CN113735905A - Cage-shaped phosphonate amine organic silicon compound-containing flame-retardant char-forming agent and preparation method and application thereof - Google Patents
Cage-shaped phosphonate amine organic silicon compound-containing flame-retardant char-forming agent and preparation method and application thereof Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 99
- 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 94
- -1 phosphonate amine Chemical class 0.000 title claims abstract description 78
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 150000003377 silicon compounds Chemical class 0.000 title claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 19
- 239000003960 organic solvent Substances 0.000 claims abstract description 14
- YLJJAVFOBDSYAN-UHFFFAOYSA-N dichloro-ethenyl-methylsilane Chemical compound C[Si](Cl)(Cl)C=C YLJJAVFOBDSYAN-UHFFFAOYSA-N 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 19
- 239000011230 binding agent Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- 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 8
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- 239000002861 polymer material Substances 0.000 claims description 7
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 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
- 239000011261 inert gas Substances 0.000 claims description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 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
- 150000003961 organosilicon compounds Chemical class 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 31
- 239000011347 resin Substances 0.000 abstract description 31
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 abstract description 25
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 abstract description 22
- 229910000071 diazene Inorganic materials 0.000 abstract description 22
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 18
- 229910052710 silicon Inorganic materials 0.000 abstract description 18
- 239000010703 silicon Substances 0.000 abstract description 18
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 4
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- 238000010521 absorption reaction Methods 0.000 description 19
- 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 15
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 239000012065 filter cake Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 125000001841 imino group Chemical group [H]N=* 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 238000002485 combustion reaction Methods 0.000 description 8
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- 238000002679 ablation Methods 0.000 description 7
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
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- 238000010438 heat treatment Methods 0.000 description 5
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 5
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- 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
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
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- 206010000369 Accident Diseases 0.000 description 2
- 239000004254 Ammonium phosphate Substances 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
- 229910019142 PO4 Inorganic materials 0.000 description 2
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 2
- 235000019289 ammonium phosphates Nutrition 0.000 description 2
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- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 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
- 239000010452 phosphate Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
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- 238000004321 preservation Methods 0.000 description 2
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- 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-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
- 230000003321 amplification Effects 0.000 description 1
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- 238000006757 chemical reactions by type Methods 0.000 description 1
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- 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
- 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
- 238000002844 melting Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
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- 231100000252 nontoxic Toxicity 0.000 description 1
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- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
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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
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- 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
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- 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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- 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
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- C08L2201/02—Flame or fire retardant/resistant
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Abstract
The invention relates to a caged phosphonate amine organic silicon compound-containing flame-retardant char forming agent, a preparation method and an application thereof, wherein the preparation method comprises the following steps: in an organic solvent, reacting methyl vinyl dichlorosilane with caged phosphonate amine, and purifying to obtain the methyl vinyl organic silicon diimine caged phosphonate. The compound has stable molecular symmetry, high flame-retardant efficiency, good char-forming performance and higher phosphorus content, and can reduce the addition of the flame retardant to achieve the aim of high-efficiency flame retardance; can be used as a flame-retardant charring agent for materials such as polyester, polyurethane, epoxy resin, unsaturated resin, glass fiber reinforced plastic, polyolefin and the like. 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 caged phosphonate amine organic silicon compound containing flame-retardant charring agent, wherein the compound is suitable for flame-retardant charring 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 daily life of people, and 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. With the improvement of consciousness of people on health and environmental protection, the development of novel halogen-free, efficient, nontoxic and environment-friendly flame retardant has become a recent research hotspot. Further exerting the synergistic flame retardant property of each halogen-free element, and improving the flame retardant efficiency of the flame retardant. The prior art provides a preparation method of a phosphate wood fire retardant and a method for treating wood by using the fire retardant, the prepared fire retardant is an expansion type annular phosphate wood fire retardant containing an acid source, a carbon source and a gas 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 and a preparation method and application thereof, wherein a copolymer is formed by the reactive phosphorus-nitrogen flame retardant and a monomer 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 and 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 and carbon formation effect needs to be improved.
