CN115746548A - Flame-retardant polyamide elastomer material and preparation method and application thereof - Google Patents
Flame-retardant polyamide elastomer material and preparation method and application thereof Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 229
- 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 218
- 229920001971 elastomer Polymers 0.000 title claims abstract description 123
- 239000000806 elastomer Substances 0.000 title claims abstract description 123
- 239000004952 Polyamide Substances 0.000 title claims abstract description 108
- 229920002647 polyamide Polymers 0.000 title claims abstract description 108
- 239000000463 material Substances 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 49
- 239000010703 silicon Substances 0.000 claims abstract description 49
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 30
- 239000011574 phosphorus Substances 0.000 claims abstract description 30
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 230000002195 synergetic effect Effects 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims description 70
- 238000002156 mixing Methods 0.000 claims description 46
- 239000007822 coupling agent Substances 0.000 claims description 24
- 229920005989 resin Polymers 0.000 claims description 24
- 239000011347 resin Substances 0.000 claims description 24
- 239000003963 antioxidant agent Substances 0.000 claims description 21
- 230000003078 antioxidant effect Effects 0.000 claims description 21
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 18
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 18
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 18
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 16
- -1 polydimethylsiloxane Polymers 0.000 claims description 14
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 13
- 239000002270 dispersing agent Substances 0.000 claims description 11
- 229910017059 organic montmorillonite Inorganic materials 0.000 claims description 11
- 229960000892 attapulgite Drugs 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 229910052625 palygorskite Inorganic materials 0.000 claims description 10
- 229920001296 polysiloxane Polymers 0.000 claims description 7
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 6
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 6
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 6
- 229920000570 polyether Polymers 0.000 claims description 6
- 229920000734 polysilsesquioxane polymer Polymers 0.000 claims description 6
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 4
- 229920002614 Polyether block amide Polymers 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229920006149 polyester-amide block copolymer Polymers 0.000 claims description 4
- 229920006146 polyetheresteramide block copolymer Polymers 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 claims description 4
- 229920002292 Nylon 6 Polymers 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- VBICKXHEKHSIBG-UHFFFAOYSA-N beta-monoglyceryl stearate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 claims description 3
- 229920001400 block copolymer Polymers 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
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- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 claims description 2
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- YGANSGVIUGARFR-UHFFFAOYSA-N dipotassium dioxosilane oxo(oxoalumanyloxy)alumane oxygen(2-) Chemical compound [O--].[K+].[K+].O=[Si]=O.O=[Al]O[Al]=O YGANSGVIUGARFR-UHFFFAOYSA-N 0.000 claims description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 2
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004898 kneading Methods 0.000 claims description 2
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- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
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- 150000003017 phosphorus Chemical class 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000001993 wax Substances 0.000 claims description 2
- 239000013536 elastomeric material Substances 0.000 claims 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims 1
- 239000005543 nano-size silicon particle Substances 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims 1
- 229920000548 poly(silane) polymer Polymers 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
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- 239000004433 Thermoplastic polyurethane Substances 0.000 description 6
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000004677 Nylon Substances 0.000 description 5
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- 239000010410 layer Substances 0.000 description 5
- 229920001778 nylon Polymers 0.000 description 5
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- 229910052736 halogen Inorganic materials 0.000 description 4
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- 239000000779 smoke Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
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- 125000005375 organosiloxane group Chemical group 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000726103 Atta Species 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
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- 231100000053 low toxicity Toxicity 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 description 1
- 229920001875 Ebonite Polymers 0.000 description 1
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229920006147 copolyamide elastomer Polymers 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
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- 150000002009 diols Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012757 flame retardant agent Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229940075507 glyceryl monostearate Drugs 0.000 description 1
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- 239000001788 mono and diglycerides of fatty acids Substances 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
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- 150000004756 silanes Chemical class 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
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- 230000005641 tunneling Effects 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a flame-retardant polyamide elastomer material, a preparation method and application thereof, wherein the flame-retardant polyamide elastomer material comprises the following components in parts by weight: polyamide elastomer, organic silicon flame retardant, inorganic silicon flame retardant and phosphorus synergistic flame retardant. The flame-retardant polyamide elastomer material disclosed by the invention has excellent mechanical properties and flame retardance, and is suitable for preparing medical equipment cables.
Description
Technical Field
The invention belongs to the field of elastomer composite materials, and particularly relates to a silicon-based flame-retardant polyamide elastomer material, and a preparation method and application thereof.
Background
With the rapid development of the polymer material industry and the improvement of the living demands of people, the development, production and application of the flame retardant and the flame retardant material are rapidly developed. As the requirements on material performance and environmental protection become stricter, the research and development of the halogen-free flame retardant technology with environmental protection, low toxicity, high efficiency and multiple functions are trending.
