CN115466431A - Smoke suppressant, preparation method thereof and polymer composite material - Google Patents
Smoke suppressant, preparation method thereof and polymer composite material Download PDFInfo
- Publication number
- CN115466431A CN115466431A CN202211069841.9A CN202211069841A CN115466431A CN 115466431 A CN115466431 A CN 115466431A CN 202211069841 A CN202211069841 A CN 202211069841A CN 115466431 A CN115466431 A CN 115466431A
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- Prior art keywords
- smoke suppressant
- salt
- flame retardant
- inorganic flame
- mass
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- 239000000779 smoke Substances 0.000 title claims abstract description 98
- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 229920000642 polymer Polymers 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title abstract description 23
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 53
- 239000012796 inorganic flame retardant Substances 0.000 claims abstract description 30
- 239000002245 particle Substances 0.000 claims abstract description 17
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 15
- 239000013110 organic ligand Substances 0.000 claims abstract description 15
- 239000011159 matrix material Substances 0.000 claims abstract description 9
- 229910001428 transition metal ion Inorganic materials 0.000 claims abstract description 5
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 51
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- 229910001593 boehmite Inorganic materials 0.000 claims description 46
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 46
- 239000003381 stabilizer Substances 0.000 claims description 21
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 20
- -1 transition metal salt Chemical class 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 claims description 16
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 16
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- 235000013539 calcium stearate Nutrition 0.000 claims description 16
- JNXDCMUUZNIWPQ-UHFFFAOYSA-N trioctyl benzene-1,2,4-tricarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C(C(=O)OCCCCCCCC)=C1 JNXDCMUUZNIWPQ-UHFFFAOYSA-N 0.000 claims description 16
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- 238000002156 mixing Methods 0.000 claims description 8
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 claims description 8
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- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 5
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- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 4
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- 229960000892 attapulgite Drugs 0.000 claims description 4
- 150000001868 cobalt Chemical class 0.000 claims description 4
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 4
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- 239000000395 magnesium oxide Substances 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- 229960000869 magnesium oxide Drugs 0.000 claims description 4
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- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 claims description 2
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- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 claims description 2
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- 150000001875 compounds Chemical class 0.000 claims description 2
- UQLDLKMNUJERMK-UHFFFAOYSA-L di(octadecanoyloxy)lead Chemical compound [Pb+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O UQLDLKMNUJERMK-UHFFFAOYSA-L 0.000 claims description 2
- OEIWPNWSDYFMIL-UHFFFAOYSA-N dioctyl benzene-1,4-dicarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C=C1 OEIWPNWSDYFMIL-UHFFFAOYSA-N 0.000 claims description 2
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims description 2
- OCWMFVJKFWXKNZ-UHFFFAOYSA-L lead(2+);oxygen(2-);sulfate Chemical compound [O-2].[O-2].[O-2].[Pb+2].[Pb+2].[Pb+2].[Pb+2].[O-]S([O-])(=O)=O OCWMFVJKFWXKNZ-UHFFFAOYSA-L 0.000 claims description 2
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- 150000002696 manganese Chemical class 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 150000002751 molybdenum Chemical class 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- 229920003192 poly(bis maleimide) Polymers 0.000 claims description 2
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- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
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- 239000008117 stearic acid Substances 0.000 claims description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims 1
- PEJVLWCOQVHCAF-UHFFFAOYSA-N dioctyl oxalate Chemical compound CCCCCCCCOC(=O)C(=O)OCCCCCCCC PEJVLWCOQVHCAF-UHFFFAOYSA-N 0.000 claims 1
- 229920013636 polyphenyl ether polymer Polymers 0.000 claims 1
- 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 abstract description 17
- 239000003063 flame retardant Substances 0.000 abstract description 17
- 239000000463 material Substances 0.000 abstract description 15
- 238000005054 agglomeration Methods 0.000 abstract description 5
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- 230000001629 suppression Effects 0.000 abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 44
- 239000000243 solution Substances 0.000 description 33
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 20
- 239000000725 suspension Substances 0.000 description 19
- 239000013096 zirconium-based metal-organic framework Substances 0.000 description 17
- 238000003756 stirring Methods 0.000 description 9
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- 238000005406 washing Methods 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
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- 238000002485 combustion reaction Methods 0.000 description 4
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Images
Classifications
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L87/00—Compositions of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- 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)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a smoke suppressant, a preparation method thereof and a polymer composite material, and relates to the technical field of polymer flame-retardant smoke suppressant materials, wherein the smoke suppressant comprises an inorganic flame retardant and metal organic framework particles loaded on the inorganic flame retardant; the metal-organic framework particles are formed by self-assembling organic ligands and metal ions through the metal ions as connection points; the metal ion is at least one selected from transition metal ions. According to the invention, the surface of the inorganic flame retardant is coated with the metal organic framework material, so that the compatibility of the inorganic flame retardant and a polymer matrix can be improved, and the agglomeration of the metal organic framework material and the inorganic flame retardant can be inhibited; thereby improving the smoke suppression effect and the mechanical property of the polymer composite material.
