CN106543718B - A kind of high flame retardant high temperature resistant nylon composite material and preparation method thereof - Google Patents
A kind of high flame retardant high temperature resistant nylon composite material and preparation method thereof Download PDFInfo
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- CN106543718B CN106543718B CN201611055071.7A CN201611055071A CN106543718B CN 106543718 B CN106543718 B CN 106543718B CN 201611055071 A CN201611055071 A CN 201611055071A CN 106543718 B CN106543718 B CN 106543718B
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- flame retardant
- composite material
- nylon composite
- expanded graphite
- temperature resistant
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 53
- 239000004677 Nylon Substances 0.000 title claims abstract description 32
- 229920001778 nylon Polymers 0.000 title claims abstract description 32
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 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 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 41
- 239000010439 graphite Substances 0.000 claims abstract description 41
- 230000004048 modification Effects 0.000 claims abstract description 16
- 238000012986 modification Methods 0.000 claims abstract description 16
- 239000003381 stabilizer Substances 0.000 claims abstract description 12
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 9
- 239000004952 Polyamide Substances 0.000 claims abstract description 7
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- 229920002647 polyamide Polymers 0.000 claims abstract description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 4
- 239000011574 phosphorus Substances 0.000 claims abstract description 4
- 239000002253 acid Substances 0.000 claims description 17
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 239000000314 lubricant Substances 0.000 claims description 8
- 238000005469 granulation Methods 0.000 claims description 7
- 230000003179 granulation Effects 0.000 claims description 7
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 239000007822 coupling agent Substances 0.000 claims description 6
- 230000003292 diminished effect Effects 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 229920006119 nylon 10T Polymers 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 4
- XCJXQCUJXDUNDN-UHFFFAOYSA-N chlordene Chemical group C12C=CCC2C2(Cl)C(Cl)=C(Cl)C1(Cl)C2(Cl)Cl XCJXQCUJXDUNDN-UHFFFAOYSA-N 0.000 claims description 4
- 229960001760 dimethyl sulfoxide Drugs 0.000 claims description 4
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 4
- 239000012312 sodium hydride Substances 0.000 claims description 4
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 101000576320 Homo sapiens Max-binding protein MNT Proteins 0.000 claims description 3
- 229920006121 Polyxylylene adipamide Polymers 0.000 claims description 3
- CSHCPECZJIEGJF-UHFFFAOYSA-N methyltin Chemical compound [Sn]C CSHCPECZJIEGJF-UHFFFAOYSA-N 0.000 claims description 3
- 229920006154 PA11T Polymers 0.000 claims description 2
- 229920006153 PA4T Polymers 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- UQLDLKMNUJERMK-UHFFFAOYSA-L di(octadecanoyloxy)lead Chemical compound [Pb+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O UQLDLKMNUJERMK-UHFFFAOYSA-L 0.000 claims description 2
- 235000019359 magnesium stearate Nutrition 0.000 claims description 2
- 229920006115 poly(dodecamethylene terephthalamide) Polymers 0.000 claims description 2
- 229920006139 poly(hexamethylene adipamide-co-hexamethylene terephthalamide) Polymers 0.000 claims description 2
- 229920006131 poly(hexamethylene isophthalamide-co-terephthalamide) Polymers 0.000 claims description 2
- 229920006117 poly(hexamethylene terephthalamide)-co- polycaprolactam Polymers 0.000 claims description 2
- 229920006128 poly(nonamethylene terephthalamide) Polymers 0.000 claims description 2
- 229920003366 poly(p-phenylene terephthalamide) Polymers 0.000 claims description 2
- 235000012424 soybean oil Nutrition 0.000 claims description 2
- 239000003549 soybean oil Substances 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- 150000003573 thiols Chemical class 0.000 claims description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims 1
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 claims 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 claims 1
- 239000011575 calcium Substances 0.000 claims 1
- 229910052791 calcium Inorganic materials 0.000 claims 1
- 150000002825 nitriles Chemical class 0.000 claims 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 4
- ZSTLPJLUQNQBDQ-UHFFFAOYSA-N azanylidyne(dihydroxy)-$l^{5}-phosphane Chemical compound OP(O)#N ZSTLPJLUQNQBDQ-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000460 chlorine Substances 0.000 abstract description 4
- 229910052801 chlorine Inorganic materials 0.000 abstract description 4
- 230000005012 migration Effects 0.000 abstract description 4
