CN117777544A - Precipitation-resistant halogen-free flame retardant, and preparation method and application thereof - Google Patents
Precipitation-resistant halogen-free flame retardant, and preparation method and application thereof Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 157
- 238000001556 precipitation Methods 0.000 title claims abstract description 52
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 124
- 239000000178 monomer Substances 0.000 claims abstract description 50
- 229920002627 poly(phosphazenes) Polymers 0.000 claims abstract description 49
- 229920000642 polymer Polymers 0.000 claims abstract description 47
- 239000000843 powder Substances 0.000 claims abstract description 38
- 239000004952 Polyamide Substances 0.000 claims abstract description 33
- IEBJFIRFEADIIQ-UHFFFAOYSA-N phosphanylurea Chemical compound NC(=O)NP IEBJFIRFEADIIQ-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229920002647 polyamide Polymers 0.000 claims abstract description 33
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 27
- 238000004132 cross linking Methods 0.000 claims abstract description 19
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000011574 phosphorus Substances 0.000 claims abstract description 17
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 17
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 15
- -1 siloxane compound Chemical class 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000011247 coating layer Substances 0.000 claims abstract description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 11
- 125000003277 amino group Chemical group 0.000 claims abstract description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 9
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 6
- 239000003085 diluting agent Substances 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 23
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- 238000005507 spraying Methods 0.000 claims description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 125000005499 phosphonyl group Chemical group 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 8
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims description 8
- HJJOHHHEKFECQI-UHFFFAOYSA-N aluminum;phosphite Chemical compound [Al+3].[O-]P([O-])[O-] HJJOHHHEKFECQI-UHFFFAOYSA-N 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 7
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 7
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- 238000007865 diluting Methods 0.000 claims description 5
- 125000000524 functional group Chemical group 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
- 239000007921 spray Substances 0.000 claims description 5
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical group C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 3
- MFIBZDZRPYQXOM-UHFFFAOYSA-N [dimethyl-[3-(oxiran-2-ylmethoxy)propyl]silyl]oxy-dimethyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical group C1OC1COCCC[Si](C)(C)O[Si](C)(C)CCCOCC1CO1 MFIBZDZRPYQXOM-UHFFFAOYSA-N 0.000 claims description 3
- 150000001555 benzenes Chemical group 0.000 claims description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N deuterated chloroform Substances [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 claims description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical group CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- WZJUBBHODHNQPW-UHFFFAOYSA-N 2,4,6,8-tetramethyl-1,3,5,7,2$l^{3},4$l^{3},6$l^{3},8$l^{3}-tetraoxatetrasilocane Chemical group C[Si]1O[Si](C)O[Si](C)O[Si](C)O1 WZJUBBHODHNQPW-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- KTLIMPGQZDZPSB-UHFFFAOYSA-M diethylphosphinate Chemical compound CCP([O-])(=O)CC KTLIMPGQZDZPSB-UHFFFAOYSA-M 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 claims 1
- REBHQKBZDKXDMN-UHFFFAOYSA-M [PH2]([O-])=O.C(C)[Al+]CC Chemical compound [PH2]([O-])=O.C(C)[Al+]CC REBHQKBZDKXDMN-UHFFFAOYSA-M 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 10
- 239000001301 oxygen Substances 0.000 abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 abstract description 10
- XSAOTYCWGCRGCP-UHFFFAOYSA-K aluminum;diethylphosphinate Chemical compound [Al+3].CCP([O-])(=O)CC.CCP([O-])(=O)CC.CCP([O-])(=O)CC XSAOTYCWGCRGCP-UHFFFAOYSA-K 0.000 description 31
- 239000000463 material Substances 0.000 description 17
- 229920006351 engineering plastic Polymers 0.000 description 14
- 239000000203 mixture Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 7
- 239000011258 core-shell material Substances 0.000 description 6
- 229920002302 Nylon 6,6 Polymers 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 description 4
- 239000007822 coupling agent Substances 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920006122 polyamide resin Polymers 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 230000001808 coupling effect Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 229920001709 polysilazane Chemical group 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- CWNOEVURTVLUNV-UHFFFAOYSA-N 2-(propoxymethyl)oxirane Chemical compound CCCOCC1CO1 CWNOEVURTVLUNV-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229920001688 coating polymer Polymers 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 229920000891 common polymer Polymers 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- DDJSWKLBKSLAAZ-UHFFFAOYSA-N cyclotetrasiloxane Chemical compound O1[SiH2]O[SiH2]O[SiH2]O[SiH2]1 DDJSWKLBKSLAAZ-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- IBDMRHDXAQZJAP-UHFFFAOYSA-N dichlorophosphorylbenzene Chemical compound ClP(Cl)(=O)C1=CC=CC=C1 IBDMRHDXAQZJAP-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
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- 239000007924 injection Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- BLTAPEIEHGWKKN-UHFFFAOYSA-N methanesulfonate;pyridin-1-ium Chemical compound CS(O)(=O)=O.C1=CC=NC=C1 BLTAPEIEHGWKKN-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention discloses an anti-precipitation halogen-free flame retardant, a preparation method and application thereof. The flame retardant comprises flame retardant powder and a coating layer coated on the flame retardant powder, wherein the flame retardant powder comprises a phosphorus-containing flame retardant, the coating layer comprises polyphosphazene, the polyphosphazene is prepared by a cross-linking reaction of a phosphino-urea polymer and a cross-linking agent, the phosphino-urea polymer is prepared by polycondensation of a phosphono-dichloro monomer and a diamino monomer, and the phosphono-dichloro monomer has a structure of formula (I):wherein,R 1 the diamino monomer comprises benzene ring, two amino groups are connected with the benzene ring and also comprise more than 1 hydroxyl or carboxyl, the cross-linking agent is siloxane compound and has more than 2 epoxy groups or amino groups. When the flame retardant is used for polyamide, the oxygen index can reach more than 37%, the mechanical strength and the heat resistance are obviously improved, the flame retardant can be used in the field of rail transit application, and the flame retardant is not precipitated.