Disclosure of Invention
One of the purposes of the invention is to provide a flame-retardant char-forming agent methylvinylbis { 1-oxo-1-phospha-2, 6, 7-trioxabicyclo [ 2.2.2 ] octyl-4 imino } silane compound which has the advantages of symmetrical molecular structure, moderate polarity and good compatibility with materials, and can overcome the defects of poor compatibility of flame retardants and materials in the prior art. As an additive flame retardant, the flame retardant also has good flame retardant and charring performance in materials such as polyester, polyurethane, epoxy resin, unsaturated resin, glass fiber reinforced plastic, polyolefin and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
a flame-retardant charring agent containing caged phosphonate amine organosilicon compound, its chemical name is methylvinylbis { 1-oxo-1-phospha-2, 6, 7-trioxabicyclo [ 2.2.2 ] octyl-4 imino } silane, its chemical structure is shown as following formula:
the invention discloses a preparation method of the caged phosphonate amine organic silicon compound containing flame-retardant charring agent, which has the advantages of simple process, easy large-scale mass production, less equipment investment and low cost, and comprises the following steps: under inert gas, dropwise adding methyl vinyl dichlorosilane into a mixture of an organic solvent, caged phosphonate amine and an acid-binding agent, and then reacting at 90-130 ℃ for 10-13 h to obtain the caged phosphonate amine-containing organic silicon compound flame-retardant char-forming agent.
Further, at the temperature of 10-15 ℃, dropwise adding methyl vinyl dichlorosilane into a mixture of an organic solvent, cage-shaped phosphonate amine and an acid-binding agent for 5-10 minutes.
And further, after reacting for 10-13 h at 90-130 ℃, filtering the reaction solution, washing the filter cake with water, and drying to obtain the cage-shaped phosphonate amine organic silicon compound flame-retardant char-forming agent.
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 of the caged phosphonate amine 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, dropwise adding phosphorus oxychloride into a mixture of an organic solvent, tris (hydroxymethyl) aminomethane hydrochloride and an acid-binding agent, and reacting at 70-100 ℃ for 6-8 h to obtain the cage-shaped phosphonate amine.
Further, at the temperature of 10-15 ℃, phosphorus oxychloride is dropwise added into a mixture of an organic solvent, tris (hydroxymethyl) aminomethane hydrochloride and an acid-binding agent for 5-10 minutes.
Further, after reacting for 6-8 h at 70-100 ℃, filtering the reaction solution, washing a filter cake with micromolecule alcohol, and drying to obtain the cage-shaped phosphonate amine.
The preparation of the caged phosphonate amine described above is schematically as follows:
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 the caged phosphonate amine and the caged phosphonate amine-containing organic silicon compound flame-retardant char-forming agent, the organic solvent and the acid-binding agent can be different or the same, 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 caged phosphonate amine organic silicon compound-containing flame-retardant charring agent which is a white solid, and has the decomposition temperature: the product yield is 83.6-91.4% at 234 ℃, and the product is used as an additive flame retardant in flame retardant charring agents of materials such as polyester, polyurethane, epoxy resin, unsaturated resin, glass fiber reinforced plastic, polyolefin and the like.
The preparation of the caged phosphonate amine organic silicon compound-containing flame-retardant char-forming agent 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 charring agent containing the cage-shaped phosphonate amine organic silicon compound. The invention discloses a novel flame retardant which is used as a unique flame retardant to improve the flame retardant performance of a pure polymer, wherein a polymer curing system is the prior art and refers to a component for curing and preparing a polymer, and preferably, the dosage of the flame retardant charring agent containing the caged phosphonate amine organic silicon compound is 15-30 wt%.
Compared with the prior art, the invention has the beneficial effects that:
the invention relates to a caged phosphonate amine organic silicon flame-retardant char-forming agent methylvinylbis { 1-oxo-1-phospha-2, 6, 7-trioxabicyclo [ 2.2.2 ] octyl-4 imino } silane, belonging to a caged structure derivative compound, wherein the cage ring structure is highly symmetrical, and the product is stable.
② the caged phosphonate amine organic silicon flame retardant char forming agent methylvinylbis { 1-oxo-1-phospha-2, 6, 7-trioxabicyclo [ 2.2.2 ] octyl-4 imino } silane compound does not contain halogen elements, and belongs to a green environment-friendly flame retardant.
The compound containing caged phosphonate amine organosilicon flame retardant charring agent methylvinylbis { 1-oxo-1-phospha-2, 6, 7-trioxabicyclo [ 2.2.2 ] octyl-4 imino } silane contains active vinyl group, can be used as a reaction type flame retardant, can also be used as an additive type flame retardant, and has wide application range.
