CN114456477A - Low-toxicity high-flame-retardant low-smoke halogen-free material and preparation method thereof - Google Patents
Low-toxicity high-flame-retardant low-smoke halogen-free material and preparation method thereof Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 129
- 239000000463 material Substances 0.000 title claims abstract description 53
- 239000000779 smoke Substances 0.000 title claims abstract description 39
- 231100000053 low toxicity Toxicity 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 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 claims abstract description 97
- 229920005989 resin Polymers 0.000 claims abstract description 24
- 239000011347 resin Substances 0.000 claims abstract description 24
- 229920000098 polyolefin Polymers 0.000 claims abstract description 17
- 239000011159 matrix material Substances 0.000 claims abstract description 15
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 13
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 13
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 13
- 239000000314 lubricant Substances 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 6
- VLCLHFYFMCKBRP-UHFFFAOYSA-N tricalcium;diborate Chemical group [Ca+2].[Ca+2].[Ca+2].[O-]B([O-])[O-].[O-]B([O-])[O-] VLCLHFYFMCKBRP-UHFFFAOYSA-N 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 25
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 claims description 16
- UMVBXBACMIOFDO-UHFFFAOYSA-N [N].[Si] Chemical compound [N].[Si] UMVBXBACMIOFDO-UHFFFAOYSA-N 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 12
- -1 polyethylene Polymers 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- 239000013067 intermediate product Substances 0.000 claims description 11
- 229920001661 Chitosan Polymers 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 235000021355 Stearic acid Nutrition 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000012065 filter cake Substances 0.000 claims description 8
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 8
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 8
- 239000008117 stearic acid Substances 0.000 claims description 8
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 claims description 7
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- 239000004743 Polypropylene Substances 0.000 claims description 5
- 238000007792 addition Methods 0.000 claims description 5
- 238000000498 ball milling Methods 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- 238000003828 vacuum filtration Methods 0.000 claims description 5
- MMCPOSDMTGQNKG-UJZMCJRSSA-N aniline;hydrochloride Chemical compound Cl.N[14C]1=[14CH][14CH]=[14CH][14CH]=[14CH]1 MMCPOSDMTGQNKG-UJZMCJRSSA-N 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- MMCPOSDMTGQNKG-UHFFFAOYSA-N anilinium chloride Chemical compound Cl.NC1=CC=CC=C1 MMCPOSDMTGQNKG-UHFFFAOYSA-N 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 238000002485 combustion reaction Methods 0.000 abstract description 3
- 238000003754 machining Methods 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract 1
- 239000000543 intermediate Substances 0.000 description 13
- 239000005038 ethylene vinyl acetate Substances 0.000 description 10
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 230000032683 aging Effects 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 229910052736 halogen Inorganic materials 0.000 description 6
- 150000002367 halogens Chemical class 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229920001912 maleic anhydride grafted polyethylene Polymers 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 150000004961 triphenylmethanes Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
-
- 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
- C08K3/38—Boron-containing compounds
- C08K2003/387—Borates
-
- 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)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a low-toxicity high-flame-retardant low-smoke halogen-free material and a preparation method thereof, belonging to the technical field of high polymer materials, wherein the low-smoke halogen-free material comprises the following raw materials in parts by weight: 5-10 parts of polyolefin, 15-25 parts of matrix resin, 4-10 parts of interfacial compatilizer, 50-60 parts of first flame retardant, 5-12 parts of second flame retardant, 0.5-2.4 parts of lubricant, 0.2-1.2 parts of cross-linking agent and 0.002-0.01 part of antioxidant. In order to improve the flame retardant performance and the low smoke performance of the material, the first flame retardant and the second flame retardant are introduced into the resin material, and the high flame retardant low smoke halogen-free flame retardant material which has small smoke amount during combustion, does not generate harmful corrosive gas and has good machining performance is obtained through the coordination effect of the first flame retardant and the second flame retardant.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a low-toxicity high-flame-retardant low-smoke halogen-free material and a preparation method thereof.