Description
Technical Field
The invention relates to an anti-precipitation halogen-free flame retardant, a preparation method and application thereof.
Background
The polyamide engineering plastic has excellent properties, and has wide application in the field of high polymer materials, a halogen-free flame retardant composition is usually added into the polyamide engineering plastic material to improve the flame retardant property of the polyamide engineering plastic material, the halogen-free flame retardant composition is usually prepared by mixing a halogen-free flame retardant and other auxiliary agents through a certain processing technology, the halogen-free flame retardant is usually a composite flame retardant system consisting of Aluminum Diethylphosphinate (ADP), aluminum phosphite or melamine polyphosphate (MPP) and the like, and the halogen-free flame retardant composition can obviously improve the flame retardant property of the polyamide engineering plastic material. However, when using such flame retardant components, firstly, the existing polyamide engineering plastic materials generally have a certain precipitation phenomenon of the flame retardant composition, which results in the influence on the appearance of the engineering plastic materials, such as coloring; secondly, one of the flame retardant indexes of the material, such as oxygen index, is generally 30% -33%, and the flame retardant degree is difficult to be used in the application fields of rail transit and the like (the oxygen index of products required by interior parts of rail transit, high-speed rail carriages and the like is generally more than 35%); again, the use of such flame retardants can make the mechanical strength of polyamide engineering plastic materials not high enough; finally, when glass fibers are added to the engineering plastic material, the processing temperature of the engineering plastic material is increased, the heat resistance requirement of the engineering plastic material is increased, and the heat resistance of the engineering plastic material is insufficient.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention provides an anti-precipitation halogen-free flame retardant, which can lead the oxygen index to reach more than 37 percent when being used for polyamide engineering plastics, obviously improve the mechanical strength and the heat resistance and can be used for high-requirement application fields such as rail transit and the like.
In order to achieve the above purpose, the invention adopts the following technical scheme:
an anti-precipitation halogen-free flame retardant comprises flame retardant powder and a coating layer coated on the flame retardant powder, wherein the flame retardant powder comprises a phosphorus-containing flame retardant, the coating layer comprises polyphosphazene, the polyphosphazene is prepared by a cross-linking reaction of a phosphino-urea polymer and a cross-linking agent, and the phosphino-urea polymer is prepared by polycondensation of a phosphono-dichloro monomer and a diamino monomer
Obtaining; the phosphonyl dichloride monomer has the structure of formula (I): i, wherein R is 1 Selected from the group consisting of C1-6 alkyl, C1-6 alkoxy, a benzene ring substituted with C1-6 alkoxy; the diamino monomer contains benzene ring, two amino groups are connected with the benzene ring, the diamino monomer also contains more than 1 hydroxyl or carboxyl functional group, the cross-linking agent is siloxane compound, and the siloxane compound has more than 2 epoxy groups or amino groups。
In the present invention, the phosphino-urea polymer means a polymer having a main chain containing phosphino-urea groups (structure) Is a polymer of (a).
In some embodiments, the anti-precipitation halogen-free flame retardant comprises 92 to 99.5 percent of flame retardant powder and 0.5 to 8 percent of polyphosphazene in percentage by mass.
In some embodiments, the polyphosphazene has a number average molecular weight of 0.5 to 3.5 ten thousand.
In some embodiments, the molar ratio of the phosphonodichloride monomer to the diamino monomer is from 10:1 to 1:1.
In some embodiments, the mass ratio of the phosphino urea polymer to the crosslinker is from 1:2 to 1:6.