Description
The technical field is as follows:
the invention relates to the technical field of polymer flame-retardant smoke-inhibiting materials, in particular to a smoke inhibitor, a preparation method thereof and a polymer composite material.
Background art:
the Metal Organic Framework (MOF) refers to a crystalline porous material synthesized by metal ions and organic ligands in a coordination mode under certain conditions. Since Yaghi research group reported the first MOF in 1995, this hybrid inorganic-organic material has attracted extensive attention worldwide. The MOFs material has the characteristics of higher specific surface area, larger pore volume, adjustable pore channel structure and the like, so that the MOFs material has great application value in the fields of gas storage, catalysis, sensing, water pollution, drug delivery and the like.
Because MOFs are essentially organic-inorganic hybrids, and the MOFs are used in the field of improving the flame retardant property of polymers by utilizing the self catalytic and adsorption properties, CO is generated in the combustion process of high molecular polymers, and the emission of toxic gases such as CO and the like in the combustion process of the polymers can be reduced by virtue of the adsorption and oxidation properties of the MOFs on CO; in addition, MOFs materials decompose NH at high temperatures 3 And the flame-retardant gas and the metal oxide can achieve the flame-retardant purpose of the polymer material by diluting the concentration of the combustion-supporting and combustible gas such as oxygen and isolating air. Although MOFs have been used in the field of improving flame retardant properties of polymers, studies on improving polymer properties as fillers are still in the initial stage, and single MOFs have problems of general flame retardant and smoke suppressant effects, easy agglomeration in polymers, low thermal stability, and the like.
In addition, when inorganic powder such as boehmite is added into a polymer matrix as a flame retardant to realize a flame retardant effect, agglomeration is easy to occur, so that dispersion is uneven, and the mechanical property of the polymer is rapidly deteriorated; even when the surface of an inorganic powder such as boehmite is modified in various ways; at high loadings, boehmite, although improving the flame retardant effect of the polymer, also severely impairs the mechanical properties of the polymer.
The invention content is as follows:
the invention aims to solve the problems that MOFs in a polymer are easy to agglomerate, the thermal stability is not high and an inorganic flame retardant seriously damages the mechanical property of the polymer in the prior art, and provides a smoke suppressant, a preparation method thereof and a polymer composite material.
In order to achieve the above object, the present invention provides in a first aspect a smoke suppressant comprising an inorganic flame retardant and metal-organic framework particles supported on the inorganic flame retardant; the metal organic framework particles are formed by self-assembling organic ligands and metal ions through the metal ions as connection points; the metal ion is at least one selected from transition metal ions.
In a second aspect, the invention provides a method for preparing a smoke suppressant, which comprises mixing an inorganic flame retardant, an organic ligand and a transition metal salt in the presence of a solvent, and transferring the mixed system obtained by mixing into a reaction kettle for reaction to obtain the smoke suppressant.
In a third aspect, the present invention provides a smoke suppressant prepared according to the foregoing process.
In a fourth aspect, the invention provides a polymer composite comprising a polymer matrix and the smoke suppressant described above.
The invention has the beneficial effects that: according to the invention, the surface of the inorganic flame retardant is coated with the metal organic framework material, and the inorganic flame retardant and the metal organic framework material can generate a good synergistic effect, so that the compatibility of the inorganic flame retardant and a polymer matrix can be improved, and the agglomeration of the metal organic framework material can be inhibited, thereby improving the smoke suppression effect and the mechanical property of the polymer composite material.