Background
At present, the existing sheath materials for flame-retardant cables at home widely adopt compounds formed by combining halogen-containing polymers or halogen flame retardants, although the traditional flame-retardant materials have excellent flame-retardant performance, when the traditional flame-retardant materials are contacted with flame, a large amount of toxic corrosive hydrogen halide gas and smoke can be generated, field personnel are easy to suffocate, fire fighting personnel are prevented from fighting fire in time, and meanwhile, the toxic gas can corrode instruments and equipment to cause secondary harm, while the low-smoke halogen-free flame-retardant polyolefin sheath materials developed at home and abroad are low in smoke and zero in halogen. But the contradiction between the flame retardant property and the mechanical and processing properties exists, namely the flame retardant property is good, and the mechanical and processing properties can not reach the standard requirements. The flame-retardant cable material disclosed in Chinese patent CN105924729A comprises the following components in parts by weight: 80-100 parts of low-density polyethylene resin, 40-60 parts of PP (polypropylene) resin, 50-60 parts of aluminum hydroxide flame retardant, 1-2 parts of coupling agent, 6-8 parts of melamine cyanurate, 2-3 parts of dimethyl disulfide, 6-10 parts of dioctyl phthalate, 0.1-0.3 part of ultraviolet absorbent, 10-15 parts of active nano calcium carbonate, 4-6 parts of paraffin, 0.2-0.4 part of stearic acid and 2-4 parts of epoxidized soybean oil. The aluminum hydroxide flame retardant is inorganic and has the defect of poor compatibility with organic matters of cable materials.
Therefore, the development of a low-smoke halogen-free material with good flame retardant property is a technical problem to be solved urgently in the field of the existing sheath material for the flame retardant cable.
Disclosure of Invention
The invention aims to provide a low-toxicity high-flame-retardant low-smoke halogen-free material and a preparation method thereof, so as to solve the technical problems in the background art.
The purpose of the invention can be realized by the following technical scheme:
a low-toxicity high-flame-retardant low-smoke halogen-free material comprises the following preparation raw materials in parts by weight: 5-10 parts of polyolefin, 15-25 parts of matrix resin, 4-10 parts of interfacial compatilizer, 50-60 parts of first flame retardant, 5-12 parts of second flame retardant, 0.5-2.4 parts of lubricant, 0.2-1.2 parts of cross-linking agent and 0.002-0.01 part of antioxidant.
Further, the polyolefin is one or a mixture of several of polyethylene, polypropylene, poly-1-butene and poly-4-methyl-1-pentene in any ratio.
Further, the matrix resin is an ethylene-vinyl acetate copolymer, and the mass content of vinyl acetate in the ethylene-vinyl acetate copolymer is 21-27%.
Further, the interfacial compatilizer is one or a mixture of more of maleic anhydride grafted polyethylene, maleic anhydride grafted ethylene vinyl acetate, maleic anhydride grafted ethylene octene copolymer and ethylene-acrylate-maleic anhydride terpolymer in any ratio.
Further, the first flame retardant is modified calcium borate and is prepared by the following steps:
mixing calcium borate ore, absolute ethyl alcohol and a film-forming agent, stirring for 1-1.5h at 70-85 ℃, then carrying out vacuum filtration, taking a filter cake, drying, carrying out ball milling, and sieving to obtain modified calcium borate, wherein the mass ratio of the calcium borate ore, the absolute ethyl alcohol and the film-forming agent is 30-50:80-100: 1.5-4.
Further, the film forming agent is formed by mixing chitosan and stearic acid according to a mass ratio of 5: 1-3.
Furthermore, the particle size of the modified calcium borate is 2-8 μm.