The caged phosphonate amine organic silicon flame-retardant char forming agent methylvinylbis { 1-oxo-1-phospha-2, 6, 7-trioxabicyclo [ 2.2.2 ] octyl-4 imino } silane compound has good char forming performance and better anti-melting and anti-dripping effects.
The preparation method of the caged phosphonate amine organic silicon flame-retardant char-forming agent methylvinylbis { 1-oxo-1-phospha-2, 6, 7-trioxabicyclo [ 2.2.2 ] octyl-4 imino } silane compound has the advantages of one-step reaction, simple process, low equipment investment, simple and convenient operation and easy large-scale mass production.
Drawings
The following figures are presented to further illustrate the structure and performance of the product.
FIG. 1 is an infrared spectrum of caged phosphonate amine;
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of caged phosphonate amine;
FIG. 3 is an infrared spectrum of methyl vinyl silicone diimine cage phosphonate;
FIG. 4 is a nuclear magnetic resonance hydrogen spectrum of methyl vinyl silicone diimine cage phosphonate;
FIG. 5 is a thermogravimetric-differential thermogram of methyl vinyl silicone diimido cage phosphonate with nitrogen at 10 deg.C/min;
FIG. 6 is a vertical burn test conducted after curing of an unsaturated resin without the addition of methylvinyl silicone diimine cage phosphonate;
FIG. 7 is a vertical burn test conducted after addition of 20% methyl vinyl silicone diimine cage phosphonate with curing of the unsaturated resin;
FIG. 8 is a scanning electron microscope microscopic morphology comparison graph of ablation products after complete combustion of unsaturated resin added with 20% methyl vinyl silicone diimine cage phosphonate and pure unsaturated resin.
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 solution of the present 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 absorption and drying device, dropwise adding phosphorus oxychloride under the protection of nitrogen, keeping the temperature of 10-15 ℃ in the dropwise adding process for 8 minutes, heating to 70-100 ℃, carrying out heat preservation reaction for 6-8 hours, filtering, washing a filter cake with absolute ethyl alcohol, and drying to obtain a light yellow solid cage-shaped ammonium phosphate, wherein the yield is 80.3-88.7%, and the initial decomposition (5%) temperature is 203 ℃.
Table 1 shows the preparation parameters and yields of caged phosphonate amine, with the molar ratio of acid-binding agent to tris (hydroxymethyl) aminomethane hydrochloride being 1: 1. FIG. 1 is an IR spectrum of caged phosphonate amine (88.7% yield); the wavelength is 3184cm-1The absorption peak of the stretching vibration characteristic of the amino (N-H) is positioned; 1550cm-1A bending vibration absorption peak at an amino group (N-H); 2942cm-1In the form of methylene (-CH)2-) a stretching vibration absorption peak; 1627cm-1In a cage structure with methylene (-CH)2-) characteristic absorption peaks; 1229cm-1A characteristic absorption peak at C-N bond; 1033cm-1A stretching vibration absorption peak at P = O bond; 862cm-1A characteristic absorption peak at the P-O-C bond; FIG. 2 is a NMR spectrum of caged phosphonate amine (88.7% yield); deuterated dimethyl sulfoxide is used as a solvent, and the chemical shift delta =7.77ppm is an amino group (-NH)2-) hydrogen peak (singlet, peak area 1.00); δ =3.52ppm is methylene (-CH) in cage structure2-) hydrogen peak (singlet, peak area 2.94); δ =2.50ppm is the solvent peak for deuterated reagent DMSO-d 6.
TABLE 1 preparation of caged phosphonate amines
For comparison, 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, 7.67g of phosphorus oxychloride is added dropwise under the protection of nitrogen, the temperature is kept at 10-15 ℃ in the dropwise adding process, the temperature is raised to 70 ℃ after 8 minutes of dropwise adding, the temperature is kept for 8 hours, then the temperature is adjusted to 40 ℃, 6.58g of triethylamine is added, the mixture is naturally cooled to room temperature and then filtered, a filter cake is washed by 50mL of absolute ethyl alcohol until the pH is 7, and the filter cake is dried to obtain faint yellow solid cage-shaped ammonium phosphate, wherein the yield is 38.6%.