In some embodiments, R 1 Selected from the group consisting of C1-4 alkyl, C1-2 alkoxy, benzene ring substituted with methoxy.
In some embodiments, the diamino monomer has the structure of formula (II):wherein R is 2 Is hydroxyl or carboxyl, m is 1,2,3 or 4. When m is 2,3 or 4, each R 2 The substituents are independent of each other and can be simultaneously hydroxyl or carboxyl, or respectively carboxyl or hydroxyl.
In some embodiments, the cross-linking agent is selected from the group consisting of polydimethylsiloxanes terminated at both ends with glycidyl ethers, 1, 3-bis (3-glycidoxypropyl) tetramethyldisiloxane, 1,3,5, 7-tetramethylcyclotetrasiloxane substituted with 2 or 3 or 4 substituents which areWherein p is 1,2,3,4,5 or 6, q is 1,2 or 3, R 3 Is epoxy or amino.
In some embodiments, the phosphonyl dichloride monomer is selected from the following structures:
in some embodiments, the diamino monomer is selected from the following structures:
in some embodiments, the crosslinking agent is selected from the following structures:
wherein n is such that the molecular weight of the polydimethylsiloxane is from 1 to 2 ten thousand.
The inventor of the application finds that the phosphonyl dichloride monomer and the diamino monomer are adopted to carry out polycondensation to synthesize the phosphino-urea polymer, the main chain of the polymer contains phosphorus and nitrogen atoms, the flame retardant property is good, at least the diamino monomer contains a benzene ring structure, so that the heat resistance of the polymer is good, then the siloxane compound cross-linking agent is adopted to carry out cross-linking on the phosphino-urea polymer, the two cross-linking are realized through the reaction of hydroxyl or carboxyl functional groups in the diamino monomer and epoxy groups or amino groups in the cross-linking agent, and simultaneously, the siloxane structure is introduced during cross-linking, so that the finally obtained polyphosphazene contains flame retardant phosphorus, nitrogen and silicon elements, and the flame retardant property of the polyphosphazene is further improved. When the modified flame retardant is used for polyamide engineering plastics, the flame retardant property and the mechanical strength of the modified flame retardant can be improved, so that the polyamide material can be used in the field of rail transit, and meanwhile, the precipitation resistance of the modified flame retardant is obviously improved, and the modified flame retardant cannot be precipitated in the polyamide material.
The anti-precipitation halogen-free flame retardant provided by the invention takes flame retardant powder as a core, and polyphosphazene polymer as a shell, and has a core-shell structure. The polyphosphazene can generate a crosslinking reaction at high temperature, so that the thermal stability of the flame retardant with the core-shell structure and modified coating can be improved, and meanwhile, the flame retardant contains flame retardant elements such as phosphorus, silicon, nitrogen and the like, and has good synergistic flame retardant effect with the phosphorus-containing flame retardant such as ADP and the like. In addition, the main chain (or the side chain) of the polyphosphazene contains a certain number of amino and other active groups, the active groups can react with the polyamide resin chemically, a bridging or coupling effect can be generated between the flame retardant and the polyamide material, the interface compatibility of the flame retardant and the polyamide matrix is improved, the improvement of the mechanical property of the flame retardant polyamide is facilitated, and the flame retardant can be prevented or reduced.
In some embodiments, the phosphorus-containing flame retardant is selected from the group consisting of one or more of aluminum diethylphosphinate, aluminum tripolyphosphate, and aluminum phosphite.
In some embodiments, the flame retardant powder further comprises zinc borate.
In some embodiments, the flame retardant powder comprises a mass ratio of 5 to 20:0-10:0-15:0-5 of diethyl phosphinate aluminum, aluminum phosphite, aluminum tripolyphosphate and anhydrous zinc borate.
The invention also provides a preparation method of the precipitation-resistant halogen-free flame retardant, which comprises the step of coating the flame retardant powder with the polyphosphazene to prepare the coating layer.
In some embodiments, the preparation method comprises diluting the polyphosphazene with a diluent to obtain a diluent; and mixing the diluent with flame retardant powder in a spray form to obtain the precipitation-resistant halogen-free flame retardant. The polyphosphazene is a polymer with a cross-linked and solidified structure, is in a high-viscosity liquid state, and is favorable for smooth spraying after being diluted. The modified flame retardant powder with the core-shell structure is formed by mixing the modified flame retardant powder with the flame retardant powder in a spray mode so that the modified flame retardant powder can be smoothly coated on the surface of the flame retardant powder.
In some embodiments, the diluent is selected from butyl acetate or ethyl acetate.
In some embodiments, the mass ratio of the diluent to polyphosphazene is from 0.5 to 1:1.
in some embodiments, the method of making comprises the steps of: 1) Diluting the polyphosphazene by adopting a diluent to obtain a diluent; 2) Spraying the diluent into the flame retardant powder, and mixing the diluent and the flame retardant powder to obtain the precipitation-resistant halogen-free flame retardant.