The existing flame retardants commonly used for high polymer materials are mainly halogen flame retardants and phosphorus flame retardants, which have certain toxicity, are not environment-friendly and damage the mechanical properties of the materials due to strong polarity. Therefore, with the strictness of environmental protection and safety regulations, the research on halogen-free and phosphorus-free flame retardant technology and the development of flame retardants are urgent. The organic silicon flame retardant is a new-generation non-halogen carbon-forming flame retardant which is efficient, eco-friendly, anti-dripping and smoke-suppressing, can improve the processing performance, mechanical performance, heat resistance and the like of a base material, and has excellent recycling effect of a flame-retardant material. Besides endowing the base material with excellent flame retardant performance, other performances of the base material such as processing performance, mechanical performance, heat resistance and the like can be improved by some silicon-containing flame retardants, so that the flame retardant material is ecological-friendly, has good recycling effect, and can meet the strict requirements of people on the flame retardant. The elastomer materials for flame retardance mainly comprise flame-retardant PVC elastomers, flame-retardant TPS, flame-retardant TPV, flame-retardant TPU and other elastomer materials, and the elastomer flame-retardant materials have certain limitations in performance, such as low tensile strength, poor rebound resilience, poor wear resistance and the like, so that a new high-performance, environment-friendly, halogen-free and phosphorus-free flame-retardant elastomer material is needed.
Polyamide elastomer (TPAE), also called thermoplastic polyamide elastomer, is a block copolymer containing polyamide hard segments and aliphatic polyester or polyether soft segments, has the characteristics of low hardness, good flexibility, high tensile strength, good elastic recovery, high low-temperature impact strength, excellent low-temperature resistance and the like, is easy to process, is widely applied to the fields of electronics and electrics, automobile industry, medical instruments, sports goods and the like, and can be used in the fields of medical supplies, medical equipment cables, natural flame retardance and the like by improving the performance of silicon-based flame retardant modification.
Currently, polyamide elastomers are less studied for flame retardancy as substrates. Chinese patent CN114410107A discloses a multi-copolymerization body flame-retardant long carbon chain polyamide composition and a preparation method thereof, wherein cage type polysilsesquioxane with a polyamine group functional group is copolymerized with a long carbon chain polyamide monomer, and a synergistic flame retardant of the flame-retardant long carbon chain polyamide composition can be silsesquioxane. U.S. Pat. No. 5, 10619016B2 discloses a flame-retardant polyamide 12 molding composition for railways, in which long-chain polyamide elastomers are used for railway applications, the coverage is not wide, and the cost is high. European patent EP2047482B1 discloses an insulated wire in electronic equipment and its use, disclosing the flame retardancy of copolyamide elastomers, however, this system is not comprehensive enough in flame retardancy and also not high in performance. In addition, chinese patent CN111234157B discloses a reactive extrusion preparation method of a flame-retardant hyperbranched polyamide 6 elastomer, which requires the re-extrusion of a preformed prepolymer, and has the disadvantages of complex steps, difficult process control and high cost. Chinese patent CN110183649A discloses a phosphorus-containing intrinsic flame-retardant thermoplastic nylon elastomer material and a preparation method thereof, wherein a carboxyl-terminated nylon prepolymer, a hydroxyl-terminated polyether polyol and a phosphorus-containing diol monomer are subjected to melt copolymerization to obtain a nylon elastomer, or the carboxyl-terminated phosphorus-containing nylon prepolymer and the hydroxyl-terminated polyether polyol are subjected to melt copolymerization to obtain the nylon elastomer. The flame-retardant elastomer is polymerized, has low flame-retardant components, general flame-retardant effect, complex process and high cost. Japanese patent publication No. JP63162759A discloses a flame retardant polyamide elastomer composition which achieves chemical resistance and flame retardancy by blending a polyamide elastomer with a compound of polybromophenyl ether and antimony. Chinese patent CN111560166A discloses a halogen-free flame-retardant polyamide elastomer composition and a preparation method thereof, and the system has general compatibility, is easy to absorb moisture and hydrolyze, has low flame-retardant efficiency, and cannot meet the flame-retardant requirement of partial materials. In addition, in the field of silicon flame retardance of polyurethane elastomers, chinese patent CN111363340B provides a halogen-free flame retardant thermoplastic polyurethane elastomer composition and a preparation method thereof, the flame retardant system is a silicon flame retardant, which endows the thermoplastic polyurethane composition with high flame retardant property and high temperature aging resistance, however, the basic mechanical properties of the thermoplastic polyurethane composition are not high compared with those of polyamide elastomers.
At present, the flame retardant performance of the elastomer on the market is realized, the mechanical performance is greatly reduced, the use requirements of certain specific environments are difficult to meet, most of the elastomer is difficult to keep the color of the original resin material unchanged, and in addition, the elastomer is poor in flexibility and high in hardness after being flame retardant, so that the flame retardant material with excellent mechanical performance and flame retardant performance is required.
Disclosure of Invention
Technical problem
In view of the problems in the prior art, the technical object of the present invention is to provide a flame retardant polyamide elastomer material using a polyamide elastomer as a base material and utilizing an organic and inorganic silicon flame retardant system and a phosphorus flame retardant to synergistically retard flame and a preparation method thereof. The flame-retardant polyamide elastomer material has the advantages of low hardness, good flexibility, greenness, no halogen, environmental protection, smoke suppression, good mechanical property and good flame-retardant efficiency.