Description of the drawings:
FIG. 1 is a chart of the infrared spectra of boehmite, zr-MOF and smoke suppressant A1 according to the invention;
FIG. 2 is an XRD pattern of boehmite, zr-MOF and a smoke suppressant A1 according to the invention;
FIG. 3 is an SEM image of a smoke suppressant A1 of the present invention;
FIG. 4 is an SEM image of a smoke suppressant A10 of the present invention;
FIG. 5 is an SEM photograph of the polyvinyl chloride composite material D1 of the present invention after burning;
FIG. 6 is an SEM photograph of the polyvinyl chloride composite material C1 of the present invention after burning.
The specific implementation mode is as follows:
in order to make the technical means, the original characteristics, the achieved purposes and the effects of the invention easy to understand, the invention is further explained by combining the specific embodiments and the drawings.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For numerical ranges, each range between its endpoints and individual point values, and each individual point value can be combined with each other to give one or more new numerical ranges, and such numerical ranges should be construed as specifically disclosed herein.
The invention provides a smoke suppressant, which comprises an inorganic flame retardant and metal organic framework particles (MOF) loaded on the inorganic flame retardant; the metal organic framework particles are formed by self-assembling organic ligands and metal ions through the metal ions as connecting points.
The metal ion is at least one selected from transition metal ions.
By coating a layer of metal organic framework material on the surface of the inorganic flame retardant, the compatibility of the inorganic flame retardant and a polymer matrix can be improved, and the agglomeration of the metal organic framework material can be inhibited, so that the smoke suppression effect and the mechanical property of the polymer composite material are improved.
The invention has no special requirements on the particle size and the appearance of the inorganic flame retardant, and the particle size can be micron-sized or nano-sized; the micro-morphology can be at least one of spherical, spheroidal, lamellar, fibrous or blocky.
In the invention, the inorganic flame retardant is an inorganic substance with flame retardant property; preferably, the inorganic flame retardant is selected from at least one of boehmite, hydrotalcite, attapulgite, magnesium oxide, aluminum oxide and hydroxide; the hydroxide may be at least one of a composite hydroxide, magnesium hydroxide and aluminum hydroxide, and the composite hydroxide may be known to those skilled in the art, and may be, for example, magnesium aluminum double hydroxide.
In the present invention, the organic ligand is at least one selected from the group consisting of terephthalic acid and its derivatives, trimellitic acid, 2-aminoterephthalic acid, 2-methylimidazole and benzimidazole.
According to the invention, the flame retardant effect of the smoke suppressant can be improved by introducing the flame retardant element; preferably, said metal ion is selected from Zr 4+ 、Zn 2+ 、Fe 3+ 、Ni 2+ 、Co 2+ 、Mo 3+ 、Sn 4+ 、Sb 5+ And Mn 2+ At least one of; further preferably Zr 4+ 、Zn 2+ 、Ni 2+ And Co 2+ At least one of (1).
According to the present invention, preferably, the mass ratio of the inorganic flame retardant to the metal-organic framework particles (MOF) is (1-10): 1, which may be, for example, 1.
The present invention also provides a method of preparing a smoke suppressant, the method comprising: in the presence of a solvent, mixing an inorganic flame retardant, an organic ligand and a transition metal salt, and then transferring a mixed system obtained by mixing into a reaction kettle for reaction to obtain the smoke suppressant.
In some preferred embodiments of the present invention, the method further comprises:
1) Dispersing an inorganic flame retardant in a solvent to obtain a suspension A;
dispersing an organic ligand in a solvent to obtain a solution B;
dispersing a transition metal salt in a solvent to obtain a solution C;
2) And then dropwise adding the solution B into the suspension A, then adding the solution C to obtain a mixed system, and then transferring the mixed system into a reaction kettle for reaction to obtain the smoke suppressant.
In the invention, the inorganic flame retardant is at least one selected from boehmite, hydrotalcite, attapulgite, magnesium oxide, aluminum oxide and hydroxide; the hydroxide may be at least one of a composite hydroxide, magnesium hydroxide and aluminum hydroxide, and the composite hydroxide may be known to those skilled in the art, and may be, for example, magnesium aluminum double hydroxide.
In the present invention, the organic ligand is at least one selected from the group consisting of terephthalic acid and its derivatives, trimellitic acid, 2-aminoterephthalic acid, 2-methylimidazole and benzimidazole.