- 238000013508 migration Methods 0.000 abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 239000011159 matrix material Substances 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- 229920005989 resin Polymers 0.000 abstract description 2
- 239000011347 resin Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 230000006872 improvement Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000003963 antioxidant agent Substances 0.000 description 5
- 230000003078 antioxidant effect Effects 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 230000002195 synergetic effect Effects 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- -1 PA5T Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000003471 anti-radiation Effects 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical group [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical class CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 229920006375 polyphtalamide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
-
- 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
- C08K5/5399—Phosphorus bound to nitrogen
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- 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
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of high flame retardant high temperature resistant nylon composite materials and preparation method thereof.The invention discloses a kind of high flame retardant high-temperature nylon composite material and preparation methods, by weight percentage, the composition of the composite material includes: polyamide 50 ~ 85%, fire retardant 6 ~ 45%, stabilizer 0.1 ~ 2%, other auxiliary agents 0.1 ~ 12%, wherein the fire retardant is hexachlorocyclotriph,sphazene graft modification expanded graphite.The present invention combines nitrogen, phosphorus, chlorine element and organic carbon, it is remarkably improved its cooperative flame retardant ability, phosphonitrile fire retardant is set to be fixed on expanded graphite surface by chemical bond, dispersibility and compatibility of the expanded graphite in resin matrix are not only increased, the problem of the easy external migration of use process small molecular fire retardant is also solved.
Description
Technical field
The present invention relates to flame-resistant high-temperature-resistant nylon synthesis technical fields, and in particular to a kind of high flame retardant high temperature resistant nylon is multiple
Condensation material and preparation method thereof.
Background technique
High temperature resistant nylon has excellent performance, has in electric industry, electronics industry industry and auto industry industry
Extensive use.Although high temperature resistant nylon has outstanding heat resistance, its flame retardant property and actual operation requirements exist
Larger gap, which greatly limits it various fields application.Therefore, the flame retardant property for improving high temperature resistant nylon has centainly
Urgency and necessity.
Hexachlorocyclotriph,sphazene is widely used as preventing fires because of nitrogen, phosphorus, chlorine element and preferable reactivity with high-content
Fire-retardant and self-extinguishing.However, the study found that when individually using hexachlorocyclotriph,sphazene and its derivative as fire retardant,
Flame retardant effect is simultaneously unsatisfactory, and need to cooperate with other fire retardants could obtain optimal effect.Chinese patent CN
Hexachlorocyclotriph,sphazene is grafted to carbon nano tube surface in 103146025 B, the two is combined synthesize it is a kind of novel
Cooperative flame retardant type fire retardant.Yang Jintao et al. described in 104558046 A of Chinese patent CN hexachlorocyclotriph,sphazene be grafted from
Preparation method of the sub- liquid as efficient high molecular fire retardant additive, realization hexachlorocyclotriph,sphazene cooperate with resistance with ionic liquid
Combustion.Hao Dongmei et al. () is by the hexachlorocyclotriph,sphazene derivative of high-content and fire-retardant association in 102504410 A of Chinese patent CN
Effect agent is directly appended in acrylic resin, is prepared using phosphazene derivative as the polypropene composition of fire retardant main body.
Since the price is very expensive for carbon nanotube and ionic liquid in above-mentioned the first two patent, it is grafted hexachlorocyclotriph,sphazene
Modification prepares the with high costs of synergistic fire retardant, there is great limitation in practical applications, is unsuitable for industrial application.In addition,
When directly addition hexachlorocyclotriph,sphazene or derivatives thereof does fire retardant, material can have the phenomenon that small molecule fire retardant external migration,
Cause material property to deteriorate, influences using effect.
Summary of the invention
The invention is intended to provide a kind of high flame retardant high temperature resistant nylon composite material and preparation method thereof, to reduce chlordene ring
Three phosphonitrile graft modifications prepare the cost of synergistic fire retardant.
