CN113735905B - Flame-retardant charring agent containing caged phosphonate amine organosilicon compound, and preparation method and application thereof - Google Patents
Flame-retardant charring agent containing caged phosphonate amine organosilicon compound, and preparation method and application thereof Download PDFInfo
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- CN113735905B CN113735905B CN202110970718.3A CN202110970718A CN113735905B CN 113735905 B CN113735905 B CN 113735905B CN 202110970718 A CN202110970718 A CN 202110970718A CN 113735905 B CN113735905 B CN 113735905B
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 105
- 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 103
- -1 phosphonate amine organosilicon compound Chemical class 0.000 title claims abstract description 80
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 20
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- YLJJAVFOBDSYAN-UHFFFAOYSA-N dichloro-ethenyl-methylsilane Chemical compound C[Si](Cl)(Cl)C=C YLJJAVFOBDSYAN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 17
- 239000011230 binding agent Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 10
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 8
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-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 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 3
- 150000003377 silicon compounds Chemical class 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 229910001873 dinitrogen Inorganic materials 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 32
- 239000011347 resin Substances 0.000 abstract description 32
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 abstract description 28
- 229910000071 diazene Inorganic materials 0.000 abstract description 28
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 abstract description 26
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 239000003822 epoxy resin Substances 0.000 abstract description 4
- 239000011152 fibreglass Substances 0.000 abstract description 4
- 229920000647 polyepoxide Polymers 0.000 abstract description 4
- 229920000728 polyester Polymers 0.000 abstract description 4
- 229920000098 polyolefin Polymers 0.000 abstract description 4
- 229920002635 polyurethane Polymers 0.000 abstract description 4
- 239000004814 polyurethane Substances 0.000 abstract description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 3
- 239000011574 phosphorus Substances 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 18
- HIHIPCDUFKZOSL-UHFFFAOYSA-N ethenyl(methyl)silicon Chemical compound C[Si]C=C HIHIPCDUFKZOSL-UHFFFAOYSA-N 0.000 description 16
- 238000010521 absorption reaction Methods 0.000 description 14
- 238000002485 combustion reaction Methods 0.000 description 13
- 238000001035 drying Methods 0.000 description 13
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 125000001841 imino group Chemical group [H]N=* 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 239000012065 filter cake Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 229910000077 silane Inorganic materials 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000002679 ablation Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000002861 polymer material Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229920000742 Cotton Polymers 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000002023 wood Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 206010000369 Accident Diseases 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 150000003008 phosphonic acid esters Chemical class 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 238000001757 thermogravimetry curve Methods 0.000 description 2
- PFOPIMVREANHLL-UHFFFAOYSA-N 1-oxo-2,6,7-trioxa-1$l^{5}-phosphabicyclo[2.2.2]octan-4-amine Chemical group C1OP2(=O)OCC1(N)CO2 PFOPIMVREANHLL-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical class [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- BHIRTUJCQXDFRD-UHFFFAOYSA-N [Si].[P].[S] Chemical compound [Si].[P].[S] BHIRTUJCQXDFRD-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Chemical group 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65748—Esters of oxyacids of phosphorus the cyclic phosphorus atom belonging to more than one ring system
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
- C08K5/5445—Silicon-containing compounds containing nitrogen containing at least one Si-N bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- General Health & Medical Sciences (AREA)
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Abstract
The invention relates to a flame-retardant char-forming agent containing caged phosphonate amine organosilicon compound, and a preparation method and application thereof, wherein the preparation method comprises the following steps: in an organic solvent, methyl vinyl dichlorosilane reacts with caged phosphonate amine, and methyl vinyl organosilicon diimine caged phosphonate is obtained through purification treatment. The compound has stable molecular symmetry, high flame retardant efficiency, good char formation performance and higher phosphorus content, and can reduce the addition amount of the flame retardant to achieve the aim of high-efficiency flame retardance; can be used as flame-retardant char-forming agent for polyester, polyurethane, epoxy resin, unsaturated resin, glass fiber reinforced plastic, polyolefin and other materials. And the preparation process is simple, the equipment investment is low, and the industrial production is easy to realize.