In the present invention, the transition metal salt is a soluble transition metal salt, and may be at least one of a transition metal sulfate, a transition metal nitrate, and a transition metal hydrochloride, for example. Preferably, the transition metal salt is selected from at least one of zirconium salt, zinc salt, iron salt, nickel salt, cobalt salt, molybdenum salt, tin salt, antimony salt and manganese salt; further preferably at least one of a zirconium salt, a zinc salt, a nickel salt and a cobalt salt.
In the present invention, the solvent should be selected reasonably according to the kinds of transition metal ions and ligands; preferably water or an organic solvent; the kind of the organic solvent may be known to those skilled in the art, and may be, for example, at least one of N, N-dimethylformamide, N-dimethylacetamide and N, N-diethylformamide.
Preferably, the molar ratio of the organic ligand to the transition metal salt is 1 (0.5-10).
Preferably, the reaction conditions include: the temperature is 120-140 ℃ and the time is 12-96h.
The invention also provides a smoke suppressant prepared by the method.
The invention also provides a polymer composite comprising a polymer matrix and the smoke suppressant.
Preferably, the polymer matrix is selected from at least one of polyvinyl chloride, polypropylene, polyethylene, polystyrene, polyphenylene oxide, polyamide, polycarbonate, epoxy resin, polyurethane, acrylic resin, polyacrylonitrile resin, polyvinyl alcohol resin, bismaleimide resin, polyimide resin, cyanate ester resin, silicone rubber, and copolymers thereof. The copolymer includes, but is not limited to, propylene/ethylene copolymer resin, ethylene/vinyl acetate copolymer resin, acrylonitrile/butadiene/styrene copolymer resin.
According to the present invention, the smoke suppressant is preferably used in an amount of 5 to 80 parts, preferably 10 to 50 parts, and more preferably 10 to 30 parts, based on 100 parts of the total weight of the polymer composite.
According to the present invention, it is preferable that at least one of a plasticizer, a stabilizer and a lubricant is further contained in the polymer composite. It is needless to say that additives such as a filler, a compatibilizer, an antistatic agent, a colorant, a flame retardant, an antioxidant, a light stabilizer, and a mold release agent may be contained.
According to the present invention, preferably, the plasticizer is selected from at least one of trioctyl trimellitate, dioctyl terephthalate, dioctyl glycol, and tricresyl phosphate. Other plasticizers known in the art may also be employed.
According to the present invention, preferably, the stabilizer is selected from at least one of zinc calcium stabilizer, bisphenol a, tribasic lead sulfate, lead stearate, and organotin compound. Other stabilizers known in the art may also be employed.
According to the present invention, preferably, the lubricant is selected from at least one of calcium stearate, liquid paraffin, stearic acid, and silicone oil. Other lubricants known in the art may also be used.
The present invention will be described in detail below by way of examples. In the following examples of the present invention,
DMF is N, N-dimethylformamide for short.
The oxygen index is tested according to the method of GB/T2406-2009, and the size of a sample bar is 130mm multiplied by 6.5mm multiplied by 3mm.
The total smoke release rate is the ratio of the total smoke released to the exposed area of the sample from the start of ignition to the time of extinction. The total smoke release rate is measured by a CCT type cone calorimeter test method according to ISO5660-1: 2002. The sample sizes were: 100mm X3.0 mm (length X width X thickness), heat flux 35KW/m 2 Exhaust flow of 86.4m 3 /h。
The tensile strength is tested according to GB/T1040.3-2006, the displacement speed is 20mm/min, dumbbell type sample bars are adopted, and the average value of the tensile strength of 5 sample bars is taken as a test result.
In the following examples, boehmite was commercially available with a particle size of 200nm.
Example 1
1. Preparation of Smoke suppressant A1
0.414g of boehmite was dispersed ultrasonically in 20mL of DMF to give suspension A.
0.181g of terephthalic acid was ultrasonically dispersed in 15mL of DMF to give solution B.
0.233g of zirconium chloride was ultrasonically dispersed in 15mL of DMF to give solution C.
Dropwise adding the solution B into the suspension A under the stirring state, after dropwise adding, dropwise adding the solution C into the suspension A to obtain a mixed system, transferring the mixed system into a 100mL high-temperature high-pressure reaction kettle, reacting at 120 ℃ for 48 hours, centrifuging, washing and drying a reaction product to obtain the smoke suppressant A1.