Technical scheme
In one aspect, the present invention provides a flame retardant polyamide elastomer material comprising: polyamide elastomer, organic silicon flame retardant, inorganic silicon flame retardant and phosphorus synergistic flame retardant.
In a specific embodiment, the flame-retardant polyamide elastomer material further comprises a coupling agent, a dispersing agent and an antioxidant.
In a specific embodiment, the flame retardant polyamide elastomer material comprises:
55 to 90 parts by weight, preferably 65 to 88 parts by weight, of a polyamide elastomer,
3 to 20 parts by weight, preferably 5 to 15 parts by weight of a silicone flame retardant,
2 to 15 parts by weight, preferably 3 to 10 parts by weight of an inorganic silicon-based flame retardant,
1 to 10 parts by weight, preferably 3 to 8 parts by weight of the phosphorus-based synergistic flame retardant,
0.1 to 2 parts by weight, preferably 0.2 to 0.6 part by weight, of a coupling agent,
0.1 to 3 parts by weight, preferably 0.3 to 0.5 part by weight, of a dispersant,
0.1 to 2 parts by weight of antioxidant, preferably 0.5 to 0.7 part by weight.
In a particular embodiment, the polyamide elastomer is one or more of long or short chain polyether block amide (PEBA), polyether ester amide (PEEA) and polyester amide (PEA) block copolymers, preferably nylon 6 type polyether block polyamide elastomers.
In particular embodiments, the silicone-based flame retardant is selected from one or more of an organosiloxane, polyhedral oligomeric silsesquioxane (POSS), and polysilaborane.
In a specific embodiment, the organosiloxane has the structure shown in formula I below:
wherein, X and R 1 Each independently selected from methyl, ethyl, hydroxyl, methylphenyl, amino, epoxy, carboxyl, alcoholic hydroxyl and sulfhydryl, a takes the integer of 0-200, b takes the integer of 0-40, c takes the integer of 0-5The integers a, b and c are not 0 at the same time, and the R/Si range is 1.2-2.
Preferably, the organosiloxane is polydimethylsiloxane.
In a specific embodiment, the cage polysilsesquioxane has the following general formula II structure,
in formula II above, R is selected from the group consisting of C2-C6 alkenyl, amino, epoxy, C1-C10 alkyl, and C6-C12 aryl.
In a specific embodiment, the inorganic silicon-based flame retardant is selected from one or more of muscovite, kaolin, serpentine, organic montmorillonite (OMMT), attapulgite, and nano silica, and is preferably attapulgite.
In a specific embodiment, the phosphorus-based synergistic flame retardant is selected from one or more of ammonium polyphosphate, phosphate ester, phosphite ester, phosphonate ester, organic phosphorus salt and phosphorus heterocyclic compound, preferably ammonium polyphosphate (APP).
In particular embodiments, the coupling agent is selected from the group consisting of silane coupling agents including KH560, KH550, KH570, KH792, and DL602; the titanate coupling agent comprises 201, 101, 105, 311 and TTS, preferably the coupling agent is KH550.
In particular embodiments, the dispersant is selected from: ethylene Bis Stearamide (EBS), glyceryl monostearate, glyceryl tristearate, polyethylene wax, liquid paraffin, metal salts of higher fatty acids, pentaerythritol stearate, preferably ethylene bis stearamide.
In particular embodiments, the antioxidant is selected from: 1098. 168, preferably, the weight ratio of the antioxidant 1098 to the antioxidant 168 is 1:2, or a mixture thereof.
In another aspect, the invention provides a preparation method of the flame-retardant polyamide elastomer material, wherein the method is one or two of the following methods:
the method comprises the following steps:
1) Putting a certain proportion of organic silicon flame retardant, inorganic silicon flame retardant, phosphorus synergistic flame retardant and coupling agent into a high-speed mixer, mixing while heating to 60-120 ℃, and mixing for full reaction to obtain a flame retardant mixture;
2) Adding polyamide elastomer resin, a dispersant and an antioxidant into the flame retardant mixture obtained in the step 1), and continuously mixing;
3) Melting, mixing and granulating the mixed materials in the step 2) in an extruder.
The second method comprises the following steps:
1') putting polyamide elastomer resin, organic silicon flame retardant, inorganic silicon flame retardant, phosphorus synergistic flame retardant, coupling agent, dispersing agent and antioxidant into an internal mixer for banburying to prepare flame-retardant master batch;
2 ') putting the flame-retardant master batch obtained in the step 1') and the polyamide elastomer resin into an extruder for melt mixing and granulation.
In a specific embodiment, in step 3) or 2'), the temperature for melt kneading is 170 to 220 ℃.
In a further aspect, the invention provides the use of the flame retardant polyamide elastomer material in the preparation of a medical article having flame retardant properties.
In a particular embodiment, the medical supply is a medical device cable.