Description
Technical Field
The invention relates to a preparation method and application of a flame-retardant char-forming agent containing caged phosphonate amine organosilicon compound, which is applicable to flame-retardant char-forming agents of materials such as polyester, polyurethane, epoxy resin, unsaturated resin, glass fiber reinforced plastic, polyolefin and the like.
Background
The polymer material greatly facilitates the daily life of people, is considered as a novel material for promoting the development of social productivity together with steel, wood and cement, but the inherent flammability of the polymer material limits the development and application of the polymer material. Along with the improvement of people's awareness of health and environmental protection, the development of novel halogen-free, efficient, nontoxic and environment-friendly flame retardants has become a recent research hotspot. Further plays the synergistic flame retardant property of each halogen-free element, and improves the flame retardant efficiency of the flame retardant. The prior art provides a preparation method of a phosphate wood flame retardant and a method for treating wood by using the flame retardant, and the prepared flame retardant is an intumescent annular phosphate wood flame retardant containing an acid source, a carbon source and an air source, and has the advantages of good expansion performance, compact carbon layer and certain strength. The prior art discloses a reactive phosphorus-nitrogen flame retardant, a preparation method and application thereof, wherein the reactive phosphorus-nitrogen flame retardant and a monomer form a copolymer to carry out flame retardant modification on a high polymer material, and the flame retardant effect on the high polymer material is improved through the synergistic flame retardant effect of phosphorus-nitrogen elements of the flame retardant, so that the use amount of the flame retardant in the high polymer material is reduced, and the cost of the flame retardant material is reduced. However, the existing flame retardant is either an additive flame retardant or a reactive flame retardant, and the flame retardant carbon forming effect needs to be improved.
Disclosure of Invention
The invention aims at providing a flame-retardant char-forming agent methyl vinyl bis { 1-oxo-1-phospha-2, 6, 7-trioxabicyclo [ 2.2.2 ] octyl-4 imino } silane compound which has symmetrical molecular structure, moderate polarity and good compatibility with materials, and can overcome the defects of poor compatibility between the flame retardant and the materials in the prior art. As an additive type flame retardant, the flame retardant has good flame retardant and char formation performance in materials such as polyester, polyurethane, epoxy resin, unsaturated resin, glass fiber reinforced plastic, polyolefin and the like.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
A flame-retardant char-forming agent containing caged phosphonate amine organosilicon compound has the chemical name of methyl vinyl bis { 1-oxo-1-phospha-2, 6, 7-trioxabicyclo [ 2.2.2 ] octanyl-4 imino } silane, and the chemical structure is shown as the following formula:
The invention discloses a preparation method of the flame-retardant char-forming agent containing caged phosphonate amine organosilicon compound, which has the advantages of simple process, easy mass production, less equipment investment and low cost, and comprises the following steps: under inert gas, methyl vinyl dichlorosilane is added into the mixture of organic solvent, caged phosphonate amine and acid binding agent in a dropwise manner, and then the mixture reacts for 10 to 13 hours at the temperature of between 90 and 130 ℃ to obtain the caged phosphonate amine-containing organosilicon compound flame-retardant char-forming agent.
Further, at the temperature of 10-15 ℃, the methyl vinyl dichlorosilane is dropwise added into the mixture of the organic solvent, the caged phosphonate amine and the acid binding agent for 5-10 minutes.
Further, after reacting for 10-13 hours at 90-130 ℃, filtering the reaction liquid, washing the filter cake with water, and drying to obtain the flame-retardant char-forming agent containing caged phosphonate amine organosilicon compound.