The smoke suppressant A1 comprises boehmite and a metal-organic framework (Zr-MOF) grown on the surface of the boehmite, wherein the mass ratio of the boehmite to the Zr-MOF is 4.
2. Preparation of polyvinyl chloride composite material C1
50 parts by mass of polyvinyl chloride, 21 parts by mass of trioctyl trimellitate, 0.5 part by mass of bisphenol A, 0.5 part by mass of calcium stearate, 3 parts by mass of a zinc-calcium stabilizer and 25 parts by mass of a smoke suppressant A1 were charged into an internal mixer, and kneaded at 170 ℃ and then vulcanized (170 ℃) in a plate vulcanizer to obtain a polyvinyl chloride composite C1, the properties of which are shown in Table 1.
FIG. 1 is an infrared spectrum of boehmite, zr-MOF and smoke suppressant A1, as can be seen in FIG. 1: after the metal organic framework (Zr-MOF) is successfully loaded, the absorption peaks of boehmite and the metal organic framework (Zr-MOF) are not obviously changed, which shows that the metal organic framework (Zr-MOF) can be well compounded with boehmite.
FIG. 2 is an XRD pattern of boehmite, zr-MOF and smoke suppressant A1, as can be seen in FIG. 2: the smoke suppressant A1 contains diffraction peaks of Zr-MOF and boehmite, and crystal forms of the two substances are quite intact, which shows that the load and preparation of a metal organic framework cannot influence the boehmite.
Fig. 3 is an SEM image of smoke suppressant A1, as can be seen from fig. 3: the boehmite surface is uniformly loaded with a nano metal organic framework.
Example 2
1. Preparation of smoke suppressant A2
0.621g of boehmite was ultrasonically dispersed in 20mL of DMF to give suspension A.
0.181g of terephthalic acid was ultrasonically dispersed in 15mL of DMF to give solution B.
0.233g of zirconium chloride was ultrasonically dispersed in 15mL of DMF to give solution C.
Dropwise adding the solution B into the suspension A under the stirring state, after dropwise adding, dropwise adding the solution C into the suspension A to obtain a mixed system, transferring the mixed system into a 100mL high-temperature high-pressure reaction kettle, reacting at 120 ℃ for 48 hours, centrifuging, washing and drying a reaction product to obtain the smoke suppressant A2.
The smoke suppressant A2 comprises boehmite and a metal organic framework (Zr-MOF) growing on the surface of the boehmite, wherein the mass ratio of the boehmite to the Zr-MOF is 6.
2. Preparation of polyvinyl chloride composite material C2
By mass, 50 parts of polyvinyl chloride, 21 parts of trioctyl trimellitate, 0.5 part of bisphenol a, 0.5 part of calcium stearate, 3 parts of zinc-calcium stabilizer and 25 parts of smoke suppressant A2 were charged into an internal mixer, and kneaded at 170 ℃, followed by vulcanization in a plate vulcanizer (170 ℃) to obtain a polyvinyl chloride composite material C2, the properties of which are shown in table 1.
Example 3
1. Preparation of smoke suppressant A3
0.828g of boehmite was ultrasonically dispersed in 20mL of DMF to give suspension A.
0.181g of terephthalic acid was ultrasonically dispersed in 15mL of DMF to give solution B.
0.233g of zirconium chloride was ultrasonically dispersed in 15mL of DMF to give solution C.
Dropwise adding the solution B into the suspension A under the stirring state, after dropwise adding, dropwise adding the solution C into the suspension A to obtain a mixed system, transferring the mixed system into a 100mL high-temperature high-pressure reaction kettle, reacting at 120 ℃ for 48 hours, centrifuging, washing and drying a reaction product to obtain the smoke suppressant A3.
The smoke suppressant A3 comprises boehmite and a metal organic framework (Zr-MOF) growing on the surface of the boehmite, wherein the mass ratio of the boehmite to the Zr-MOF is 8.
2. Preparation of polyvinyl chloride composite material C3
50 parts by mass of polyvinyl chloride, 21 parts by mass of trioctyl trimellitate, 0.5 part by mass of bisphenol A, 0.5 part by mass of calcium stearate, 3 parts by mass of a zinc-calcium stabilizer and 25 parts by mass of a smoke suppressant A3 were charged into an internal mixer, and kneaded at 170 ℃ and then vulcanized (170 ℃) in a plate vulcanizer to obtain a polyvinyl chloride composite C3 having the properties shown in Table 1.