Further, the second flame retardant is a reactive nitrogen-silicon flame retardant and is prepared by the following steps:
dissolving triglycidyl isocyanurate into N, N-dimethylformamide, stirring and heating to 50-60 ℃ under the protection of nitrogen, then dropwise adding an N, N-dimethylformamide solution of an organic silicon intermediate at the dropping speed of 1-3 drops/second, continuing to perform heat preservation stirring reaction for 12-16h after complete dropwise addition, and decompressing and evaporating the solvent to obtain the reactive nitrogen-silicon flame retardant, wherein the mass ratio of the triglycidyl isocyanurate to the organic silicon intermediate is 30: 138-.
Further, the silicone intermediate is made by the steps of:
step one, after 4-hydroxybenzaldehyde and dimethyl sulfoxide are uniformly mixed, adding potassium carbonate and potassium iodide, stirring and heating to 95-115 ℃, then dropwise adding (3-chloropropyl) trimethoxy silane at the dropping speed of 1-3 drops/second, reacting for 9-12h at the temperature of 95-115 ℃ after complete dropwise adding, finishing the reaction, separating the reactant through a column (the volume ratio of methanol to chloroform is 1:3) to obtain an intermediate product, wherein the molar ratio of the 4-hydroxybenzaldehyde to the (3-chloropropyl) trimethoxy silane to the potassium carbonate is 1:1:1.5-2, the adding mass of the potassium iodide is 0.4-1% of the adding mass of the 4-hydroxybenzaldehyde, and introducing a silicon methoxy end capping on a benzene ring by utilizing etherification reaction of phenolic hydroxyl and chlorinated hydrocarbon;
secondly, mixing the intermediate product, aniline and aniline hydrochloride, heating to 115 ℃ under the protection of nitrogen, reacting for 2-2.5h, heating to 135-140 ℃, stirring for reacting for 1.5-2h, cooling, distilling under reduced pressure, dissolving the rest substances with hydrochloric acid, filtering, neutralizing the filtrate with sodium hydroxide solution, standing, aging, filtering after aging is completed, washing filter cake with ethanol for 2-3 times, and drying in vacuum to obtain an organosilicon intermediate, wherein the mass ratio of the intermediate product, aniline and aniline hydrochloride is 28-30:33-48:0.05-0.5, and the condensation reaction of aldehyde group in the intermediate product and hydrogen para-position of amino group in aniline is carried out in the presence of aniline hydrochloride to obtain the organosilicon intermediate, so that the organosilicon intermediate is a derivative of triphenylmethane, wherein two benzene rings are connected with amino groups, the other benzene ring is linked with siloxane chain containing ether group.
The second aspect of the invention provides a preparation method of a low-toxicity high-flame-retardant low-smoke halogen-free material, which at least comprises the following steps:
(1) putting polyolefin and matrix resin into an internal mixer, and mixing for 5-8min to obtain a first mixture;
(2) and then putting the interfacial compatilizer, the first flame retardant, the second flame retardant, the cross-linking agent, the lubricant and the antioxidant into an internal mixer, continuously mixing the interfacial compatilizer, the first flame retardant, the second flame retardant, the cross-linking agent, the lubricant and the antioxidant with the first mixture for 5-10min, extruding and granulating to obtain the flame-retardant resin.
