is 1, 4-benzenedimethanol.
3. The flame retardant according to claim 2, wherein at least one of (1) to (2) is satisfied,
(1) The initial expansion temperature of the expandable graphite is 100-200 ℃, and the expansion degree is 200-300;
(2) The number of layers of the multi-wall carbon nano tube is at least 2.
4. A flame retardant according to any of claims 1-3, wherein the raw materials of the flame retardant comprise esterification products of 1, 4-benzenedimethanol with [ (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] succinic acid, expandable graphite, chitosan and melamine.
5. The flame retardant according to claim 1, wherein the acid source is prepared by sequentially reacting a benzene ring-containing dimethanol with [ (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] butanedioic acid in the presence of a first catalyst.
6. The flame retardant according to claim 5, wherein at least one of (1) to (6) is satisfied,
(1) The temperature of the first reaction is 145-180 ℃ and the time is 4-6h;
(2) The temperature of the second reaction is 200-230 ℃, and the vacuum degree is-0.09 MPa to-0.1 MPa;
(3) The mass ratio of the dihydric alcohol containing benzene ring to [ (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] succinic acid is 1 (1.5-2.5);
(4) The first catalyst is at least one of antimony acetate, ethylene glycol antimony and antimony trioxide;
(5) The method further comprises the step of adding an antioxidant before the first reaction is carried out;
(6) The rotating speed of the ball milling is 100-300r/min.
7. The flame retardant according to claim 6, wherein the mass of the first catalyst is 2 to 4% of the benzene ring-containing diol.
8. The flame retardant according to claim 6, wherein the antioxidant is 0.1 to 0.5% by mass of the benzene ring-containing diol.
9. Use of a flame retardant according to any of claims 1 to 7 in silicone rubber, characterized in that the specific step of application comprises mixing a silicone rubber matrix, the flame retardant and a second catalyst, curing.
10. The use according to claim 9, wherein at least one of (1) to (3) is satisfied,
(1) The mass ratio of the silicon rubber matrix to the flame retardant to the second catalyst is 100 (10-20) (1-3);
(2) The mass ratio of the second catalyst is (0.5-1): a mixture of ethyl orthosilicate and dibutyltin dilaurate of (1-2.5);
(3) The curing time is 12-24 hours.
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| CN103073751A (en) * | 2012-11-22 | 2013-05-01 | 中国科学院宁波材料技术与工程研究所 | Expansive type fire retardant, flame retardation polymer composition containing fire retardant and fiber enhanced polymer-based flame retardation composite material |
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| CN112175242A (en) * | 2019-08-14 | 2021-01-05 | 北京服装学院 | Microcapsule intumescent flame retardant and preparation method and application thereof |
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