Example 4
The process of example 3 was followed except that: the mass ratio of boehmite to Zr-MOF was 2.
The polyvinyl chloride composite material C4 is obtained, and the properties of the polyvinyl chloride composite material are shown in Table 1.
TABLE 1
As can be seen from table 1: when the mass ratio of the boehmite to the Zr-MOF is 4.
Example 5
50 parts by mass of polyvinyl chloride, 21 parts by mass of trioctyl trimellitate, 0.5 part by mass of bisphenol A, 0.5 part by mass of calcium stearate, 3 parts by mass of a zinc-calcium stabilizer and 5 parts by mass of a smoke suppressant A1 were charged into an internal mixer, and kneaded at 170 ℃ and then vulcanized (170 ℃) in a plate vulcanizer to obtain a polyvinyl chloride composite C5 having the properties shown in Table 2.
Example 6
50 parts by mass of polyvinyl chloride, 21 parts by mass of trioctyl trimellitate, 0.5 part by mass of bisphenol A, 0.5 part by mass of calcium stearate, 3 parts by mass of a zinc-calcium stabilizer and 10 parts by mass of a smoke suppressant A1 were charged into an internal mixer, and kneaded at 170 ℃ and then vulcanized (170 ℃) in a plate vulcanizer to obtain a polyvinyl chloride composite C6 having the properties shown in Table 2.
Example 7
50 parts by mass of polyvinyl chloride, 21 parts by mass of trioctyl trimellitate, 0.5 part by mass of bisphenol A, 0.5 part by mass of calcium stearate, 3 parts by mass of a zinc-calcium stabilizer and 15 parts by mass of a smoke suppressant A1 were charged into an internal mixer, and kneaded at 170 ℃ and then vulcanized (170 ℃) in a plate vulcanizer to obtain a polyvinyl chloride composite C7, the properties of which are shown in Table 2.
Example 8
50 parts by mass of polyvinyl chloride, 21 parts by mass of trioctyl trimellitate, 0.5 part by mass of bisphenol A, 0.5 part by mass of calcium stearate, 3 parts by mass of a zinc-calcium stabilizer and 20 parts by mass of a smoke suppressant A1 were charged into an internal mixer, and kneaded at 170 ℃ and then vulcanized (170 ℃) in a plate vulcanizer to obtain a polyvinyl chloride composite C8, the properties of which are shown in Table 2.
TABLE 2
As can be seen from table 2: under the condition that other conditions are not changed, the higher the using amount of the smoke suppressant is, the higher the oxygen index of the polyvinyl chloride composite material is, the lower the total smoke release rate is, and the higher the tensile strength is; the metal MOF and the inorganic flame retardant can generate a synergistic effect, and the smoke suppressant provided by the application can not cause the deterioration of the mechanical property of the polyvinyl chloride, but can greatly improve the mechanical property of the polyvinyl chloride.
Example 9
1. Preparation of smoke suppressant A9
0.414g of boehmite was ultrasonically dispersed in 20mL of DMF to give suspension A.
0.181g of terephthalic acid was ultrasonically dispersed in 15mL of DMF to give solution B.
0.162g of ferric chloride was ultrasonically dispersed in 15mL of DMF to give solution C.
Dropwise adding the solution B into the suspension A under the stirring state, after dropwise adding, dropwise adding the solution C into the suspension A to obtain a mixed system, transferring the mixed system into a 100mL high-temperature high-pressure reaction kettle, reacting at 140 ℃ for 72 hours, centrifuging, washing and drying a reaction product to obtain the smoke suppressant A9.
The smoke suppressant A9 comprises boehmite and a metal-organic framework (Fe-MOF) growing on the surface of the boehmite, wherein the mass ratio of the boehmite to the Fe-MOF is 4;
2. preparation of polyvinyl chloride composite material C9
By mass, 50 parts of polyvinyl chloride, 21 parts of trioctyl trimellitate, 0.5 part of bisphenol a, 0.5 part of calcium stearate, 3 parts of zinc-calcium stabilizer and 25 parts of smoke suppressant A9 were charged into an internal mixer, and kneaded at 170 ℃, followed by vulcanization in a plate vulcanizer (170 ℃) to obtain a polyvinyl chloride composite material C9, the properties of which are shown in table 3.