The invention has the beneficial effects that:
in order to improve the flame retardant property and low smoke property of the material, a first flame retardant (modified calcium borate) and a second flame retardant (reactive nitrogen silicon flame retardant) are introduced into a resin material to obtain a high-flame-retardant low-smoke halogen-free flame retardant material which has small smoke quantity during combustion, does not generate harmful corrosive gas and has good machining property, and the modified calcium borate and the reactive nitrogen silicon flame retardant play the following explanation:
firstly, the modified calcium borate is a borate flame retardant, not only has the characteristic that the borate flame retardant absorbs trace halogen, but also utilizes chitosan and stearic acid as film forming agents to carry out surface modification on the borate flame retardant, so that the agglomeration of the calcium borate in a resin base material is reduced, the dispersion of the calcium borate in the resin base material is promoted, and the processing performance of the flame retardant material is improved, particularly, the chitosan is a flame retardant of a carbon source, so that the flame retardant performance of the borate flame retardant is further enhanced;
the reactive nitrogen-silicon flame retardant takes triglycidyl isocyanurate as a core and takes an organosilicon intermediate as a shell, has a branched structure, has the safe halogen-free characteristic of the nitrogen-silicon flame retardant, and silicon methoxyl contained in the polymerization inhibitor has high reactivity and can be grafted into a macromolecular chain of a resin base material to coordinate the branched structure, so that the formation of an interpenetrating network structure of the flame retardant material is promoted, and the mechanical property of the flame retardant material is improved;
thirdly, the modified calcium borate and the reactive nitrogen-silicon flame retardant play a role in coordination, so that the flame retardant performance and low smoke performance of the flame retardant material are greatly improved, and the obtained flame retardant material meets the harsh toxicity requirement in a special application scene: the modified calcium borate plays a role in absorbing trace halogen, can absorb trace halogen contained in the reactive nitrogen-silicon flame retardant (introduced in the synthesis process), and silicon methoxyl in the reactive nitrogen-silicon flame retardant can react with hydroxyl on the surface of the modified calcium borate to anchor the modified calcium borate, so that the migration of the modified calcium borate in the flame-retardant material is avoided, and the agglomeration of the modified calcium borate in the flame-retardant material is further reduced; the modified calcium borate is used as a carbon source (provided by chitosan), the characteristics of the boric acid flame retardant are exerted, the reactive nitrogen-silicon flame retardant is used as a nitrogen source, the silicon flame retardant is exerted, the flame retardant principles are different, and the flame retardant is endowed with high flame retardant and low smoke performance.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Preparation of organosilicon intermediates:
step one, after 0.1mol of 4-hydroxybenzaldehyde and 100mL of dimethyl sulfoxide are uniformly mixed, 0.15mol of potassium carbonate and 0.04-0.13g of potassium iodide are added, the mixture is stirred and heated to 95 ℃, then 0.1mol of (3-chloropropyl) trimethoxysilane is dropwise added at the dropping speed of 1 drop/second, after the dropwise addition is completed, the reaction is finished at the temperature of 95 ℃ for 12 hours, and reactants are separated by a column (the volume ratio of methanol to chloroform is 1:3) to obtain an intermediate product;
and secondly, mixing 28g of intermediate product, 33g of aniline and 0.05g of aniline hydrochloride, heating to 115 ℃ under the protection of nitrogen, reacting for 2 hours, heating to 135 ℃, stirring, reacting for 2 hours, cooling, distilling under reduced pressure, dissolving the rest substances with hydrochloric acid, filtering, neutralizing the filtrate with sodium hydroxide solution, standing, aging, filtering after aging is completed, washing the filter cake with ethanol for 2 times, and drying in vacuum to obtain the organosilicon intermediate.
Example 2
Preparation of organosilicon intermediates:
step one, after 0.1mol of 4-hydroxybenzaldehyde and 100mL of dimethyl sulfoxide are uniformly mixed, 0.2mol of potassium carbonate and 0.13g of potassium iodide are added, the mixture is stirred and heated to 115 ℃, then 0.1mol of (3-chloropropyl) trimethoxysilane is dropwise added at a dropping speed of 3 drops/second, after the dropwise addition is completed, the reaction is finished at 115 ℃ for 9 hours, and a reactant is subjected to column separation (the volume ratio of methanol to chloroform is 1:3) to obtain an intermediate product;
and secondly, mixing 30g of intermediate product, 48g of aniline and 0.5g of aniline hydrochloride, heating to 115 ℃ under the protection of nitrogen, reacting for 2.5h, heating to 140 ℃, stirring and reacting for 1.5h, cooling, carrying out reduced pressure distillation, dissolving the rest substances with hydrochloric acid, filtering, neutralizing the filtrate with sodium hydroxide solution, standing and aging, filtering after aging is completed, washing the filter cake with ethanol for 3 times, and carrying out vacuum drying to obtain the organosilicon intermediate.