The present inventors completed the present invention based on the following principles: the flame retardant material is a polyamide elastomer flame retardant system consisting of an organic silicon flame retardant, an inorganic silicon flame retardant and a phosphorus synergistic flame retardant. The organic silicon flame retardant is based on a condensed phase flame retardant mechanism, namely, the flame retardant effect is realized by generating a cracked carbon layer and improving the inoxidizability of the carbon layer, after the organic silicon flame retardant is added into the polyamide elastomer material, the organic silicon flame retardant mostly migrates to the surface of the material to form a high molecular gradient material of which the surface is an organic silicon flame retardant enrichment layer, once the material is burnt, an inorganic oxygen-insulating and heat-insulating protective layer which is peculiar to polysiloxane and contains Si bonds and (or) Si-C bonds is generated, so that the escape of combustion decomposition products is prevented, the thermal decomposition of the high molecular material is inhibited, and the purposes of flame retardance, low smoke, low toxicity and the like are achieved. The secondary fire retardant, inorganic silicon fire retardant, is mainly fully mixed with the high polymer in a physical dispersion state, and plays a role in fire retardation through chemical or physical change in a gas phase or condensed phase. When a fire breaks out, the inorganic silicon flame retardant rapidly forms a Si-O-Si network structure, which has oxidation resistance and fire resistance, thereby improving the flame retardancy of the material.
After the phosphorus-based synergistic flame retardant is introduced into the silicon-based flame retardant system, the flame retardant synergistic effect of phosphorus and silicon is formed. At high temperatures, phosphorus contributes to the formation of char, silicon increases the thermal stability of these char layers, and the flame retardant synergy of the phosphorus/silicon elements is further enhanced with siloxanes rather than silanes.
The cage-type framework structure of POSS used in the application enables the POSS to have good dielectric property and optical property, meanwhile, in the toughening aspect, POSS nano particles can stop the development of microcracks and can trigger the rearrangement of silver stripes or shear bands or molecular chains, and the elasticity of a cage can play a role similar to marble; the inorganic core composed of the silicon-oxygen frameworks in Si-O alternate connection can inhibit the chain motion of polymer molecules so as to endow the hybrid material with good thermal stability, mechanical property and flame retardance; the three-dimensional size of POSS is in the range of nanometer scale, is a typical nanometer compound, and has the small-size effect of nanometer particles, the surface and interface effect, the quantum size effect and the macroscopic quantum tunneling effect, so that the POSS has stronger comprehensive performance; meanwhile, POSS can be grafted or polymerized with polymers through reactive R groups, so that chemical bonding effect between the polymers is generated, POSS groups are introduced, uniform dispersion on molecular layers is realized, and the performance of the POSS and the polymers is improved. When the R group is an inert group, such as alkyl, aryl and the like, the compatibility between the POSS nano structure and the polymer can be adjusted.
Advantageous effects
1) The application adopts a silicon-based flame-retardant and phosphorus-based synergistic flame-retardant system, is halogen-free, low-smoke, nontoxic and environment-friendly.
2) The organic silicon flame retardant enables the flame-retardant polyamide elastomer material to have low hardness and good flexibility, and the silicon/phosphorus flame-retardant system has high flame-retardant efficiency and less addition, and can not reduce the mechanical strength of raw materials.
3) The silicone flame retardant elastomer resin has the advantages that the silicone flame retardant is adopted, and the natural color of the elastomer resin can be well maintained.
4) In the application, the traditional plastic and other elastomer materials are abandoned, the polyamide elastomer is used as the base material of the flame retardant material, the polyamide elastomer has strong polarity and good compatibility with the flame retardant, and particularly, the polyether modified silicon flame retardant, or other silicon flame retardants, polysiloxane and the like.
5) The polyamide elastomer has excellent mechanical property, so that the mechanical property, flexibility and low-temperature resistance of the flame-retardant material system are better.
6) The addition of the organic siloxane and the dispersing agent can improve the luster and the leveling effect of the flame retardant material, and reduce the viscosity and the processing difficulty.
Detailed Description
The present invention is described in detail below by way of specific examples, however, the scope of the present invention is not limited thereto.
Important materials and equipment instrument models:
polyamide elastomer: AS1222 cangzhou xuyang chemical company, ltd, the polyamide elastomer was prepared by the following method:
adding 20g of polyethylene glycol with the number average molecular weight of 2000, 80g of caprolactam, 3g of deionized water, 3g of sulfuric acid and 1g of adipic acid into a reactor, heating to 240 ℃ under the protection of nitrogen, and reacting for 1.5 hours under the condition of mechanical stirring at 800 rpm; then the mixture is vacuumized to 40Pa and continuously reacted for 2.5 hours under the mechanical stirring of 800rpm, and then the mixture is extracted by boiling water and dried to obtain the polyamide elastomer resin TPAE6 used in the application.