Example 10
1. Preparation of smoke suppressant A10
1) Preparation of magnesium-aluminum layered double hydroxide (MgAl-LDH):
MgCl is added according to the ratio of the mass 3 2 ·6H 2 O and AlCl 3 ·6H 2 Dispersing O into deionized water with the temperature of 60 ℃ and the volume of 1000mL, dropwise adding 25% ammonia water to adjust the pH value of the mixed solution to 9-9.5, then heating to 80 ℃, and reacting for 8 hours under a stirring state. And after the reaction is finished, cooling to room temperature, filtering the product, washing with deionized water and ethanol, and drying in an oven at the temperature of 90 ℃ for 24 hours to obtain MgAl-LDH.
2) Growing metal organic framework (Zr-MOF) on surface of magnesium-aluminum layered double hydroxide
0.414g of MgAl-LDH was ultrasonically dispersed in 20mL of DMF to give suspension A.
0.181g of terephthalic acid was ultrasonically dispersed in 15mL of DMF to give solution B.
0.162g of zirconium chloride was ultrasonically dispersed in 15mL of DMF to give solution C.
Dropwise adding the solution B into the suspension A under the stirring state, after dropwise adding, dropwise adding the solution C into the suspension A to obtain a mixed system, transferring the mixed system into a 100mL high-temperature high-pressure reaction kettle, and reacting at 120 ℃ for 48 hours to obtain the smoke suppressant A10.
The smoke suppressant A10 comprises magnesium-aluminum layered double hydroxide (MgAl-LDH) and a metal organic framework (Zr-MOF) growing on the surface of the magnesium-aluminum layered double hydroxide, wherein the mass ratio of the magnesium-aluminum layered double hydroxide to the Zr-MOF is 4.
Fig. 4 is an SEM image of smoke suppressant a10, as can be seen from fig. 4: the surface of the magnesium-aluminum layered double hydroxide (MgAl-LDH) is uniformly loaded with a nano metal organic framework.
2. Preparation of polyvinyl chloride composite material C10
50 parts by mass of polyvinyl chloride, 21 parts by mass of trioctyl trimellitate, 0.5 part by mass of bisphenol A, 0.5 part by mass of calcium stearate, 3 parts by mass of a zinc-calcium stabilizer and 25 parts by mass of a smoke suppressant A10 were charged into an internal mixer, and kneaded at 170 ℃ and then vulcanized (170 ℃) in a plate vulcanizer to obtain a polyvinyl chloride composite C10, the properties of which are shown in Table 3.
Example 11
1. Preparation of smoke suppressant A11
0.414g of boehmite was ultrasonically dispersed in 20mL of DMF to give suspension A.
0.36g of 2-methylimidazole is taken and dissolved in 96mL of deionized water, 5.80mL of triethylamine is added, and the triethylamine is fully dissolved by adopting an ultrasonic oscillation method to obtain a solution B.
0.298g of Zn (NO) is taken 3 ) 2 ·6H 2 O was dissolved in 24mL deionized water to give solution C.
And uniformly mixing the solution B and the solution C at room temperature, adding the boehmite suspension, continuously stirring for 10 hours, centrifuging the solution (4000 r/min,3 minutes) after stirring is finished, transferring the mixed system into a 100mL high-temperature high-pressure reaction kettle, reacting for 72 hours at 130 ℃, centrifuging, washing and drying the reaction product to obtain the smoke suppressant A11.
The smoke suppressant A11 comprises boehmite and a metal organic framework (ZIF-8) growing on the surface of the boehmite, wherein the mass ratio of the boehmite to the ZIF-8 is 4;
2. preparation of polyvinyl chloride composite material C11
By mass, 50 parts of polyvinyl chloride, 21 parts of trioctyl trimellitate, 0.5 part of bisphenol a, 0.5 part of calcium stearate, 3 parts of zinc-calcium stabilizer and 25 parts of smoke suppressant a11 were charged into an internal mixer, and kneaded at 170 ℃, followed by vulcanization in a plate vulcanizer (170 ℃) to obtain a polyvinyl chloride composite material C11, the properties of which are shown in table 3.