In order to achieve the above objectives, first foundation technical solution of the invention is as follows: a kind of high flame retardant high temperature resistant nylon is multiple
Condensation material, the polyamide for being 50 ~ 85% including weight percent, the fire retardant that weight percent is 6 ~ 45%, weight percent are
0.1 ~ 2% stabilizer, the auxiliary agent that weight percent is 0.1 ~ 12%；Fire retardant includes through the swollen of the modified grafting of hexachlorocyclotriph,sphazene
The molar ratio of swollen graphite, hexachlorocyclotriph,sphazene and expanded graphite is 0.1 ~ 10.
The advantages of this programme is: expanded graphite has extremely strong resistance to pressure, flexibility, plasticity and self-lubrication；It is extremely strong
Anti- high and low temperature, anticorrosive, anti-radiation characteristic；Extremely strong shock-resistance features；Extremely strong conductivity；It is extremely strong anti-aging, anti-twist
Characteristic；The fusing and infiltration of various metals can be resisted；It is nontoxic, be free of any carcinogenic substance, be safe from harm to environment；Expand stone
Ink is heated when reaching certain temperature, decomposes due to being occluded in compound in interlayer dot matrix, expanded graphite just starts to expand, referred to as rise
Beginning expansion temperature expands completely at 1000 DEG C, reaches maximum volume.200 times or more when swelling volume can achieve initial.
Graphite after expansion becomes the very low vermiform of density by former flakey, forms an extraordinary heat insulation layer.Expanded graphite
It is both the carbon source and heat insulation layer in intumescent system, can be effectively heat-insulated, have rate of heat release low in a fire, mass loss is small,
The few feature of the flue gas of generation.Hexachlorocyclotriph,sphazene graft modification expanded graphite is high as synergistic fire retardant preparation high flame retardant
Nitrogen, phosphorus, chlorine element and organic carbon are combined, are remarkably improved its cooperative flame retardant ability, passing through by warm nylon composite materials
Learning key makes phosphonitrile fire retardant be fixed on expanded graphite surface, not only increases dispersibility and phase of the expanded graphite in resin matrix
Capacitive also solves the external migration problem of use process small molecular fire retardant.Compared with prior art, which uses
Efficient synergistic fire retardant has better high flame resistance, can also reduce production cost, on the other hand also prevent chlordene ring
The external migration phenomenon of three phosphonitriles and its derivative has good mechanical performance.
Preferred embodiment one, as a kind of improvement of first foundation scheme, polyamide be PA4T, PA46, PA5T, PA6T,
PA66、MXD6、PA9T、PA10T、PXD10、PA11T、PA12T、PPTA、PA6T/6、PA6T/66、PA6T/610、PA6T/6I、
At least one of PA6T/10T, PA10T/12T.Above-mentioned material is nylon, belongs to yield maximum in five large-engineering plastics, uses
The most wide kind in way, is widely applied in industrial application, and it is convenient to obtain, low in cost, has excellent mechanical property, heat-resisting
Property, rub resistance and electrical insulating property, manufactured product high temperature resistance are more preferable.
Preferred embodiment two, as a kind of improvement of first foundation scheme, auxiliary agent is antioxidant, lubricant, carbon forming agent, coupling
At least one of agent.Antioxidant can prevent the thermal oxidative degradation in process, its processing and forming is enable to go on smoothly；Lubrication
Agent can improve the mobility in Raw material processing forming process；Carbon forming agent can generate active carbon and form insulating layer prevention heat transmitting, make
High-temperature resistant result is more preferable；Coupling agent can improve the interface performance of material, improve the processing performance of material.
Preferred embodiment three, as a kind of improvement of first foundation scheme, stabilizer is calcium stearate, magnesium stearate, tristearin
At least one of sour barium, zinc stearate, lead stearate, epoxidized soybean oil, methyl tin, thiol methyl tin.Using these stabilizations
Agent can increase the stability of nylon composite materials, can slow down reaction, keep chemical balance, reduce surface tension, prevent light,
The effects of thermal decomposition or oxygenolysis.
Preferred embodiment four, a preferably improvement any to preferred embodiment three, the granularity of expanded graphite is 80 ~
200 mesh, expansion multiplying power are 230ml/g ~ 300ml/g.The grafting rate of such expanded graphite and hexachlorocyclotriph,sphazene is higher.