Examples
The preparation method of the flame-retardant charring agent containing the caged phosphonate amine organic silicon compound comprises the following steps: adding an organic solvent, cage-shaped 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 absorption and drying device, dropwise adding methyl vinyl dichlorosilane under the protection of nitrogen, keeping the temperature at 10-15 ℃ in the dropwise adding process, after 7 minutes of dropwise adding, heating to 90-130 ℃, carrying out heat preservation reaction for 10-13 hours, filtering, washing a filter cake with water, and drying to obtain a white solid which is a flame-retardant char-forming agent containing cage-shaped phosphonate amine organosilicon compounds.
Specific preparation examples: 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 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, 7.05g (0.05 mol) of methyl vinyl dichlorosilane is dripped under the protection of nitrogen, the temperature is kept at 10-15 ℃ in the dripping process, the dripping is finished within 7 minutes, the temperature is raised to 100 ℃, the reaction is kept for 13 hours, the filtration is carried out, a filter cake is washed by water until the pH is 7, and the white solid methyl vinyl organic silicon diimido caged phosphonate (containing caged phosphonate amine organic silicon compound flame retardant char forming agent) is obtained with the yield of 91.4 percent. FIG. 3 is an infrared spectrum of methyl vinyl silicone diimine cage phosphonate; the wavelength is 3367cm-1A stretching vibration absorption peak of an amino group (N-H); 2936cm-1In a double cage structure as methylene (-CH)2-) stretching vibrationAn absorption peak; 1753cm-1And 1701cm-1Is the absorption peak of the stretching vibration of the vinyl group (CH2= CH-); 1023cm-1A stretching vibration absorption peak at P = O bond; 909cm-1A characteristic absorption peak at the P-O-C bond; 756cm-1A bending vibration absorption peak at a C-Si bond; FIG. 4 is a nuclear magnetic resonance hydrogen spectrum of methyl vinyl silicone diimine cage phosphonate; using deuterated dimethyl sulfoxide as a solvent, wherein chemical shift delta =7.47ppm is a hydrogen peak of an imino group (-NH-) (single peak, peak area is 2.07); δ =6.71ppm is vinyl (CH)2Hydrogen peak of monohydrogen on = CH-) (singlet, peak area 1.16); δ =5.51ppm is vinyl (CH)2Hydrogen peak of hydrogen on = CH-) (singlet, peak area 2.03); δ =3.30ppm is H2Hydrogen peak of O; δ =2.50ppm is the solvent peak for deuterated reagent DMSO-d 6; δ =1.42ppm is a methylene group (-CH) of cage structure2-) hydrogen peak (singlet, peak area 12.15); δ =0.91ppm is methyl (-CH)3) Hydrogen peak (singlet, peak area 2.85); FIG. 5 is a thermogravimetric-differential thermogram of methyl vinyl silicone diimido cage phosphonate; the initial thermal decomposition (5%) temperature was 234 ℃; when the temperature is continuously raised to 368 ℃, the weight loss rate of the product is 50 percent; when the final heating temperature of 800 ℃ was reached, there was still 17.6% residue, indicating that the synthesized product had good thermal stability.
Table 2 shows examples with different preparation parameters, wherein the molar ratio of the acid-binding agent to the caged phosphoric acid ester amine is 1: 1, and white solid methyl vinyl organic silicon diimine caged phosphonate, namely the caged phosphonic acid ester amine-containing organic silicon compound flame-retardant char-forming agent, is obtained.
Table 2 example for the preparation of methylvinylsilicone diimine caged phosphonates
Comparative example 1
Adding 19.0g (0.115 mol) of caged phosphonate amine, 110mL of benzyl alcohol and 11.64g (0.115 mol) of triethylamine 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, beginning to dropwise add 7.05g (0.05 mol) of methylvinyl dichlorosilane under the protection of nitrogen, keeping the temperature at 10-15 ℃ in the dropwise adding process, heating to 100 ℃ after 7 minutes of dropwise adding, preserving the temperature for reaction for 12 hours, filtering, washing a filter cake with water to ph =7, and drying to obtain white solid methylvinyl organic silicon diimido caged phosphonate. Yield 28.4%, initial thermal decomposition (5%) temperature was also tested at 233 ℃.
Comparative example No. two
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 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, under the protection of nitrogen, 6.45g (0.05 mol) of dimethyldichlorosilane is dripped, the temperature is kept at 10-15 ℃ in the dripping process, the temperature is increased to 100 ℃ after 7 minutes of dripping is finished, the reaction is kept for 13 hours, the filtration is carried out, a filter cake is washed by water until the ph is 7, and the drying is carried out, thus the yield of the product dimethyl organic silicon diimido caged phosphonate ester is 79.7%.