Example 3
The second flame retardant is a reactive nitrogen-silicon flame retardant and is prepared by the following steps:
dissolving 30g of triglycidyl isocyanurate into 70mL of N, N-dimethylformamide, stirring and heating to 50 ℃ under the protection of nitrogen, then dropwise adding 70mL of N, N-dimethylformamide solution containing 138g of organic silicon intermediate at the dropping speed of 3 drops/second, continuing to keep the temperature and stir for reaction for 16h after dropwise adding is completed, and decompressing and evaporating the solvent to obtain the reactive nitrogen-silicon flame retardant.
Example 4
The second flame retardant is a reactive nitrogen-silicon flame retardant and is prepared by the following steps:
dissolving 30g of triglycidyl isocyanurate into 70mL of N, N-dimethylformamide, stirring and heating to 60 ℃ under the protection of nitrogen, then dropwise adding 70mL of N, N-dimethylformamide solution containing 146g of organosilicon intermediate at the dropping speed of 1-3 drops/second, continuously keeping the temperature and stirring for reaction for 12 hours after the dropwise adding is completed, and decompressing and distilling out the solvent to obtain the reactive nitrogen-silicon flame retardant.
Example 5
The preparation method of the low-toxicity high-flame-retardant low-smoke halogen-free material comprises the following steps:
step one, preparing the first flame retardant: mixing 30g of calcium borate ore, 80g of absolute ethyl alcohol and 1.5g of film-forming agent, stirring at 70 ℃ for 1.5h, then carrying out vacuum filtration, taking a filter cake, drying, carrying out ball milling and sieving to obtain modified calcium borate, wherein the film-forming agent is formed by mixing chitosan and stearic acid according to the mass ratio of 5: 1;
step two, preparing the following preparation raw materials in parts by weight: 5 parts of polyolefin, 15 parts of matrix resin, 4 parts of interfacial compatilizer, 50 parts of first flame retardant, 5 parts of second flame retardant prepared in example 3, 0.5 part of lubricant, 0.2 part of cross-linking agent and 0.002 part of antioxidant, wherein the polyolefin is polyethylene; the matrix resin is an ethylene-vinyl acetate copolymer, and the mass content of vinyl acetate in the ethylene-vinyl acetate copolymer is 21%; the interfacial compatilizer is maleic anhydride grafted polyethylene.
Step three, putting the polyolefin and the matrix resin into an internal mixer, and internally mixing for 5min to obtain a first mixture; and then putting the interfacial compatilizer, the first flame retardant, the second flame retardant, the cross-linking agent, the lubricant and the antioxidant into an internal mixer, continuously mixing the mixture and the first mixture for 5min, extruding and granulating to obtain the flame-retardant modified flame-retardant rubber.
Example 6
The preparation method of the low-toxicity high-flame-retardant low-smoke halogen-free material comprises the following steps:
step one, preparing the first flame retardant: mixing 40g of calcium borate ore, 90g of absolute ethyl alcohol and 2g of film-forming agent, stirring for 1h at 80 ℃, then carrying out vacuum filtration, taking a filter cake, drying, carrying out ball milling, and sieving to obtain modified calcium borate, wherein the film-forming agent is formed by mixing chitosan and stearic acid according to the mass ratio of 5: 2;
step two, preparing the following preparation raw materials in parts by weight: 7 parts of polyolefin, 20 parts of matrix resin, 6 parts of interfacial compatilizer, 55 parts of first flame retardant, 7 parts of second flame retardant prepared in example 4, 1 part of lubricant, 0.8 part of crosslinking agent and 0.006 part of antioxidant, wherein the polyolefin is polypropylene; the matrix resin is an ethylene-vinyl acetate copolymer, and the mass content of vinyl acetate in the ethylene-vinyl acetate copolymer is 27%; the interfacial compatilizer is maleic anhydride grafted ethylene vinyl acetate.