In the invention, the caged phosphonate amine is 4-amino-1 oxo-1-phospha-2, 6, 7-trioxabicyclo [ 2.2.2 ] octane, and the chemical structure is shown as the following formula:
The invention discloses a preparation method of the caged phosphonate amine, which comprises the following steps: under inert gas, phosphorus oxychloride is added into a mixture of an organic solvent, tris (hydroxymethyl) aminomethane hydrochloride and an acid binding agent in a dropwise manner, and then the mixture reacts for 6 to 8 hours at the temperature of between 70 and 100 ℃ to obtain the caged phosphonate amine.
Further, at the temperature of 10-15 ℃, phosphorus oxychloride is added into the mixture of the organic solvent, the tris (hydroxymethyl) aminomethane hydrochloride and the acid binding agent in a dropwise manner for 5-10 minutes.
Further, after the reaction is carried out for 6 to 8 hours at the temperature of between 70 and 100 ℃, the reaction liquid is filtered, then the filter cake is washed by small molecule alcohol, and then the cage-shaped phosphonate amine is obtained after drying.
The preparation of the caged phosphonate amines described above is schematically shown below:
In the invention, the organic solvent is one or more of diethylene glycol dimethyl ether, 1, 4-dioxane, acetonitrile and N, N-dimethylformamide; the acid binding agent is one or more of triethylamine, pyridine and N, N-diisopropylethylamine. When preparing caged phosphonate amine and preparing the organic silicon compound flame-retardant char-forming agent containing caged phosphonate amine, the organic solvent and the acid-binding agent can be different or the same, and preferably, the molar ratio of the acid-binding agent to the caged phosphonate amine is 1:1; or the molar ratio of the acid binding agent to the tris (hydroxymethyl) aminomethane hydrochloride is 1:1.
The invention discloses a flame-retardant char-forming agent containing caged phosphonate amine organosilicon compound, which is white solid and has the decomposition temperature: according to the preparation method, the product yield is 83.6-91.4%, and the flame retardant and the char forming agent are used as additive flame retardants for materials such as polyester, polyurethane, epoxy resin, unsaturated resin, glass fiber reinforced plastic, polyolefin and the like.
The preparation of the flame-retardant char-forming agent containing caged phosphonate amine organosilicon compound is schematically shown as follows:
The invention discloses a polymer flame-retardant material, which is prepared by mixing and curing a polymer curing system and the flame-retardant char-forming agent containing caged phosphonate amine organosilicon compound. The invention discloses a novel flame retardant, which is used as the only flame retardant to improve the flame retardant property of a pure polymer, and preferably, the flame retardant char-forming agent containing caged phosphonate amine organosilicon compound is 15-30wt%.
Compared with the prior art, the invention has the beneficial effects that:
① The invention relates to a flame retardant char forming agent methyl vinyl bis { 1-oxo-1-phospha-2, 6, 7-trioxabicyclo [ 2.2.2 ] octyl-4 imino } silane containing caged phosphonate amine organosilicon, belonging to a derivative compound with a caged structure, wherein the cage structure is highly symmetrical, and the product is stable.
② The invention relates to a flame retardant char forming agent methyl vinyl bis { 1-oxo-1-phospha-2, 6, 7-trioxabicyclo [ 2.2.2 ] octyl-4 imino } silane compound containing caged phosphonate amine organosilicon, which does not contain halogen elements, and belongs to a green environment-friendly flame retardant.
③ The flame retardant char forming agent methyl vinyl bis { 1-oxo-1-phospha-2, 6, 7-trioxabicyclo [ 2.2.2 ] octyl-4 imino } silane compound containing active vinyl can be used as a reactive flame retardant, can also be used as an additive flame retardant, and has wide application range.
④ The flame-retardant charring agent methyl vinyl bis { 1-oxo-1-phospha-2, 6, 7-trioxabicyclo [ 2.2.2 ] octyl-4 imino } silane compound containing caged phosphonate amine has good charring performance and better anti-dripping effect.