Cage Polysilsesquioxane (POSS): 9502024 Forsmin technologies (Beijing) Inc
PDMS：PMX-200Dow Corning
Attapulgite (atta.): min-U-Gel 400 USA Ai Difu International mining company, inc. (AMI)
Organic montmorillonite (OMMT): DK2 Zhejiang Feng Hong New materials Co., ltd
Ammonium polyphosphate (APP): CF-APP201, hay chemical corporation 37025
TPU: WHT-8254 Wanhua Chemicals
High mixing machine: HSM-50 Jiangsu Bell machine
A double-screw extruder: HK36 Nanjing Kogya chemical complete sets Co., ltd
An injection molding machine: UN120SM Guangdong Yi dense precision machinery Ltd
Electric heating constant temperature air blast drying cabinet: tister instruments Ltd, 101-3AB Tianjin
Horizontal vertical burning apparatus: CZF-5 Beijing Zhonghang times Instrument and Equipment Co., ltd
Glowing filament tester: ZRS-2 Beijing Zhonghang times Instrument and Equipment Co Ltd
Electronic universal material testing machine: zwick/Roell Z020 Shanghai Z Wei Ke mechanical equipment, inc. pendulum impact tester: zwick/RoellHIT50P Shanghai Yangz Wei Ke mechanical Equipment Limited
Incision instrument: b1120.26.10 Shanghai Zxft Wei Ke machinery Equipment Limited
Shore durometer: TYLX-A Jiangsu Tianyuan test Equipment Co Ltd
Shore durometer: TYLX-D Jiangsu Tianyuan test Equipment Co Ltd
Example 1:
preparing a flame retardant polyamide elastomer material by:
(1) Adding 5 parts by weight of POSS, 4 parts by weight of attapulgite (Atta.), 3 parts by weight of APP and 0.2 part by weight of silane coupling agent KH550 (diluted by alcohol-water solution (volume ratio 1:5)) into a high-speed mixer in a spray form for high-speed mixing, mixing and heating to 80 ℃ to obtain a flame retardant mixture subjected to surface treatment;
(2) Adding 86.8 parts by weight of polyamide elastomer resin (TPAE 6), 0.4 part by weight of EBS and 0.6 part by weight of antioxidant mixture (0.2 part by weight of 1098 and 0.4 part by weight of 168) into the flame retardant mixture subjected to surface treatment, continuing to fully blend for 5 to 8 minutes in a high-speed mixer, and discharging to obtain a flame-retardant polyamide elastomer raw material mixture.
(3) And adding the flame-retardant polyamide elastomer raw material mixture into a flat double extruder, carrying out melt mixing at the temperature of 170-220 ℃, cooling and granulating to obtain the flame-retardant polyamide elastomer material.
Example 2:
preparing a flame-retardant polyamide elastomer material by the following steps:
(1) Adding 8 parts by weight of POSS, 4 parts by weight of attapulgite, 3 parts by weight of APP and 0.2 part by weight of silane coupling agent KH550 coupling agent (diluted as above) into a high-speed mixer in a spray form for high-speed mixing, mixing and heating to 80 ℃ to obtain a flame retardant mixture subjected to surface treatment;
(2) 83.9 parts by weight of polyamide elastomer resin (TPAE 6), 0.3 part by weight of EBS and 0.6 part by weight of antioxidant mixture (0.2 part by weight of 1098 and 0.4 part by weight of 168) are added into the flame retardant mixture after surface treatment, and the mixture is continuously and fully blended for 5 to 8 minutes in a high-speed mixer, and then discharged, so that the flame-retardant polyamide elastomer raw material mixture is obtained.
(3) And adding the flame-retardant polyamide elastomer raw material mixture into a flat double extruder, carrying out melt mixing at the temperature of 170-220 ℃, cooling and granulating to obtain the flame-retardant polyamide elastomer material.
Example 3:
preparing a flame retardant polyamide elastomer material by:
(1) Adding 8 parts by weight of POSS, 10 parts by weight of attapulgite, 8 parts by weight of APP and 0.4 part by weight of silane coupling agent KH550 coupling agent (diluted) into a high-speed mixer in a spray manner for high-speed mixing, mixing and heating to 80 ℃ to obtain a flame retardant mixture subjected to surface treatment;
(2) Adding 72.7 parts by weight of polyamide elastomer resin (TPAE 6), 0.3 part by weight of EBS and 0.6 part by weight of antioxidant mixture (0.2 part by weight of 1098 and 0.4 part by weight of 168) into the flame retardant mixture subjected to surface treatment, continuing to fully blend for 5 to 8 minutes in a high-speed mixer, and discharging to obtain a flame-retardant polyamide elastomer raw material mixture.
(3) And adding the flame-retardant polyamide elastomer raw material mixture into a flat double extruder, carrying out melt mixing at the temperature of 170-220 ℃, cooling and granulating to obtain the flame-retardant polyamide elastomer material.