Second basic technology scheme of the invention is as follows: a kind of high flame retardant high temperature resistant nylon composite material and its preparation side
Method, comprising the following steps:
One, expanded graphite is dispersed in mixed acid, is ultrasonically treated 2 ~ 4 hours at 60 DEG C, is filtered under diminished pressure, is gone
The expanded graphite of carboxylated is obtained after ionized water and methanol washing, vacuum drying；
Two, the expanded graphite of carboxylated is dispersed in the first solvent, sodium hydride is added, reflux 1 ~ 1.5 is small at 50 DEG C
When；
Three, the first solvent dissolved with 2 ~ 5g hexachlorocyclotriph,sphazene, drop are slowly added dropwise in the solvent after flowing back into step 2
It is reacted 12 ~ 18 hours at 80 DEG C after adding；
Four, the solvent in step 3 is filtered under diminished pressure, chlordene ring is made after deionized water and acetone washing, vacuum drying
Three phosphonitrile graft modification expanded graphites；
Five, by hexachlorocyclotriph,sphazene graft modification expanded graphite obtained and stabilizer, polyamide and auxiliary agent high-speed stirring
It mixes machine to be uniformly mixed, high flame retardant high-temperature nylon composite material can be obtained through double screw extruder granulation.
The advantages of this programme, is: by expanded graphite by mixed acid and ultrasonic treatment carboxylated, making the hexatomic ring knot of graphite
Structure has the group that can be grafted with hexachlorocyclotriph,sphazene, and high-temperature nylon composite material obtained is in addition to hexachlorocyclotriph,sphazene
With expanded graphite outside excellent flame retardant property, since raw material is the common raw material of industry, so that cost is lower, also have good
Mechanical performance, which is simple and efficient, applied widely, is conducive to industrialization promotion and implements.
Preferred embodiment five, as a kind of improvement of the second base case, mixed acid is the mixed acid of perchloric acid and concentrated nitric acid.
Preferred embodiment six, as a kind of improvement of the second base case, mixed acid is the mixed acid of the concentrated sulfuric acid and concentrated nitric acid.
Preferred embodiment seven, as a kind of improvement of the second base case, the Hammett acidity function HO value of mixed acid is less than-
10。
Preferred embodiment eight, preferably five or preferred embodiment six a kind of improvement, the first solvent is dry N, N-
At least one of dimethyl formamide solution, dimethyl sulphoxide solution and N-Methyl pyrrolidone solution.
Specific embodiment
Below by specific embodiment, the present invention is described in further detail, and following embodiment is only applicable to this
Invention is further described, rather than limiting the scope of the invention.
Percentage in following embodiment forms the composition that is weight percentage:
Embodiment 1 in the present embodiment, under ultrasonic wave effect, takes the expanded graphite of 2.0g to be dispersed in 200ml high chlorine
In the mixed acid (Hammett acidity function HO value is less than -10) of acid and concentrated nitric acid, then 60 DEG C of 2 ~ 3h of continual ultrasonic are warming up to, through subtracting
Press filtration, a large amount of deionized waters and methanol repeatedly washs, be dried in vacuo after obtain the expanded graphite of carboxylated.
The expanded graphite for weighing 1.1g carboxylated is dispersed in the dry dimethyl sulphoxide solution of 100ml, is added 0.2g's
Flow back at 50 DEG C 1h after sodium hydride, then 50ml is slowly added dropwise dissolved with the dimethyl sulphoxide solution of 2g hexachlorocyclotriph,sphazene, is added dropwise
After, 80 DEG C are warming up to the reaction was continued 12h, is filtered under diminished pressure, after a large amount of deionized waters and acetone are repeatedly washed, are dried in vacuo
Hexachlorocyclotriph,sphazene graft modification expanded graphite can be obtained, measuring grafting rate is 71.2%.
The hexachlorocyclotriph,sphazene graft modification expanded graphite 25% that will be prepared, PA10T 70%, stabilizer 1.5%, antioxygen
Agent 0.5%, lubricant 1.5%, coupling agent 1.5% are uniformly mixed with high-speed mixer, can be obtained through double screw extruder granulation high
Anti-flammability high-temperature nylon composite material.