⑤ The preparation method of the caged phosphonate amine organosilicon flame retardant char forming agent methyl vinyl bis { 1-oxo-1-phospha-2, 6, 7-trioxabicyclo [ 2.2.2 ] octyl-4 imino } silane compound is a one-step reaction, and has the advantages of simple process, low equipment investment, simple and convenient operation and easy large-scale mass production.
Drawings
The following figures are presented for further illustration of the structure and performance of the product.
FIG. 1 is an infrared spectrum of caged phosphonate amines;
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of caged phosphonate amines;
FIG. 3 is an infrared spectrum of methyl vinyl silicone diimine caged phosphonate;
FIG. 4 is a nuclear magnetic resonance hydrogen spectrum of a methylvinyl silicone diimine caged phosphonate;
FIG. 5 is a thermogram of methylvinyl silicone diimine caged phosphonate with nitrogen at 10 ℃/min;
FIG. 6 is a vertical burn test performed after curing of an unsaturated resin without added methyl vinyl silicone diimine caged phosphonate;
FIG. 7 is a vertical burn test performed after curing with the addition of 20% methyl vinyl silicone diimine caged phosphonate and unsaturated resin;
FIG. 8 is a graph comparing the microscopic morphology of an ablation product of a 20% methyl vinyl silicone diimine caged phosphonate added unsaturated resin and a pure unsaturated resin after complete combustion.
Detailed Description
The raw materials involved in the invention are all existing products, and the specific preparation operation and the testing method are all conventional methods. The technical scheme of the invention is further described below with reference to the specific embodiments.
Synthesis example
The preparation method of the caged phosphonate amine disclosed by the invention comprises the following steps: adding an organic solvent, tris (hydroxymethyl) aminomethane hydrochloride and an acid binding agent into a reactor which is provided with a stirrer, a thermometer and a reflux condenser and is connected with a hydrogen chloride tail gas absorbing and drying device in parallel, dropwise adding phosphorus oxychloride under the protection of nitrogen, keeping the temperature at 10-15 ℃ in the dropwise adding process, heating to 70-100 ℃ after 8 minutes, carrying out heat preservation reaction for 6-8 hours, filtering, washing a filter cake with absolute ethyl alcohol, and drying to obtain light yellow solid caged phosphate amine, wherein the yield is 80.3-88.7%, and the initial decomposition (5%) temperature is 203 ℃.
Table 1 shows the parameters of the preparation and yields of caged phosphonate amines, the molar ratio of acid-binding agent to tris (hydroxymethyl) aminomethane hydrochloride being 1:1. FIG. 1 is an infrared spectrum of caged phosphonate amine (yield 88.7%); a characteristic absorption peak of the stretching vibration with the wavelength of 3184cm -1 being an amino group (N-H); a bending vibration absorption peak of an amino group (N-H) at 1550cm -1; a methylene (-CH 2 -) telescopic vibration absorption peak is arranged at the position of 2942cm -1; the 1627cm -1 is a characteristic absorption peak of methylene (-CH 2 -) on the cage structure; a characteristic absorption peak for C-N bonds at 1229cm -1; a stretching vibration absorption peak of p=o bond at 1033cm -1; characteristic absorption peak of P-O-C bond is at 862cm -1; FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of caged phosphonate amine (yield 88.7%); deuterated dimethyl sulfoxide is taken as a solvent, and the chemical shift delta=7.77 ppm is hydrogen peak (unimodal, peak area is 1.00) on amino (-NH 2 -); delta=3.52 ppm is the hydrogen peak (unipeak, peak area 2.94) of methylene (-CH 2 -) in the cage structure; delta = 2.50ppm is the solvent peak of deuterated reagent DMSO-d 6.