Example 4:
preparing a flame retardant polyamide elastomer material by:
(1) Adding 15 parts by weight of POSS, 3 parts by weight of organic montmorillonite (OMMT), 4 parts by weight of APP and 0.2 part by weight of silane coupling agent KH550 coupling agent (diluted) into a high-speed mixer in a spray manner for high-speed mixing, mixing and heating to 80 ℃ to obtain a flame retardant mixture subjected to surface treatment;
(2) 76.9 parts by weight of polyamide elastomer resin (TPAE 6), 0.3 part by weight of EBS and 0.6 part by weight of antioxidant mixture (0.2 part by weight of 1098 and 0.4 part by weight of 168) are added into the flame retardant mixture after surface treatment, and the mixture is continuously and fully blended for 5 to 8 minutes in a high-speed mixer, and then discharged, so that the flame-retardant polyamide elastomer raw material mixture is obtained.
(3) And adding the flame-retardant polyamide elastomer raw material mixture into a flat double extruder, carrying out melt mixing at the temperature of 170-220 ℃, cooling and granulating to obtain the flame-retardant polyamide elastomer material.
Example 5:
preparing a flame retardant polyamide elastomer material by:
(1) Adding 8 parts by weight of Polydimethylsiloxane (PDMS), 4 parts by weight of attapulgite, 3 parts by weight of APP and 0.6 part by weight of silane coupling agent KH550 coupling agent (diluted) into a high-speed mixer in a spray manner for high-speed mixing, mixing and heating to 80 ℃ to obtain a surface-treated flame retardant mixture;
(2) Adding 83.4 parts by weight of polyamide elastomer resin (TPAE 6), 0.4 part by weight of EBS and 0.6 part by weight of antioxidant mixture (0.2 part by weight of 1098 and 0.4 part by weight of 168) into the flame retardant mixture subjected to surface treatment, continuing to fully blend for 5 to 8 minutes in a high-speed mixer, and discharging to obtain a flame-retardant polyamide elastomer raw material mixture.
(3) And adding the flame-retardant polyamide elastomer raw material mixture into a flat double extruder, carrying out melt mixing at the temperature of 170-220 ℃, cooling and granulating to obtain the flame-retardant polyamide elastomer material.
Example 6:
preparing a flame retardant polyamide elastomer material by:
(1) Adding 8 parts by weight of PDMS, 5 parts by weight of OMMT, 4 parts by weight of APP and 0.2 part by weight of silane coupling agent KH550 coupling agent (diluted) into a high-speed mixer in a spray form for high-speed mixing, mixing and heating to 80 ℃ to obtain a flame retardant mixture subjected to surface treatment;
(2) Adding 81.9 parts by weight of polyamide elastomer resin (TPAE 6), 0.3 part by weight of EBS and 0.6 part by weight of antioxidant mixture (1098 is 0.2 part by weight and 168 is 0.4 part by weight) into the flame retardant mixture subjected to surface treatment, continuously and fully blending for 5-8 minutes in a high-speed mixer, and discharging to obtain a flame-retardant polyamide elastomer raw material mixture.
(3) And adding the flame-retardant polyamide elastomer raw material mixture into a flat double extruder, carrying out melt mixing at the temperature of 170-220 ℃, cooling and granulating to obtain the flame-retardant polyamide elastomer material.
Comparative example 1:
preparing a flame retardant polyurethane elastomer material by the following steps:
(1) Adding 8 parts by weight of POSS, 4 parts by weight of attapulgite, 3 parts by weight of APP and 0.2 part by weight of silane coupling agent KH550 coupling agent (diluted) into a high-speed mixer in a spray form for high-speed mixing, mixing and heating to 70 ℃ to obtain a flame retardant mixture subjected to surface treatment;
(2) Adding 83.9 parts by weight of polyurethane elastomer resin (TPU), 0.3 part by weight of EBS and 0.6 part by weight of antioxidant mixture (1098 is 0.2 part by weight and 168 is 0.4 part by weight) into the flame retardant mixture subjected to surface treatment, continuously and fully blending for 5-8 minutes in a high-speed mixer, and discharging to obtain a flame-retardant polyurethane elastomer raw material mixture.
(3) And (2) adding the flame-retardant polyurethane elastomer raw material mixture into a flat double extruder, carrying out melting mixing at the temperature of 160-220 ℃, and cooling and granulating to obtain the flame-retardant polyurethane elastomer material.
Comparative example 2:
preparing a flame-retardant polyamide elastomer material by the following steps:
(1) Adding 86.9 parts by weight of polyamide elastomer resin (TPAE 6), 0.3 part by weight of EBS, 0.6 part by weight of antioxidant mixture (1098 is 0.2 part by weight and 168 is 0.4 part by weight), 12 parts by weight of POSS and 0.2 part by weight of silane coupling agent KH550 coupling agent (diluted) into a high-speed mixer in a spray shape for high-speed mixing, mixing and heating to 80 ℃ to obtain a flame retardant mixture subjected to surface treatment;
(2) And adding the flame-retardant polyamide elastomer raw material mixture into a flat double extruder, carrying out melt mixing at the temperature of 170-220 ℃, cooling and granulating to obtain the flame-retardant polyamide elastomer material.