Application examples
The prepared product methyl vinyl organic silicon diimine cage-shaped phosphonate is applied to 886 unsaturated resin, specifically, the methyl vinyl organic silicon diimine cage-shaped phosphonate, 886 unsaturated resin (Jiangsu Ruimei plastics Co., Ltd., industrial grade) and methyl ethyl ketone peroxide are uniformly mixed according to the proportion in the table 3, poured into a mold, then placed into a drying oven at 110 ℃ for heating for 2.5 hours, and a standard sample strip is prepared and subjected to flame retardant property test.
One of the flame retardant property tests is a limit oxygen index test, the limit oxygen index of a sample to be tested is measured by referring to GB/T2406-2008 'Plastic burning property test method-oxygen index method', the limit oxygen index is measured by using an FC900-2 limit oxygen index tester, and the standard sample strip specification is 150mm multiplied by 10mm multiplied by 3 mm. An index value below 25.0% is considered a combustible material, an index value between 25.0% and 30.0% is a combustible material, and an index value above 30.0% is defined as a flame-resistant material.
The second test of flame retardant property is vertical burning test, which is to test the vertical burning of the sample to be tested by CZF-3 type vertical-horizontal burning testerThe sample is ignited twice at an interval of ten seconds, and the time from the ignition of the sample twice to the automatic extinction of the sample is recorded as S1And S2。S1+ S2The grade is V-2 grade when the absorbent cotton below the resin sample strip is ignited by the molten drops; s1+ S2The time is less than or equal to 10s, and the absorbent cotton below the resin sample strip is V-1 grade without being ignited by the molten drops; s1+ S2Is less than or equal to 10s, and the absorbent cotton below the resin sample strip is V-0 grade without being ignited by the molten drops.
TABLE 3 unsaturated resin System and flame retardancy test results
As can be seen from Table 3, when no flame retardant is added, the limit oxygen index of the unsaturated resin is 18.4%, the unsaturated resin can be immediately combusted when meeting fire, and the resin has no self-extinguishing property, so that high-temperature molten drops can rapidly fall off during combustion, and secondary fire accidents are easily caused; when the mass fraction of the added methylvinyl organic silicon diimine cage-shaped phosphonate is 20%, the limit oxygen index of the flame-retardant resin sample strip reaches 28.4%, the flame-retardant grade is achieved, the flame-retardant resin self obtains self-extinguishing performance, no high-temperature molten drops drop during combustion is caused, and the V-0 grade is achieved. And when the addition amount of the flame retardant reaches 30%, the limit oxygen index of the flame retardant reaches more than 30%. Therefore, the methyl vinyl organic silicon diimine cage-shaped phosphonate disclosed by the invention has good flame retardant property when being applied to unsaturated resin. For comparison, a sample obtained under the same curing conditions after replacing 20wt% of methylvinyl silicone diimido caged phosphonate with 20wt% of caged phosphonate amine had a limiting oxygen index of 21.8% and did not char. After replacing 20wt% of methylvinylsilicone diimine cage phosphonate with 20wt% of the product of comparative example, the same curing conditions gave a sample with a limiting oxygen index of 24.9%. After 30wt% of methylvinyl organic silicon diimine cage-shaped phosphonate was replaced with 30wt% of the existing DPSSPE (sulfur-phosphorus-silicon flame retardant with two benzene rings), the limited oxygen index of the sample obtained under the same curing conditions was 28.9%.