In some embodiments, the spraying is for a period of 2-5 minutes.
In some embodiments, the mixing is performed in a high speed mixer with a stirring speed of 600 to 1200r/min.
In some embodiments, the temperature of the mixing is 120 to 160 ℃.
In some embodiments, the mixing is for a period of 30 to 60 minutes.
In some embodiments, the method further comprises the steps of polycondensing the phosphono-dichloro monomer with a diamino monomer to produce the phosphino-urea polymer, and cross-linking the phosphino-urea polymer with a cross-linking agent to produce the polyphosphazene.
In some embodiments, the polycondensation is performed at a temperature of-10 to 35 ℃. By performing the polycondensation at the lower temperature, the phosphonyl dichloride monomer can be more easily polycondensed with diamino on the diamino monomer to form a phosphino urea polymer with a phosphino urea group on the main chain, and the side reaction degree of the phosphonyl dichloride monomer and hydroxyl or carboxyl on the diamino monomer can be controlled to be minimum.
The polycondensation reaction formula of the above two monomers can be, for example, as follows:
in some embodiments, the polycondensation is performed in a solvent selected from one or more of acetonitrile, N Dimethylformamide (DMF), tetrahydrofuran, ethanol, methanol, isopropanol, toluene, xylene, diethyl ether, ethyl acetate, acetone, dimethylsulfoxide (DMSO), deuterated chloroform, dichloromethane, cyclohexane, 1, 4-dioxane, pyridine.
In some embodiments, the crosslinking reaction includes the step of heating at 60-100 ℃ for 30-180 minutes, 80-150 ℃ for 30-120 minutes, 100-200 ℃ for 15-150 minutes. If the phosphino-urea polymer is crosslinked and cured by a direct one-step temperature rising method, the crosslinking and curing degree of the phosphino-urea polymer is difficult to control, so that the molecular weight of the phosphino-urea polymer is uncontrollable, and the stepped temperature programming is adopted, so that the curing rate can be slowed down, the curing degree of the phosphino-urea polymer is better controlled, and the molecular weight of the final coating layer polyphosphazene is better controlled.
In some embodiments, the cross-linking reaction is performed by dropping the phosphino urea polymer into the cross-linking agent.
Further, the phosphino-urea polymer is added dropwise to the crosslinking agent in the form of a solution. The solvent of the solution may be the same as that of the polymerization reaction. The polymer solution obtained after the polycondensation reaction can also be directly added into the crosslinking agent in a dropwise manner.
The invention also provides application of the precipitation-resistant halogen-free flame retardant to polyamide.
The polyamide may be any of the conventional polyamides, preferably the polyamide is polyamide 66.
The invention also provides a flame-retardant polyamide composition, which comprises polyamide and the anti-precipitation halogen-free flame retardant. Due to the addition of the anti-precipitation halogen-free flame retardant, the composition has obviously improved flame retardant performance, especially oxygen index, heat resistance and mechanical strength, and the flame retardant is free from precipitation.
Further, the flame retardant polyamide composition comprises, by weight, 30-75 parts of polyamide 66, 5-40 parts of reinforcing agent, 0-10 parts of lubricant, 0-5 parts of coupling agent and 5-30 parts of the anti-precipitation halogen-free flame retardant.
Further, the reinforcing agent may be glass fiber.
Further, the lubricant may be an ethylene hard fatty acid amide.
Further, the coupling agent may be a silane coupling agent, preferably KH550.
Compared with the prior art, the invention has the following advantages:
the invention firstly adopts phosphonyl dichloride monomer and diamino monomer to carry out polycondensation to synthesize a phosphino urea polymer, the main chain of the polymer contains phosphorus and nitrogen atoms, the flame retardant property is better, at least the diamino monomer contains benzene ring structure, so that the heat resistance of the polymer is better, then adopts siloxane compound cross-linking agent to carry out cross-linking on the phosphino urea polymer, the two cross-linking agents react with epoxy groups or amino groups in the cross-linking agent through hydroxyl or carboxyl functional groups in the diamino monomer, and simultaneously, the siloxane structure is introduced during cross-linking, so that the finally obtained polyphosphazene contains flame retardant phosphorus, nitrogen and silicon elements. The polyphosphazene is used as a coating layer of flame retardant powder such as a phosphorus-containing flame retardant, so that the precipitation-resistant halogen-free flame retardant takes the flame retardant powder as a core, and the polyphosphazene polymer as a shell, and has a core-shell structure. The shell can effectively prevent flame retardant powder such as ADP and the like from migrating to the surface of the polyamide product, and improves the precipitation resistance of the modified flame retardant. The polyphosphazene can generate a crosslinking reaction at high temperature, so that the thermal stability of the flame retardant with the core-shell structure and modified coating can be improved, and meanwhile, the flame retardant contains flame retardant elements such as phosphorus, silicon, nitrogen and the like, and has good synergistic flame retardant effect with the phosphorus-containing flame retardant. In addition, the main chain (or the side chain) of the polyphosphazene contains a certain number of amino and other active groups, the active groups can react with the polyamide resin chemically, a bridging or coupling effect can be generated between the flame retardant and the polyamide material, the interface compatibility of the flame retardant and the polyamide matrix is improved, the improvement of the mechanical property of the flame retardant polyamide is facilitated, and the flame retardant can be prevented or reduced.