Comparative example 3:
preparing a flame retardant polyamide elastomer material by:
(1) Adding 10 parts by weight of OMMT, 5 parts by weight of APP and 0.4 part by weight of silane coupling agent KH550 coupling agent (diluted) into a high-speed mixer in a spray form for high-speed mixing, mixing and heating to 80 ℃ to obtain a flame retardant mixture subjected to surface treatment;
(2) Adding 83.5 parts by weight of polyamide elastomer resin (TPAE 6), 0.5 part by weight of EBS and 0.6 part by weight of antioxidant mixture (0.2 part by weight of 1098 and 0.4 part by weight of 168) into the flame retardant mixture subjected to surface treatment, continuing to fully blend for 5 to 8 minutes in a high-speed mixer, and discharging to obtain a flame-retardant polyamide elastomer raw material mixture.
(3) And adding the flame-retardant polyamide elastomer raw material mixture into a flat double extruder, carrying out melt mixing at the temperature of 170-220 ℃, cooling and granulating to obtain the flame-retardant polyamide elastomer material.
Comparative example 4:
preparing a flame retardant polyamide elastomer material by:
(1) Adding 6 parts by weight of MCA (melamine cyanurate), 4 parts by weight of PER (pentaerythritol), 15 parts by weight of APP (ammonium polyphosphate) and 0.4 part by weight of silane coupling agent KH550 coupling agent (diluted) into a high-speed mixer in a spray form for high-speed mixing, mixing and heating to 80 ℃ to obtain a flame retardant mixture subjected to surface treatment;
(2) Adding 73 parts by weight of polyamide elastomer resin (TPAE 6), 1 part by weight of EBS and 0.6 part by weight of antioxidant mixture (1098 is 0.2 part by weight and 168 is 0.4 part by weight) into the flame retardant mixture subjected to surface treatment, continuously and fully blending for 5-8 minutes in a high-speed mixer, and discharging to obtain a flame-retardant polyamide elastomer raw material mixture.
(3) And adding the flame-retardant polyamide elastomer raw material mixture into a flat double extruder, carrying out melt mixing at the temperature of 170-220 ℃, cooling and granulating to obtain the flame-retardant polyamide elastomer material.
The specific ingredients and amounts of examples 1-6 and comparative examples 1-4 are summarized in table 1 below.
TABLE 1
Testing mechanical property and flame retardant property:
the flame retardant performance and the mechanical property of the composite materials of the examples 1 to 6 and the comparative examples 1 to 4 are tested, the test results are shown in the following table 2, and the performance evaluation method and the test standard are as follows:
the extruded, pelletized composite was dried at 90 ℃ for 1-2 hours and then test specimens (each set of specimens comprised 5 tensile, impact test specimens and 10 flame retardant test specimens) were molded using an injection molding machine equipped with a standard test specimen mold.
And (3) testing mechanical properties: the tensile properties of the composite were tested using a universal tensile tester according to the ASTM D638-2003 Standard for tensile Properties of plastics, american society for testing materials. Tensile testing was performed on at least 5 replicates per group and the results averaged. The composite material is tested according to the plastic cantilever beam impact standard in ISO180-2001, and each group of impact tests at least guarantees 5 parallel samples, and the average value of the results is taken.
And (3) testing the flame retardant property: the flame retardant property of the flame retardant is tested according to UL94-2006 standard, and the standard of a spline is 125x15x1.6mm.
And (3) hardness testing: according to GB/T2411-2008 & lt & gt hardness of plastic and hard rubber, the test is carried out by using a hardness tester to measure the indentation hardness (Shore hardness), and the size of a sample is phi 50x4mm.
TABLE 2
And (4) conclusion: the results of flame retardant and mechanical tests (table 2 above) show that the flame retardant polyamide elastomer system in examples 1-6 can achieve a flame retardant effect of more than UL94-V1 by adding a small amount of silicon flame retardant and a small amount of phosphorus synergistic flame retardant, and can maintain the low hardness, low smoke, no halogen, environmental protection and excellent mechanical properties of the elastomer material, so that the flame retardant polyamide elastomer material is an ideal flame retardant elastomer material.
In comparative example 1, a polyurethane elastomer commonly used in the market is adopted to prepare the flame retardant material, the flame retardant property is slightly inferior to that of polyamide elastomer resin by the same addition and proportion, the difference between the tensile strength and the flame retardant composite material of the polyamide elastomer base material is larger, the good mechanical property advantage of the polyamide elastomer is shown, and the compatibility between the polyurethane elastomer resin and the silicon flame retardant is relatively poor.
In comparative examples 2 to 4, in the case that the flame retardant system is lack of the inorganic silicon flame retardant, the phosphorus synergistic flame retardant (comparative example 2) and the inorganic silicon flame retardant (comparative example 3), respectively, the flame retardant effect of the system is not ideal, while the other flame retardant system (comparative example 4) has better flame retardant effect but the mechanical property and flexibility of the material are not as good as those of the systems in the examples. In addition, it can also be seen from the values of comparative example 2 that the flame retardant polyamide elastomer material shows inferior mechanical properties in the absence of both inorganic silicon-based flame retardants and phosphorus-based synergistic flame retardants, which also reflects that mixing a polyamide elastomer resin with the specific silicon/phosphorus flame retardant system of the present application results in a flame retardant polyamide elastomer material with improved mechanical properties.