TABLE 1 preparation of caged phosphonate amines
In contrast, 10.2g of tris (hydroxymethyl) aminomethane hydrochloride and 100mL of diethylene glycol dimethyl ether are added into a reactor which is provided with a stirrer, a thermometer and a reflux condenser and is connected with a hydrogen chloride tail gas absorption and drying device in parallel, 7.67g of phosphorus oxychloride is dropwise added under the protection of nitrogen, the temperature is kept between 10 ℃ and 15 ℃ in the dropwise adding process, the temperature is raised to 70 ℃ after 8 minutes, the temperature is kept for 8 hours, the temperature is adjusted to 40 ℃, 6.58g of triethylamine is added, the temperature is naturally cooled to room temperature, the mixture is filtered, and a filter cake is washed with 50mL of absolute ethyl alcohol until ph is 7, and is dried, so that the yellowish solid caged phosphoric acid ester amine is obtained, and the yield is 38.6%.
Examples
The preparation method of the flame-retardant char-forming agent containing caged phosphonate amine organosilicon compound comprises the following steps: adding an organic solvent, caged phosphonate amine and an acid binding agent into a reactor which is provided with a stirrer, a thermometer and a reflux condenser and is connected with a hydrogen chloride tail gas absorbing and drying device in parallel, dropwise adding methyl vinyl dichlorosilane under the protection of nitrogen, keeping the temperature at 10-15 ℃ in the dropwise adding process, heating to 90-130 ℃ after 7 minutes, carrying out heat preservation reaction for 10-13 h, filtering, washing a filter cake with water, and drying to obtain a white solid which is the flame-retardant charring agent containing caged phosphonate amine organosilicon compound.
Specific preparation examples: in a reactor which is provided with a stirrer, a thermometer, a reflux condenser and is connected with a hydrogen chloride tail gas absorbing and drying device in parallel, 19.0g (0.115 mol) of caged phosphonate amine, 100mL of diethylene glycol dimethyl ether and 14.86g (0.115 mol) of N, N-diisopropylethylamine are added, 7.05g (0.05 mol) of methyl vinyl dichlorosilane are added dropwise under the protection of nitrogen, the temperature is kept between 10 ℃ and 15 ℃ in the dropwise adding process, the temperature is raised to 100 ℃ after 7 minutes, the temperature is kept for 13 hours for reaction, the filtration and the filter cake is washed with water until ph is 7, And (3) drying to obtain white solid methyl vinyl organosilicon diimine caged phosphonate (containing caged phosphonate amine organosilicon compound flame retardant char forming agent) with the yield of 91.4%. FIG. 3 is an infrared spectrum of methyl vinyl silicone diimine caged phosphonate; a telescopic vibration absorption peak with a wavelength of 3367cm -1 being an amino group (N-H); 2936cm -1 is the methylene (-CH 2 -) telescopic vibration absorption peak in the double-cage structure; The 1753cm -1 and 1701cm -1 are the telescopic vibration absorption peaks of vinyl (ch2=ch-); a telescopic vibration absorption peak of p=o bond at 1023cm -1; characteristic absorption peak of P-O-C bond at 909cm -1; A flexural vibration absorption peak of C-Si bond at 756cm -1; FIG. 4 is a nuclear magnetic resonance hydrogen spectrum of a methylvinyl silicone diimine caged phosphonate; deuterated dimethyl sulfoxide is used as a solvent, and chemical displacement delta=7.47 ppm is hydrogen peak (unimodal, peak area is 2.07) of imino (-NH-); delta=6.71 ppm is the hydrogen peak (unipeak, peak area 1.16) of the monohydrogen on vinyl (CH 2 =ch-); Delta=5.51 ppm is the hydrogen peak (unipeak, peak area 2.03) of dihydro on vinyl (CH 2 =ch-); delta = 3.30ppm hydrogen peak for H 2 O; delta = 2.50ppm is the solvent peak of deuterated reagent DMSO-d 6; delta=1.42 ppm is hydrogen peak (unipeak, peak area 12.15) of cage structure methylene (-CH 2 -); Delta = 0.91ppm hydrogen peak (unimodal, peak area 2.85) for methyl (-CH 3); FIG. 5 is a thermogram of methylvinyl silicone diimine caged phosphonate; the initial thermal decomposition (5%) temperature was 234 ℃; when the temperature is continuously increased to 368 ℃, the weight loss rate of the product is 50%; when the final heating temperature of 800 ℃ was reached, there was 17.6% residue, indicating good heat stability of the synthesized product.