After tested, above-mentioned composite material oxygen index (OI) is 32, tensile strength 103Mpa.
Embodiment 2, the present embodiment is the difference from embodiment 1 is that swollen by the hexachlorocyclotriph,sphazene graft modification being prepared
Swollen graphite 25%, PA6T 50%, PA66 20%, stabilizer 1.5%, antioxidant 0.5%, lubricant 1.5%, coupling agent 1.5%, with height
Fast blender is uniformly mixed, and can obtain high flame retardant high-temperature nylon composite material through double screw extruder granulation.
After tested, above-mentioned composite material oxygen index (OI) is 31, tensile strength 92Mpa.
Embodiment 3 in the present embodiment, under ultrasonic wave effect, takes the expanded graphite of 5.0g to be dispersed in the dense sulphur of 400ml
In the mixed acid (Hammett acidity function HO value is less than -9) of acid and concentrated nitric acid, then 60 DEG C of 3 ~ 4h of continual ultrasonic are warming up to, through subtracting
Press filtration, a large amount of deionized waters and ethyl alcohol repeatedly washs, be dried in vacuo after obtain the expanded graphite of carboxylated.
The expanded graphite for weighing 3g carboxylated is dispersed in the dry n,N-Dimethylformamide solution of 200ml, is added
Flow back at 50 DEG C 1.5h after the sodium hydride of 0.5g, then 150ml is slowly added dropwise dissolved with the N of 5g hexachlorocyclotriph,sphazene, N- dimethyl
Formamide solution after being added dropwise, is warming up to 80 DEG C the reaction was continued 18h, be filtered under diminished pressure, a large amount of deionized waters and acetone it is multiple
Hexachlorocyclotriph,sphazene graft modification expanded graphite can be obtained after washing, vacuum drying, measuring grafting rate is 75.7%.
The hexachlorocyclotriph,sphazene graft modification expanded graphite 20% that will be prepared, PA46 75%, stabilizer 1.5%, antioxygen
Agent 0.8%, lubricant 1.5%, coupling agent 1.2% are uniformly mixed with high-speed mixer, can be obtained through double screw extruder granulation high
Anti-flammability high-temperature nylon composite material.
After tested, above-mentioned composite material oxygen index (OI) is 30, tensile strength 86Mpa.
The difference of embodiment 4, the present embodiment and embodiment 3 is only that the hexachlorocyclotriph,sphazene graft modification that will be prepared
Expanded graphite 20%, PA10T/12T 75%, stabilizer 1.5%, antioxidant 0.8%, lubricant 1.5%, coupling agent 1.2%, with high speed
Blender is uniformly mixed, and can obtain high flame retardant high-temperature nylon composite material through double screw extruder granulation.
After tested, above-mentioned composite material oxygen index (OI) is 29, tensile strength 101Mpa.
The difference of embodiment 5, the present embodiment and embodiment 3 is only that the hexachlorocyclotriph,sphazene graft modification that will be prepared
Expanded graphite 18%, MXD6 60%, PPA 17%, stabilizer 1.5%, antioxidant 1.2%, lubricant 1.5%, carbon forming agent 0.8%, with height
Fast blender is uniformly mixed, and can obtain high flame retardant high-temperature nylon composite material through double screw extruder granulation.
After tested, above-mentioned composite material oxygen index (OI) is 27, tensile strength 83Mpa.
What has been described above is only an embodiment of the present invention, and the common sense such as well known specific structure and/or characteristic are herein in scheme
It does not describe excessively.It should be pointed out that for those skilled in the art, without departing from the structure of the invention, also
Several modifications and improvements can be made, these also should be considered as protection scope of the present invention, these all will not influence of the invention real
The effect and patent practicability applied.The scope of protection required by this application should be based on the content of the claims, specification
In the records such as specific embodiment can be used for explaining the content of claim.