In conclusion, through the selection of the resin base material and the silicon/phosphorus synergistic flame-retardant system, the flame-retardant material disclosed by the application shows excellent balance of flame-retardant performance and mechanical performance, and is green, environment-friendly and low in cost.
Claims (9)
1. A flame retardant polyamide elastomeric material comprising: polyamide elastomer, organic silicon flame retardant, inorganic silicon flame retardant and phosphorus synergistic flame retardant.
2. The flame retardant polyamide elastomer material of claim 1 further comprising a coupling agent, a dispersant and an antioxidant.
3. The flame retardant polyamide elastomeric material of claim 2, comprising:
55 to 90 parts by weight, preferably 65 to 88 parts by weight, of a polyamide elastomer,
3 to 20 parts by weight, preferably 5 to 15 parts by weight of a silicone flame retardant,
2 to 15 parts by weight, preferably 3 to 10 parts by weight of an inorganic silicon-based flame retardant,
1 to 10 parts by weight, preferably 3 to 8 parts by weight of the phosphorus-based synergistic flame retardant,
0.1 to 2 parts by weight, preferably 0.2 to 0.6 part by weight, of a coupling agent,
0.1 to 3 parts by weight, preferably 0.3 to 0.5 part by weight, of a dispersant,
0.1 to 2 parts by weight of an antioxidant, preferably 0.5 to 0.7 part by weight.
4. The flame retardant polyamide elastomer material according to claim 2,
the polyamide elastomer is selected from one or more of long-chain or short-chain polyether block amide (PEBA), polyether ester amide (PEEA) and polyester amide (PEA) block copolymers, and is preferably nylon 6 type polyether block polyamide elastomer; and/or
The organic silicon flame retardant is selected from one or more of organic siloxane, cage type Polysilsesquioxane (POSS) and polysilane, and is preferably polydimethylsiloxane and cage type polysilsesquioxane; and/or
The inorganic silicon flame retardant is selected from one or more of muscovite, kaolin, serpentine, organic montmorillonite (OMMT), attapulgite and nano silicon dioxide, and is preferably attapulgite and organic montmorillonite; and/or
The phosphorus-based synergistic flame retardant is selected from one or more of ammonium polyphosphate (APP), phosphate, phosphite, phosphonate, organic phosphorus salt and a phosphorus heterocyclic compound, and is preferably ammonium polyphosphate; and/or
The coupling agent is selected from silane coupling agents and titanate coupling agents, and the silane coupling agents comprise KH560, KH550, KH570, KH792 and DL602; the titanate coupling agent comprises 201, 101, 105, 311 and TTS, preferably the coupling agent is KH550; and/or
The dispersing agent is selected from one or more of Ethylene Bis Stearamide (EBS), stearic acid monoglyceride, tristearin, polyethylene wax, liquid paraffin, metal salts of higher fatty acid and pentaerythritol stearate, and preferably is ethylene bis stearamide; and/or
The antioxidant is selected from one or two of 1098 and 168, and preferably, the antioxidant is a mixture of 1098 and 168 in a weight ratio of 1:2.
5. A process for preparing a flame retardant polyamide elastomer material according to any of claims 2-4, comprising the steps of:
1) Putting the organic silicon flame retardant, the inorganic silicon flame retardant, the phosphorus synergistic flame retardant and the coupling agent into a high-speed mixer, mixing while heating to 60-120 ℃, and mixing for full reaction to obtain a flame retardant mixture;
2) Adding polyamide elastomer resin, a dispersant and an antioxidant into the flame retardant mixture obtained in the step 1), and continuously mixing;
3) Melting, mixing and granulating the mixed materials in the step 2) in an extruder.
6. A process for the preparation of a flame retardant polyamide elastomer material according to any of claims 2-4, said process comprising the steps of:
1') putting polyamide elastomer resin, organic silicon flame retardant, inorganic silicon flame retardant, phosphorus synergistic flame retardant, coupling agent, dispersing agent and antioxidant into an internal mixer for banburying to prepare flame-retardant master batch;
2 ') putting the flame-retardant master batch obtained in the step 1') and the polyamide elastomer resin into an extruder for melt mixing and granulation.
7. The method according to claim 5 or 6, wherein the temperature of melt-kneading in step 3) and step 2') is 170 to 220 ℃.
8. Use of a flame retardant polyamide elastomer material according to any of claims 1 to 4 for the preparation of a medical article.
9. The use of claim 8, wherein the medical supply is a medical device cable.
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| CN107011654A (en) * | 2017-05-24 | 2017-08-04 | 武汉理工大学 | A kind of halogen-free flameproof enhancing PA6/PBT alloys and preparation method thereof |
| CN109370207A (en) * | 2018-10-24 | 2019-02-22 | 江苏亿超工程塑料有限公司 | A kind of halogen-free flame-retardant polyamide material and preparation method thereof |
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