Table 2 shows examples of different preparation parameters, wherein the molar ratio of the acid binding agent to the caged phosphonic acid ester amine is 1:1, and the white solid methyl vinyl organosilicon diimine caged phosphonic acid ester, namely the organic silicon compound containing the caged phosphonic acid ester amine flame retardant char forming agent, is obtained.
TABLE 2 preparation examples of methyl vinyl organosilicon diimine cage phosphonates
Comparative example one
In a reactor equipped with a stirrer, a thermometer, a reflux condenser and a hydrogen chloride tail gas absorbing and drying device, 19.0g (0.115 mol) of caged phosphonate amine, 110mL of benzyl alcohol and 11.64g (0.115 mol) of triethylamine are added, under the protection of nitrogen, 7.05g (0.05 mol) of methyl vinyl dichlorosilane is dropwise added, the temperature is kept between 10 ℃ and 15 ℃ in the dropwise adding process, the temperature is raised to 100 ℃ after 7 minutes, the reaction is kept for 12 hours, the filtration is carried out, the filter cake is washed to ph=7 by water, and the white solid methyl vinyl organosilicon diimine caged phosphonate is obtained after drying. The yield was 28.4%, and the initial thermal decomposition (5%) temperature was also tested at 233 ℃.
Comparative example two
In a reactor equipped with a stirrer, a thermometer, a reflux condenser and a hydrogen chloride tail gas absorbing and drying device, 19.0g (0.115 mol) of caged phosphonate amine, 100mL of diethylene glycol dimethyl ether and 14.86g (0.115 mol) of N, N-diisopropylethylamine are added, under the protection of nitrogen, 6.45g (0.05 mol) of dimethyl dichlorosilane is dropwise added, the dropwise adding process keeps the temperature at 10-15 ℃ for 7 minutes, the temperature is raised to 100 ℃, the reaction is kept for 13 hours, the filtration is carried out, the filter cake is washed with water until the pH is 7, and the drying is carried out, so that the yield of the product dimethyl organosilicon diimine caged phosphonate is 79.7%.
Application examples
The methyl vinyl organosilicon diimine cage phosphonate which is the product prepared above is applied to 886 unsaturated resin, specifically, the methyl vinyl organosilicon diimine cage phosphonate, 886 unsaturated resin (Jiangsu Ruimei plastics Co., ltd., industrial grade) and methyl ethyl ketone peroxide are uniformly mixed according to the proportion shown in Table 3, poured into a mold, and then put into an oven at 110 ℃ to be heated for 2.5 hours, so as to prepare standard sample bars, and the flame retardant property of the standard sample bars is tested.
One of the flame retardant property tests is a limiting oxygen index test, the limiting oxygen index of a sample to be tested is measured by referring to GB/T2406-2008 "Plastic Combustion Performance test method-oxygen index method", and the limiting oxygen index is measured by using an FC900-2 limiting oxygen index determinator, wherein standard spline specifications are 150mm multiplied by 10mm multiplied by 3mm. An index value below 25.0% may be considered flammable material, with an index value between 25.0% and 30.0% being flammable material and an index value above 30.0% being defined as flame retardant material.
The second flame retardant property test is a vertical combustion test, a CZF-3 vertical-horizontal combustion tester is used for carrying out the vertical combustion test on a sample to be tested, the sample to be tested is ignited twice at intervals of ten seconds, the time from the ignition of the sample twice to the automatic extinction of the sample is recorded as S 1 and S 2.S1+ S2 is less than or equal to 30S, and the grade of the absorbent cotton below a resin spline is V-2 grade when the absorbent cotton is ignited by molten drops; s 1+ S2 is less than or equal to 10S, and the absorbent cotton below the resin sample strip is V-1 grade without being ignited by molten drops; s 1+ S2 is less than or equal to 10S, and the absorbent cotton below the resin sample bar is V-0 grade without being ignited by molten drops.