When the anti-precipitation halogen-free flame retardant is used for polyamide engineering plastics, the oxygen index of the flame retardant can reach more than 37%, the mechanical strength and the heat resistance of the flame retardant are obviously improved, the flame retardant can be used in the high-requirement application fields of rail transit and the like, and meanwhile, the flame retardant is free from precipitation in polyamide. All the properties of the flame retardant are obviously superior to those of the common phosphorus-containing flame retardant or the common polymer-coated flame retardant in the prior art.
Drawings
FIG. 1 is an SEM image of the uncoated aluminum diethyl phosphinate ADP of example 1;
fig. 2 is an SEM image of the aluminum diethylphosphinate ADP coating in example 1.
Detailed Description
The invention provides an anti-precipitation halogen-free flame retardant, which is mainly characterized in that a flame retardant powder is coated with a polyphosphazene polymer, and the polymer is synthesized by the following steps: firstly, a phosphonyl dichloride monomer and a diamino monomer are adopted for polycondensation to synthesize a phosphino-urea polymer, then a siloxane compound cross-linking agent is adopted to cross-link the phosphino-urea polymer, and the two are reacted with epoxy groups or amino groups in the cross-linking agent through hydroxyl or carboxyl functional groups in the diamino monomer to realize cross-linking. The polyphosphazene polymer contains flame-retardant phosphorus, nitrogen and silicon elements, and the main chain (or a side chain) contains a certain number of amino and other active groups, and the active groups can react with polyamide resin chemically and can play a part of a coupling agent at the same time. When the flame retardant is adopted, the oxygen index, the mechanical property and the thermal stability of the polyamide are obviously improved, and the flame retardant cannot be separated out.
The invention further innovates a process for preparing the anti-precipitation halogen-free flame retardant, wherein the flame retardant is prepared in a spray mode, the polyphosphazene is diluted by adopting a diluent to obtain a diluent, and the diluent is mixed with flame retardant powder in a spray mode, so that the polyphosphazene can be better coated outside the flame retardant powder to form the anti-precipitation halogen-free flame retardant with a core-shell structure.
The invention is further described below with reference to examples. The present invention is not limited to the following examples. The implementation conditions adopted in the embodiments can be further adjusted according to different requirements of specific use, and the implementation conditions which are not noted are conventional conditions in the industry. The technical features of the various embodiments of the present invention may be combined with each other as long as they do not collide with each other.
Example 1
The embodiment provides an anti-precipitation flame retardant, which is prepared by the following steps:
1) First, a coating polymer was prepared, the reaction formula was as follows:
1.25mol of 2, 5-diamino-1, 4-dihydroxybenzene dihydrochloride (purchased from Aba Ding Shiji) and 5.34mol of phenylphosphonic dichloride were dissolved in acetonitrile, the temperature was controlled to be 2-3 ℃, and the two were subjected to a low temperature polycondensation reaction to obtain an acetonitrile solution of a phosphino urea polymer (containing 1200g of the phosphino urea polymer).
Part of the acetonitrile solution of the above-mentioned phosphino-urea polymer (containing 750g of the phosphino-urea polymer) was slowly dropped into 2250g of a siloxane-based compound (2, 4,6, 8-tetramethyl-2, 4,6, 8-tetra (propylglycidyl ether) cyclotetrasiloxane) (having the structural formulaPurchased from Aba Ding Shiji), after the dripping is finished, rapidly stirring for 30 minutes, vacuum defoaming, heating in an oven at 60 ℃ for 30 minutes, heating at 80 ℃ for 30 minutes, heating at 100 ℃ for 15 minutes, and curing and crosslinking to obtain the polyphosphazene with the number average molecular weight of 1.6-2.0 ten thousand.