Step three, putting the polyolefin and the matrix resin into an internal mixer, and carrying out internal mixing for 8min to obtain a first mixture; and then putting the interfacial compatilizer, the first flame retardant, the second flame retardant, the cross-linking agent, the lubricant and the antioxidant into an internal mixer, continuously mixing the mixture and the first mixture for 10min, extruding and granulating to obtain the flame-retardant modified flame-retardant rubber.
Example 7
The preparation of a low-toxicity high-flame-retardant low-smoke halogen-free material comprises the following steps:
step one, preparing the first flame retardant: mixing 50g of calcium borate ore, 100g of absolute ethyl alcohol and 4g of film-forming agent, stirring for 1h at 85 ℃, then carrying out vacuum filtration, taking a filter cake, drying, carrying out ball milling, and sieving to obtain modified calcium borate, wherein the film-forming agent is formed by mixing chitosan and stearic acid according to the mass ratio of 5: 3;
step two, preparing the following preparation raw materials in parts by weight: 10 parts of polyolefin, 25 parts of matrix resin, 10 parts of interfacial compatilizer, 60 parts of first flame retardant, 12 parts of second flame retardant prepared in example 3, 2.4 parts of lubricant, 1.2 parts of cross-linking agent and 0.01 part of antioxidant, wherein the polyolefin is poly-4-methyl-1-pentene; the matrix resin is an ethylene-vinyl acetate copolymer, and the mass content of vinyl acetate in the ethylene-vinyl acetate copolymer is 27%; the interfacial compatilizer is ethylene-acrylate-maleic anhydride terpolymer.
Step three, putting the polyolefin and the matrix resin into an internal mixer, and carrying out internal mixing for 8min to obtain a first mixture; and then putting the interfacial compatilizer, the first flame retardant, the second flame retardant, the cross-linking agent, the lubricant and the antioxidant into an internal mixer, continuously mixing the mixture and the first mixture for 10min, extruding and granulating to obtain the flame-retardant modified flame-retardant rubber.
Comparative example 1
The preparation method of the low-toxicity high-flame-retardant low-smoke halogen-free material comprises the following steps: the first flame retardant was replaced with calcium borate as compared to example 5, and the rest was the same.
Comparative example 2
The preparation method of the low-toxicity high-flame-retardant low-smoke halogen-free material comprises the following steps: the first flame retardant was deleted and the rest was the same as in example 5.
Comparative example 3
The preparation method of the low-toxicity high-flame-retardant low-smoke halogen-free material comprises the following steps: in comparison with example 6, the second flame retardant was replaced by (3-chloropropyl) trimethoxysilane, the rest being identical.
Comparative example 4
The preparation method of the low-toxicity high-flame-retardant low-smoke halogen-free material comprises the following steps: the second flame retardant was deleted and the rest was the same as in example 6.
Example 8
The halogen-free materials obtained in examples 5 to 7 and comparative examples 1 to 4 were subjected to the following performance tests:
tensile strength: testing according to GB/T1040.3; vertical burning grade: testing according to GB/T2408; LOI: testing according to GB/T2406.1; smoke density: testing according to GB/T8323.2, adopting a flameless combustion mode, wherein the test radiation intensity is 25kW/m, and the test time is 20 min;
the above tests are shown in table 1.
TABLE 1
As can be seen from the data in Table 1, the halogen-free materials of examples 5-7 have excellent flame retardant properties and low smoke properties.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (10)
1. A low-toxicity high-flame-retardant low-smoke halogen-free material is characterized in that: the feed comprises the following raw materials in parts by weight: 5-10 parts of polyolefin, 15-25 parts of matrix resin, 4-10 parts of interfacial compatilizer, 50-60 parts of first flame retardant, 5-12 parts of second flame retardant, 0.5-2.4 parts of lubricant, 0.2-1.2 parts of cross-linking agent and 0.002-0.01 part of antioxidant;
the first flame retardant is modified calcium borate and is prepared by the following steps:
mixing calcium borate ore, absolute ethyl alcohol and a film-forming agent, stirring for 1-1.5h at 70-85 ℃, then carrying out vacuum filtration, taking a filter cake, drying, carrying out ball milling, and sieving to obtain modified calcium borate, wherein the mass ratio of the calcium borate ore, the absolute ethyl alcohol and the film-forming agent is 30-50:80-100:1.5-4, and the film-forming agent is formed by mixing chitosan and stearic acid.