TABLE 3 unsaturated resin systems and flame retardant Property test results
As shown in Table 3, when no flame retardant is added, the limit oxygen index of the unsaturated resin is 18.4%, the unsaturated resin can be burnt when meeting fire, the resin has no self-extinguishing performance, and the unsaturated resin can quickly drop high-temperature molten drops when being burnt, so that secondary fire accidents are easily caused; when the mass fraction of the added methyl vinyl organosilicon diimine caged phosphonate is 20%, the limiting oxygen index of the flame-retardant resin sample strip reaches 28.4%, the flame-retardant resin sample strip reaches the flame-retardant level, the flame-retardant resin self obtains self-extinguishing performance, and no high-temperature molten drops drop during combustion, and the V-0 level is reached. When the addition amount of the flame retardant reaches 30%, the limiting oxygen index of the flame retardant reaches more than 30%. Therefore, the methyl vinyl organosilicon diimine cage phosphonate disclosed by the invention has good flame retardant property when applied to unsaturated resin. In contrast, a sample obtained under the same curing conditions, with a limiting oxygen index of 21.8%, was not char, after replacing 20wt% of the methylvinyl silicone diimine caged phosphonate with 20wt% of the caged phosphonate amine. After 20wt% of methyl vinyl silicone diimine cage phosphonate was changed to 20wt% of the comparative example two product, the same curing conditions gave a sample with a limiting oxygen index of 24.9%. After 30wt% of methyl vinyl silicone diimine cage phosphonate was replaced with 30wt% of the existing DPSSPE (sulfur phosphorus silicon flame retardant with two benzene rings), the same curing conditions gave a sample with a limiting oxygen index of 28.9%.
FIG. 6 is a vertical burn test performed after curing of an unsaturated resin without added methyl vinyl silicone diimine caged phosphonate; the unsaturated resin without flame retardant is observed to be continuously combusted after 10s of primary ignition combustion, and when the resin is continuously combusted for 80s, obvious dripping condition of molten drops can be observed, and the dripping speed is higher. The unsaturated resin without the flame retardant is a very inflammable material, has no self-extinguishing performance, and is easy to drop high-temperature molten drops during combustion, so that secondary fire accidents are caused;
FIG. 7 is a vertical burn test performed after curing with the addition of 20% methyl vinyl silicone diimine caged phosphonate and unsaturated resin; the phenomenon that the sample strip is automatically extinguished can be observed at intervals of 6 seconds and 4 seconds after the ignition is performed twice, no obvious molten drops are generated in the combustion process, the dripping speed of the molten drops is greatly reduced to the speed that the molten drops are not dropped compared with the quick dripping without adding the flame retardant;
FIG. 8 is a graph comparing the microscopic morphology of an ablation product of a 20% methyl vinyl silicone diimine caged phosphonate added unsaturated resin and a pure unsaturated resin after complete combustion. a. c and e are respectively scanning electron microscope images of different magnification of the ablation product of the pure unsaturated resin, and b, d and f are respectively scanning electron microscope images of different magnification of the ablation product of the added 20% methyl vinyl organosilicon diimine cage phosphonate. As can be seen from the comparison of the figures, the ablation product of the pure unsaturated resin exhibits closely connected thin strips. Continuing to scale up to 10 μm, it was observed that the surface of the strands had adhered to the solids that had linked to the flakes, and that heat transfer could not be effectively prevented, indicating that the ablated product layer from the pure unsaturated resin could not effectively prevent the continuous combustion process. The ablation product after the addition of 20% methyl vinyl silicone diimine cage phosphonate was observed to have a number of pore structures within the ablation product due to the fact that upon combustion the substrate material was melted by heat to produce non-combustible gases (e.g., ammonia) which were released from the system and resulted in the formation of pore structures.