FIG. 6 is a vertical burn test conducted after curing of an unsaturated resin without the addition of methylvinyl silicone diimine cage phosphonate; after the unsaturated resin without the flame retardant is ignited for 10s, the resin is observed to be continuously combusted, and after the unsaturated resin is continuously combusted for 80s, the obvious condition of dripping of molten drops can be observed, and the dripping speed is high. The unsaturated resin without the added flame retardant is an extremely flammable material, has no self-extinguishing performance, and is easy to drip high-temperature molten drops during combustion to cause secondary fire accidents;
FIG. 7 is a vertical burn test conducted after addition of 20% methyl vinyl silicone diimine cage phosphonate with curing of the unsaturated resin; the phenomenon that the sample strip is automatically extinguished can be observed after 6 seconds and 4 seconds of twice ignition, no obvious molten drop drops in the combustion process, and the dropping speed of the molten drop is greatly reduced to the extent that the molten drop does not drop, so that the rapid dropping is greatly improved compared with the rapid dropping when no flame retardant is added;
FIG. 8 is a scanning electron microscope microscopic morphology comparison graph of ablation products after complete combustion of unsaturated resin added with 20% methyl vinyl silicone diimine cage phosphonate and pure unsaturated resin. a. c and e are respectively scanning electron microscope images of pure unsaturated resin ablation products amplified by different times, and b, d and f are respectively scanning electron microscope images of ablation products amplified by different times by adding 20% of methyl vinyl organic silicon diimine cage-shaped phosphonate. As can be seen from the comparison in the figure, the ablation product of the pure unsaturated resin exhibits closely connected thin stripes. On further amplification to 10 μm, it was observed that the surface of the sliver was adhered with a solid linked to a sheet, which was not effective in preventing heat transfer, indicating that the ablation product layer generated from pure unsaturated resin could not effectively prevent the continuous combustion process. After 20% of methylvinyl organosilicone diimine cage phosphonate is added, a plurality of pore structures are observed in the ablation product, and the pore structures are generated due to the fact that a base material is heated and melted to generate non-combustible gas (such as ammonia gas) during combustion, and the non-combustible gas is continuously released from the system to the outside.
The invention discloses a preparation method and application of a flame-retardant char-forming agent methylvinylbis { 1-oxo-1-phospha-2, 6, 7-trioxabicyclo [ 2.2.2 ] octyl-4 imino } silane compound. 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 takes the caged phosphonate amine and the methyl vinyl dichlorosilane as raw materials to prepare the methyl vinyl organic silicon diimine caged acid ester, has simple process and low cost, and is easy to convert into industrial production; the flame retardant disclosed by the invention has the advantages of high phosphorus content, high flame retardant efficiency, good carbon forming property, symmetrical molecular structure, good material compatibility and the like. Particularly, the molecule contains active vinyl, the high molecular material with the flame retardant can be prepared by polymerization, and the flame retardant does not migrate and does not deteriorate the physical properties of the material due to the addition of the flame retardant. In addition, when the symmetry of molecules is balanced by introducing a cage-shaped structure, the synergistic flame-retardant efficiency of each element can be further improved, and the purpose of high-efficiency flame retardance is achieved. Therefore, the flame retardant has very good application and development prospects.
Claims (10)
1. A flame-retardant char-forming agent containing caged phosphonate amine organosilicon compound is characterized in that the chemical structure is as shown in the following formula:
2. the method for preparing the caged phosphonate amine organosilicon compound-containing flame retardant char-forming agent of claim 1, comprising the steps of: under inert gas, dropwise adding methyl vinyl dichlorosilane into a mixture of an organic solvent, caged phosphonate amine and an acid-binding agent, and then reacting at 90-130 ℃ for 10-13 h to obtain the caged phosphonate amine-containing organic silicon compound flame-retardant char-forming agent.
3. The method for preparing the caged phosphonate amine organosilicon compound containing flame retardant char-forming agent according to claim 2, wherein the methyl vinyl dichlorosilane is dripped into the mixture of the organic solvent, the caged phosphonate amine and the acid-binding agent at 10-15 ℃ under nitrogen gas, and the dripping time is 5-10 minutes.
4. The method for preparing the caged phosphonate amine organosilicon compound containing flame retardant char-forming agent according to claim 2, wherein the structure of the caged phosphonate amine is as shown in the following formula:
5. the preparation method of the caged phosphonate amine organic silicon compound containing flame retardant charring agent as claimed in claim 2, wherein phosphorus oxychloride is added dropwise into a mixture of an organic solvent, tris (hydroxymethyl) aminomethane hydrochloride and an acid-binding agent under inert gas, and then the mixture is reacted at 70-100 ℃ for 6-8 h to obtain the caged phosphonate amine.
6. The method for preparing the caged phosphonate amine organosilicon compound containing flame retardant charring agent as claimed in claim 2, wherein 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.
7. A preparation method of caged phosphonate amine is characterized by dropwise adding phosphorus oxychloride into a mixture of an organic solvent, tris (hydroxymethyl) aminomethane hydrochloride and an acid-binding agent under inert gas, and then reacting at 70-100 ℃ for 6-8 h to obtain the caged phosphonate amine.