2) Preparation of precipitation-resistant flame retardant
49Kg of aluminum diethylphosphinate ADP (SEM image of which is shown in FIG. 1) was weighed and poured into a high-speed mixer, and the stirring speed of the high-speed mixer was set to 900r/min. Diluting 1Kg of polyphosphazene by adopting a diluent butyl acetate, wherein the mass ratio of the diluent to the polyphosphazene is 0.7:1, obtaining polyphosphazene diluent, spraying the polyphosphazene diluent into a stirring high-speed mixer in a spraying mode, controlling the spraying time to be 4min, and controlling the mixing temperature in the high-speed mixer to be 150 ℃ and the mixing time to be 50min. After mixing, the polyphosphazene is uniformly coated on the surface of the aluminum diethylphosphinate particles to form a coating layer, and finally the anti-precipitation flame retardant is obtained, and an SEM (scanning electron microscope) diagram is shown in figure 2, so that the polyphosphazene is uniformly coated on the surface of the aluminum diethylphosphinate particles, and a layer of compact polymer shell is formed on the surface of ADP powder. As can be seen from fig. 1, the morphology of the uncoated ADP particles is an aggregate consisting of a certain cubic crystal. As can be seen from fig. 2, the treated coated ADP surface forms a coating shell formed from polyphosphazene.
Example 2
This example provides an anti-precipitation flame retardant, which is prepared in the same manner as in example 1, except that: in step 2), aluminum diethylphosphinate ADP was replaced with 48Kg and polyphosphazene was replaced with 2Kg.
Example 3
This example provides an anti-precipitation flame retardant, which is prepared in the same manner as in example 1, except that: in step 2), 49Kg of aluminum diethylphosphinate ADP was replaced with a mixture of 38Kg of aluminum diethylphosphinate and 9.5Kg of aluminum phosphite, and polysilazane was replaced with 2.5Kg.
Example 4
This example provides an anti-precipitation flame retardant, which is prepared in the same manner as in example 1, except that: in step 2), 49Kg of aluminum diethylphosphinate ADP was replaced with a mixture of 43Kg of aluminum diethylphosphinate and 4.5Kg of aluminum tripolyphosphate, and polysilazane was replaced with 2.5Kg.
Example 5
This example provides an anti-precipitation flame retardant, which is prepared in the same manner as in example 1, except that: in step 2), 49Kg of aluminum diethylphosphinate ADP was replaced with a mixture of 43Kg of aluminum diethylphosphinate and 3.5Kg of aluminum tripolyphosphate, and polyphosphazene was replaced with 3.5Kg.
Example 6
This example provides an anti-precipitation flame retardant, which is prepared in the same manner as in example 1, except that: in step 2), 49Kg of aluminum diethylphosphinate ADP was replaced with a mixture of 42Kg of aluminum diethylphosphinate and 5.5Kg of anhydrous zinc borate, and polyphosphazene was replaced with 2.5Kg.
Example 7
This example provides an anti-precipitation flame retardant, which is prepared in the same manner as in example 1, except that: in step 2), 49Kg of aluminum diethylphosphinate ADP was replaced with a mixture of 42Kg of aluminum diethylphosphinate and 4.5Kg of anhydrous zinc borate, and polyphosphazene was replaced with 3.5Kg.
Example 8
This example provides an anti-precipitation flame retardant, which is prepared in the same manner as in example 1, except that: in step 1), the diamino monomer is replaced bySubstitution of phosphonyl dichloride monomersThe cross-linking agent is replaced by polydimethyl siloxane with both ends blocked by glycidyl ether, and the structural formula is +.>Wherein n is such that the molecular weight of the polymer is from 1 to 2 ten thousand.
Example 9
This example provides an anti-precipitation flame retardant, which is prepared in the same manner as in example 1, except that: in step 1), the diamino monomer is replaced bySubstitution of phosphonodichloride monomer with +.>The cross-linking agent is replaced by polydimethyl siloxane with both ends blocked by glycidyl ether, and the structural formula isWherein n is such that the molecular weight of the polymer is from 1 to 2 ten thousand.
Example 10
This example provides an anti-precipitation flame retardant, which is prepared in the same manner as in example 1, except that: in step 1), the diamino monomer is replaced bySubstitution of phosphonodichloride monomer with +.>The cross-linking agent is replaced by 1, 3-bis (3-glycidoxypropyl) tetramethyl disiloxane
Comparative example 1
49Kg of aluminum diethyl phosphinate ADP was weighed and poured into a high-speed mixer, and the stirring paddle rotation speed of the high-speed mixer was set to 900r/min. 1Kg of polydiallyl dimethyl ammonium chloride is dissolved in 1Kg of water to obtain a solution, the solution is sprayed into a stirring high-speed mixer in a spraying mode, the spraying time is controlled to be 4min, the mixing temperature in the high-speed mixer is 150 ℃, and the mixing time is 50min, so that the flame retardant is obtained.