2. The low-toxicity high-flame-retardant low-smoke halogen-free material according to claim 1, characterized in that: the mass ratio of the calcium borate ore, the absolute ethyl alcohol and the film forming agent is 30-50:80-100: 1.5-4.
3. The low-toxicity high-flame-retardant low-smoke halogen-free material according to claim 1, characterized in that: the mass ratio of the chitosan to the stearic acid in the film forming agent is 5: 1-3.
4. The low-toxicity high-flame-retardant low-smoke halogen-free material according to claim 1, characterized in that: the polyolefin is one or a mixture of a plurality of polyethylene, polypropylene, poly-1-butene and poly-4-methyl-1-pentene in any ratio.
5. The low-toxicity high-flame-retardant low-smoke halogen-free material according to claim 1, characterized in that: the second flame retardant is a reactive nitrogen-silicon flame retardant and is prepared by the following steps:
dissolving triglycidyl isocyanurate into N, N-dimethylformamide, stirring and heating to 50-60 ℃ under the protection of nitrogen, then dropwise adding an N, N-dimethylformamide solution of an organosilicon intermediate, continuously keeping the temperature and stirring for reaction for 12-16h after complete dropwise addition, and decompressing and evaporating the solvent to obtain the reactive nitrogen-silicon flame retardant.
6. The low-toxicity high-flame-retardant low-smoke halogen-free material according to claim 5, characterized in that: the mass ratio of the triglycidyl isocyanurate to the organosilicon intermediate is 30: 138-146.
7. The low-toxicity high-flame-retardant low-smoke halogen-free material according to claim 5, characterized in that: the organosilicon intermediate is prepared by the following steps:
step one, uniformly mixing 4-hydroxybenzaldehyde and dimethyl sulfoxide, adding potassium carbonate and potassium iodide, stirring and heating to 95-115 ℃, then dropwise adding (3-chloropropyl) trimethoxysilane, continuously reacting for 9-12h after completely dropwise adding, finishing the reaction, and separating the reactant through a column to obtain an intermediate product;
and secondly, mixing the intermediate product, aniline and aniline hydrochloride, heating to 115 ℃ under the protection of nitrogen, reacting for 2-2.5h, then heating to 135-140 ℃, reacting for 1.5-2h, and performing post-treatment to obtain the organosilicon intermediate.
8. The low-toxicity high-flame-retardant low-smoke halogen-free material according to claim 7, characterized in that: in the first step, the molar ratio of 4-hydroxybenzaldehyde, (3-chloropropyl) trimethoxy silane and potassium carbonate is 1:1:1.5-2, and the adding mass of potassium iodide is 0.4-1% of that of 4-hydroxybenzaldehyde.
9. The low-toxicity high-flame-retardant low-smoke halogen-free material according to claim 7, characterized in that: in the second step, the mass ratio of the intermediate product to the aniline hydrochloride is 28-30:33-48: 0.05-0.5.
10. The preparation method of the low-toxicity high-flame-retardant low-smoke halogen-free material according to claim 1 is characterized in that: the method comprises the following steps:
(1) putting polyolefin and matrix resin into an internal mixer, and carrying out internal mixing for 5-8min to obtain a first mixture;
(2) and then putting the interfacial compatilizer, the first flame retardant, the second flame retardant, the cross-linking agent, the lubricant and the antioxidant into an internal mixer, continuously mixing the interfacial compatilizer, the first flame retardant, the second flame retardant, the cross-linking agent, the lubricant and the antioxidant with the first mixture for 5-10min, extruding and granulating to obtain the flame-retardant resin.
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