8. Use of a caged phosphonate amine containing organosilicon compound flame retardant char-forming agent as defined in claim 1 or a caged phosphonate amine as defined in claim 7 as a flame retardant.
9. A polymer flame-retardant material, characterized in that a polymer curing system is mixed with the caged phosphonate amine organic silicon compound flame-retardant char-forming agent of claim 1 and then cured to obtain the polymer flame-retardant material.
10. The flame retardant polymer material according to claim 9, wherein the flame retardant char-forming agent containing caged phosphonate amine organosilicon compound is used in an amount of 15 to 30 wt%.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116554954A (en) * | 2023-05-11 | 2023-08-08 | 铜陵兢强电子科技股份有限公司 | Environment-friendly enameled wire surface lubricating oil and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3562207A (en) * | 1968-02-23 | 1971-02-09 | Emery Industries Inc | Polymeric materials containing caged boron-nitrogen compounds |
| CN103980430A (en) * | 2014-05-22 | 2014-08-13 | 西南科技大学 | Preparation method of unsaturated polyester flame-retardant composite material |
| CN104479077A (en) * | 2014-12-09 | 2015-04-01 | 东华大学 | Vinyl silicon-containing cage-shaped phosphate flame retardant and preparation method thereof |
| CN106167505A (en) * | 2016-07-04 | 2016-11-30 | 华北理工大学 | A kind of siliceous caged thiophosphate fire retardant and preparation method thereof |
| CN109336930A (en) * | 2018-09-18 | 2019-02-15 | 苏州科技大学 | Fire retardant phenyl phosphono-N, N '-two young laying ducks in cage amine compounds and preparation method thereof |
| CN111961252A (en) * | 2020-08-06 | 2020-11-20 | 苏州科技大学 | Fire retardant phenylphosphonyl methyl silicone cage-shaped ester amine compound and preparation method thereof |
| CN111978351A (en) * | 2020-08-06 | 2020-11-24 | 苏州科技大学 | Fire retardant cage-shaped organic silicon phosphoramide compound and preparation method thereof |
| CN112279873A (en) * | 2020-10-27 | 2021-01-29 | 苏州科技大学 | Reactive flame retardant vinyl organosilicon caged phosphorothioate compound, and preparation method and application thereof |
-
2021
- 2021-08-23 CN CN202110970718.3A patent/CN113735905A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3562207A (en) * | 1968-02-23 | 1971-02-09 | Emery Industries Inc | Polymeric materials containing caged boron-nitrogen compounds |
| CN103980430A (en) * | 2014-05-22 | 2014-08-13 | 西南科技大学 | Preparation method of unsaturated polyester flame-retardant composite material |
| CN104479077A (en) * | 2014-12-09 | 2015-04-01 | 东华大学 | Vinyl silicon-containing cage-shaped phosphate flame retardant and preparation method thereof |
| CN106167505A (en) * | 2016-07-04 | 2016-11-30 | 华北理工大学 | A kind of siliceous caged thiophosphate fire retardant and preparation method thereof |
| CN109336930A (en) * | 2018-09-18 | 2019-02-15 | 苏州科技大学 | Fire retardant phenyl phosphono-N, N '-two young laying ducks in cage amine compounds and preparation method thereof |
| CN111961252A (en) * | 2020-08-06 | 2020-11-20 | 苏州科技大学 | Fire retardant phenylphosphonyl methyl silicone cage-shaped ester amine compound and preparation method thereof |
| CN111978351A (en) * | 2020-08-06 | 2020-11-24 | 苏州科技大学 | Fire retardant cage-shaped organic silicon phosphoramide compound and preparation method thereof |
| CN112279873A (en) * | 2020-10-27 | 2021-01-29 | 苏州科技大学 | Reactive flame retardant vinyl organosilicon caged phosphorothioate compound, and preparation method and application thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116554954A (en) * | 2023-05-11 | 2023-08-08 | 铜陵兢强电子科技股份有限公司 | Environment-friendly enameled wire surface lubricating oil and preparation method thereof |
| CN116554954B (en) * | 2023-05-11 | 2024-05-28 | 铜陵兢强电子科技股份有限公司 | Environment-friendly enameled wire surface lubricating oil and preparation method thereof |
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