Claims (9)
1. a kind of high flame retardant high temperature resistant nylon composite material, which is characterized in that including weight percent be 50~85% it is poly-
Amide, the fire retardant that weight percent is 6~45%, the stabilizer that weight percent is 0.1~2%, weight percent 0.1
~12% auxiliary agent；The fire retardant includes the expanded graphite through the modified grafting of hexachlorocyclotriph,sphazene, hexachlorocyclotriph,sphazene with it is swollen
The molar ratio of swollen graphite is 0.1~10, and the granularity of the expanded graphite is 80~200 mesh, expansion multiplying power be 230ml/g~
300ml/g。
2. high flame retardant high temperature resistant nylon composite material according to claim 1, it is characterised in that: the polyamide is
PA4T、PA46、PA5T、PA6T、PA66、MXD6、PA9T、PA10T、PXD10、PA11T、PA12T、PPTA、PA6T/6、PA6T/
66, at least one of PA6T/610, PA6T/6I, PA6T/10T, PA10T/12T.
3. high flame retardant high temperature resistant nylon composite material according to claim 1, it is characterised in that: the auxiliary agent is antioxygen
At least one of agent, lubricant, carbon forming agent, coupling agent.
4. high flame retardant high temperature resistant nylon composite material according to claim 1, it is characterised in that: the stabilizer is hard
At least one of resin acid calcium, magnesium stearate, barium stearate, zinc stearate, lead stearate, epoxidized soybean oil, thiol methyl tin.
5. a kind of preparation method of high flame retardant high temperature resistant nylon composite material according to any one of claims 1 to 4, including
Following steps:
One, expanded graphite is dispersed in mixed acid, is ultrasonically treated 2~4 hours at 60 DEG C, be filtered under diminished pressure, go from
The expanded graphite of carboxylated is obtained after sub- water and methanol washing, vacuum drying；
Two, the expanded graphite of carboxylated is dispersed in the first solvent, sodium hydride is added, flows back 1~1.5 hour at 50 DEG C；
Three, the first solvent dissolved with 2~5g hexachlorocyclotriph,sphazene is slowly added dropwise in the solvent after flowing back into step 2, drips
It is reacted 12~18 hours at 80 DEG C after finishing；
Four, the solvent in step 3 is filtered under diminished pressure, three phosphorus of chlordene ring is made after deionized water and acetone washing, vacuum drying
Nitrile graft modification expanded graphite；
Five, by hexachlorocyclotriph,sphazene graft modification expanded graphite obtained and stabilizer, polyamide and auxiliary agent high-speed mixer
It is uniformly mixed, high flame retardant high-temperature nylon composite material can be obtained through double screw extruder granulation.
6. the preparation method of high flame retardant high temperature resistant nylon composite material according to claim 5, it is characterised in that: described
Mixed acid is the mixed acid of perchloric acid and concentrated nitric acid.
7. the preparation method of high flame retardant high temperature resistant nylon composite material according to claim 5, it is characterised in that: described
Mixed acid is the mixed acid of the concentrated sulfuric acid and concentrated nitric acid.
8. the preparation method of high flame retardant high temperature resistant nylon composite material according to claim 5, it is characterised in that: described
The Hammett acidity function HO value of mixed acid is less than -10.
9. the preparation method of high flame retardant high temperature resistant nylon composite material according to claim 6 or 7, it is characterised in that:
First solvent is dry N,N-dimethylformamide solution, the dimethyl sulphoxide solution of drying and the N- methyl pyrrole of drying
At least one of pyrrolidone solution.
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| CN102153870A (en) * | 2011-01-24 | 2011-08-17 | 江苏大学 | Method for preparing graphene polyphosphazene nano composite material |
| CN102604372A (en) * | 2012-02-17 | 2012-07-25 | 南京聚隆科技股份有限公司 | Polyamide composite material with flame retardance and heat conduction and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102153870A (en) * | 2011-01-24 | 2011-08-17 | 江苏大学 | Method for preparing graphene polyphosphazene nano composite material |
| CN102604372A (en) * | 2012-02-17 | 2012-07-25 | 南京聚隆科技股份有限公司 | Polyamide composite material with flame retardance and heat conduction and preparation method thereof |
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Denomination of invention: A high flame retardant and high-temperature resistant nylon composite material and its preparation method Effective date of registration: 20231127 Granted publication date: 20190531 Pledgee: Guangdong Qingxin Rural Commercial Bank Co.,Ltd. Taiping Branch Pledgor: GUANGDONG JUHANG INSTITUTE FOR ADVANCED MATERIALS Co.,Ltd. Registration number: Y2023980067643 |