The invention discloses a preparation method and application of a flame retardant carbonizing agent methyl vinyl bis { 1-oxo-1-phospha-2, 6, 7-trioxabicyclo [ 2.2.2 ] octyl-4 imino } silane compound, wherein the flame retardant containing organic silicon element is a novel flame retardant system and has the advantages of green, non-toxicity, halogen-free, low smoke, low combustion heat value, low flame propagation speed, no change of original physical properties of a base material, recycling and the like. The organic silicon flame-retardant product containing the caged phosphonate amine structural unit has three flame-retardant elements of phosphorus, nitrogen and silicon, has the advantages of high flame-retardant efficiency, good carbonization performance and the like, and has great market application requirements. The invention prepares methyl vinyl organosilicon diimine cage acid ester by taking cage phosphonate amine and methyl vinyl dichlorosilane as raw materials, has simple process and low cost, and is easy to be converted into industrial production; the flame retardant has the advantages of high phosphorus content, high flame retardant efficiency, good carbon forming property, symmetrical molecular structure, good material compatibility and the like. In particular, the molecule contains active vinyl, so that the bulk flame-retardant high polymer material can be prepared through polymerization, the flame retardant does not migrate, and the physical properties of the material are not deteriorated by the addition of the flame retardant. In addition, the synergistic flame-retardant efficiency of each element can be further improved while the balance molecular symmetry of the cage-shaped structure is introduced, so that the aim of high-efficiency flame retardance is fulfilled. Therefore, the flame retardant has very good application and development prospect.
Claims (8)
1. The preparation method of the flame-retardant char-forming agent containing caged phosphonate amine organosilicon compound is characterized by comprising the following steps: dropwise adding methyl vinyl dichlorosilane into a mixture of an organic solvent, caged phosphonate amine and an acid binding agent under inert gas, and then reacting for 10-13 h at 90-130 ℃ to obtain the caged phosphonate amine-containing organosilicon compound flame-retardant char-forming agent; the organic solvent is one or more of diethylene glycol dimethyl ether, 1, 4-dioxane, acetonitrile and N, N-dimethylformamide; the chemical structure of the flame-retardant char-forming agent containing caged phosphonate amine organosilicon compound is shown as the following formula:
；
The structure of the caged phosphonate amine is shown as the following formula:
。
2. The method for preparing the flame-retardant char-forming agent containing caged phosphonate amine organosilicon compound according to claim 1, wherein methyl vinyl dichlorosilane is dropwise added into the mixture of organic solvent, caged phosphonate amine and acid-binding agent at 10-15 ℃ under nitrogen gas for 5-10 minutes.
3. The method for preparing the flame-retardant char-forming agent containing organic silicon compound of caged phosphonate amine according to claim 1, wherein phosphorus oxychloride is added dropwise into the mixture of organic solvent, tris (hydroxymethyl) aminomethane hydrochloride and acid-binding agent under inert gas, and then reacted for 6-8 hours at 70-100 ℃ to obtain the caged phosphonate amine.
4. The method for preparing the flame-retardant char-forming agent containing caged phosphonate amine organosilicon compound according to claim 1, wherein the acid-binding agent is one or more of triethylamine, pyridine and N, N-diisopropylethylamine.
5. The flame retardant char-forming agent comprising caged phosphonate amine organosilicon compound prepared by the preparation method of the flame retardant char-forming agent comprising caged phosphonate amine organosilicon compound according to claim 1.
6. The use of a flame retardant char-forming agent comprising a caged phosphonate amine organosilicon compound according to claim 5 as a flame retardant.
7. A polymer flame-retardant material is characterized in that a polymer curing system is mixed with the flame-retardant char-forming agent containing caged phosphonate amine organosilicon compound according to claim 5 and then cured, so as to obtain the polymer flame-retardant material.
8. The polymeric flame retardant material of claim 7, wherein the flame retardant char-forming agent comprises a caged phosphonate amine organosilicon compound in an amount of 15 to 30wt%.
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