Comparative example 2
38Kg of aluminum diethylphosphinate ADP, 9.5Kg of aluminum phosphite and 2.5Kg of vinyl-terminated dimethylpolysiloxane (with the number average molecular weight of 28000) are weighed, poured into a high-speed mixer, the rotation speed of a stirring paddle of the high-speed mixer is controlled to be 900r/min, the mixing temperature in the high-speed mixer is 150 ℃, and the mixing time is 50min, so that the flame retardant is obtained.
Comparative example 3
38Kg of aluminum diethylphosphinate ADP and 9.5Kg of aluminum tripolyphosphate were weighed out and poured into a high-speed mixer, and the rotation speed of a stirring paddle of the high-speed mixer was controlled to be 900r/min. 2.5Kg of polydiallyl dimethyl ammonium chloride is dissolved in 2.5Kg of water to obtain a solution, the solution is sprayed into a stirring high-speed mixer in a spraying mode, the spraying time is controlled to be 4min, the mixing temperature in the high-speed mixer is 150 ℃, and the mixing time is 50min, so that the flame retardant is obtained.
Comparative example 4
42Kg of aluminum diethyl phosphinate ADP, 5.5Kg of anhydrous zinc borate, 2Kg of vinyl-terminated dimethylpolysiloxane (with the number average molecular weight of 28000) and 0.5Kg of polydiallyl dimethyl ammonium chloride are weighed, firstly, the aluminum diethyl phosphinate ADP, the anhydrous zinc borate and the vinyl-terminated dimethylpolysiloxane are poured into a high-speed mixer, the rotation speed of a stirring paddle of the high-speed mixer is controlled to be 900r/min, then 0.5Kg of polydiallyl dimethyl ammonium chloride is dissolved in 0.5Kg of water to obtain a solution, the solution is sprayed into the stirred high-speed mixer in a spraying mode, the mixing temperature in the high-speed mixer is 150 ℃, and the mixing time is 50min, so that the flame retardant is obtained.
The flame retardants of the above examples and comparative examples were tested for thermal weight loss performance using the GB/T36065-2018 standard, and the results are shown in Table 1 below:
table 1 thermal weight loss properties of flame retardants of examples and comparative examples
The flame retardants of the above examples and comparative examples were used in polyamides, and the specific procedure is as follows: 18 parts of each flame retardant, 51.3 parts of polyamide 66, 0.4 part of ethylene hard fatty acid amide (EBS), 0.3 part of silane coupling agent (KH 550) and 30 parts of long glass fiber are mixed by weight, and the mixture is granulated by a double-screw extrusion granulator to obtain a flame-retardant PA66 material, and a standard sample is injection molded, and the tensile strength, impact strength, bending strength, vertical combustibility, oxygen index and precipitation resistance of the flame-retardant PA66 material are tested according to national standards. Wherein the tensile strength is tested according to GB/T1040.2 2006; flexural strength was tested according to GB/T9341-2008; oxygen index was measured according to GB/T2406.2 2009; vertical burn was tested according to GB/T2408 2008 and resistance to precipitation was tested according to GB/T2423.3-2006 test Cab constant wet heat. The results are shown in Table 2 below.
Table 2 properties of the flame retardants of examples, comparative examples for use in polyamides
Therefore, the invention adopts specific polyphosphazene to coat and modify the flame retardant powder containing the phosphorus flame retardant, when the modified flame retardant is used for polyamide, the mechanical property, heat resistance and oxygen index of the flame retardant can be obviously improved, and the flame retardant cannot be separated out from the polyamide.
The above embodiments are provided to illustrate the technical concept and features of the present invention and are intended to enable those skilled in the art to understand the content of the present invention and implement the same, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
Claims (16)
1. An anti-precipitation halogen-free flame retardant comprises flame retardant powder and a coating layer coated on the flame retardant powder, wherein the flame retardant powder comprises a flame retardant core, a flame retardant coating layer and a flame retardant coating layerThe flame retardant powder comprises a phosphorus-containing flame retardant and is characterized in that: the coating layer comprises polyphosphazene, wherein the polyphosphazene is prepared by a cross-linking reaction of a phosphino-urea polymer and a cross-linking agent, and the phosphino-urea polymer is prepared by polycondensation of a phosphono-dichloro monomer and a diamino monomer; the phosphonyl dichloride monomer has the structure of formula (I):
wherein R is 1 Selected from the group consisting of C1-6 alkyl, C1-6 alkoxy, a benzene ring substituted with C1-6 alkoxy; the diamino monomer contains benzene rings, two amino groups are connected with the benzene rings, the diamino monomer also contains more than 1 hydroxyl or carboxyl functional groups, the cross-linking agent is a siloxane compound, and the siloxane compound has more than 2 epoxy groups or amino groups.
2. The precipitation-resistant halogen-free flame retardant according to claim 1, wherein: the anti-precipitation halogen-free flame retardant comprises 92-99.5% of flame retardant powder and 0.5-8% of polyphosphazene by mass percent; and/or the number average molecular weight of the polyphosphazene is 0.5-3.5 ten thousand.
3. The precipitation-resistant halogen-free flame retardant according to claim 1, wherein: the molar ratio of the phosphonyl dichloride monomer to the diamino monomer is 10:1-1:1; and/or the mass ratio of the phosphino-urea polymer to the cross-linking agent is 1:2-1:6.
4. The precipitation-resistant halogen-free flame retardant according to claim 1, wherein: r is R 1 Selected from C1-4 alkyl, C1-2 alkoxy, benzene ring substituted by methoxy; and/or the diamino monomer has the structure of formula (II):wherein R is 2 Is hydroxyl or carboxyl, m is 1,2,3 or 4; and/or the cross-linking agent is selected fromPolydimethylsiloxanes capped at both ends with glycidyl ether, 1, 3-bis (3-glycidoxypropyl) tetramethyldisiloxane, 1,3,5, 7-tetramethylcyclotetrasiloxane substituted with 2 or 3 or 4 substituents, said substituents beingWherein p is 1,2,3,4,5 or 6, q is 1,2 or 3,
R 3 is epoxy or amino.
5. The precipitation-resistant halogen-free flame retardant according to claim 5, wherein: the phosphonyl dichloride monomer is selected from the following structures: and/or the diamino monomer is selected from the following structures:
6. the precipitation-resistant halogen-free flame retardant according to claim 1, wherein: the crosslinking agent is selected from the following structures: wherein n is such that the molecular weight of the polydimethylsiloxane is from 1 to 2 ten thousand.
7. The precipitation-resistant halogen-free flame retardant according to claim 1, wherein: the phosphorus-containing flame retardant is selected from one or a combination of more of diethyl aluminum phosphinate, aluminum tripolyphosphate and aluminum phosphite; and/or, the flame retardant powder further comprises zinc borate.
8. The precipitation-resistant halogen-free flame retardant according to claim 1, wherein: the flame retardant powder comprises the following components in percentage by mass: 0-10:0-15:0-5 of diethyl phosphinate aluminum, aluminum phosphite, aluminum tripolyphosphate and anhydrous zinc borate.
9. A method for preparing the precipitation-resistant halogen-free flame retardant according to any one of claims 1 to 8, characterized in that: the preparation method comprises the step of coating the flame retardant powder with the polyphosphazene to prepare the coating layer.
10. The method of manufacturing according to claim 9, wherein: the preparation method comprises the steps of diluting the polyphosphazene by adopting a diluent to obtain a diluent; and mixing the diluent with flame retardant powder in a spray form to obtain the precipitation-resistant halogen-free flame retardant.
11. The method of manufacturing according to claim 9, wherein: the preparation method comprises the following steps: 1) Diluting the polyphosphazene by adopting a diluent to obtain a diluent; 2) Spraying the diluent into the flame retardant powder, and mixing the diluent and the flame retardant powder to obtain the precipitation-resistant halogen-free flame retardant.
12. The method of manufacturing according to claim 11, wherein: the diluent is selected from butyl acetate or ethyl acetate; and/or the mass ratio of the diluent to the polyphosphazene is 0.5-1:1, a step of; and/or the spraying time is 2-5min.
13. The method of manufacturing according to claim 11, wherein: the mixing is carried out in a high-speed mixer, and the stirring rotating speed of the high-speed mixer is 600-1200 r/min; and/or, the temperature of the mixing is 120-160 ℃;
and/or the mixing time is 30-60 min.
14. The method of manufacturing according to claim 9, wherein: the preparation method further comprises the steps of carrying out polycondensation on a phosphono-dichloro monomer and a diamino monomer to prepare the phosphino-urea polymer, and carrying out a crosslinking reaction on the phosphino-urea polymer and a crosslinking agent to prepare the polyphosphazene.
15. The method of manufacturing according to claim 14, wherein: the polycondensation is carried out at a temperature of-10 to 35 ℃; and/or the polycondensation is performed in a solvent selected from one or more of acetonitrile, N dimethylformamide, tetrahydrofuran, ethanol, methanol, isopropanol, toluene, xylene, diethyl ether, ethyl acetate, acetone, dimethyl sulfoxide, deuterated chloroform, dichloromethane, cyclohexane, 1, 4-dioxane, pyridine; and/or, the crosslinking reaction comprises the steps of heating at 60-100 ℃ for 30-180 minutes, 80-150 ℃ for 30-120 minutes, and 100-200 ℃ for 15-150 minutes; and/or, dripping the phosphino-urea polymer into the cross-linking agent to carry out the cross-linking reaction.
16. Use of the precipitation-resistant halogen-free flame retardant according to any of claims 1 to 8 for polyamides.
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