TABLE 3
Comparative example 1
The process of example 1 was followed except that: the smoke suppressant is not added, and the concrete steps are as follows:
50 parts by mass of polyvinyl chloride, 21 parts by mass of trioctyl trimellitate, 0.5 part by mass of bisphenol A, 0.5 part by mass of calcium stearate, and 3 parts by mass of a zinc-calcium stabilizer were charged into an internal mixer, and kneaded at 170 ℃ and then vulcanized (170 ℃) in a press vulcanizer to obtain a polyvinyl chloride composite material D1, the properties of which are shown in Table 4.
Comparative example 2
The process of example 1 was followed except that: boehmite was used instead of smoke suppressant A1, as follows:
50 parts by mass of polyvinyl chloride, 21 parts by mass of trioctyl trimellitate, 0.5 part by mass of bisphenol A, 0.5 part by mass of calcium stearate, 3 parts by mass of a zinc-calcium stabilizer and 25 parts by mass of boehmite were charged into an internal mixer, and they were kneaded at 170 ℃ and then vulcanized in a plate vulcanizer (170 ℃ C.) to obtain a polyvinyl chloride composite D2 whose properties are shown in Table 4.
Comparative example 3
The process of example 1 was followed except that: when the smoke suppressant is prepared, boehmite is not added, namely metal organic framework particles (MOF) are adopted as the smoke suppressant, and the specific steps are as follows:
1. preparation of smoke suppressant B3 (Zr-MOF):
0.181g of terephthalic acid was ultrasonically dispersed in 15mL of DMF to give solution B.
0.233g of zirconium chloride was ultrasonically dispersed in 15mL of DMF to give solution C.
Dropwise adding the solution C into the solution B under the stirring state to obtain a mixed system, transferring the mixed system into a 100mL high-temperature high-pressure reaction kettle, reacting at 120 ℃ for 48 hours, centrifuging, washing and drying a reaction product to obtain a smoke suppressant B3; the smoke suppressant B3 is Zr-MOF.
2. Preparation of polyvinyl chloride composite material D3
50 parts by mass of polyvinyl chloride, 21 parts by mass of trioctyl trimellitate, 0.5 part by mass of bisphenol A, 0.5 part by mass of calcium stearate, 3 parts by mass of a zinc-calcium stabilizer and 25 parts by mass of a smoke suppressant B3 were charged into an internal mixer, and kneaded at 170 ℃ and then vulcanized (170 ℃) in a plate vulcanizer to obtain a polyvinyl chloride composite D3, the properties of which are shown in Table 4.
Comparative example 4
1. Preparation of smoke suppressant B4: physically blending boehmite and a smoke suppressant B3 according to the mass ratio of 4;
2. preparation of polyvinyl chloride composite D4
By mass, 50 parts of polyvinyl chloride, 21 parts of trioctyl trimellitate, 0.5 part of bisphenol a, 0.5 part of calcium stearate, 3 parts of zinc-calcium stabilizer and 25 parts of smoke suppressant B4 were charged into an internal mixer, and kneaded at 170 ℃, followed by vulcanization in a plate vulcanizer (170 ℃) to obtain a polyvinyl chloride composite material D4, the properties of which are shown in table 4.
TABLE 4
As can be seen from table 4: the adoption of boehmite as a smoke suppressant, the adoption of metal organic framework particles (MOF) as a smoke suppressant, or the adoption of a mixture of boehmite and metal organic framework particles (MOF) as a smoke suppressant cannot achieve flame-retardant and smoke-suppressing performances and mechanical properties comparable to those of the smoke suppressant.
FIG. 5 is an SEM photograph of the polyvinyl chloride composite D1 after burning; as can be seen from fig. 5: the carbon layer formed after the polyvinyl chloride composite material E is combusted obviously has a loose and porous structure, large pores and irregular surface.
FIG. 6 is an SEM image of polyvinyl chloride composite C1 after combustion; as can be seen in fig. 6: the carbon layer formed after the polyvinyl chloride composite material C1 is burnt is compact, the porosity is low, and the surface of the carbon layer is smooth. This also explains why the flame retardant and smoke suppressant properties of the PVC material are greatly improved after the smoke suppressant of the present invention is added, because the dense carbon layer prevents the ingress of oxygen, slowing the combustion of the PVC, and also inhibits the escape of small particle smoke, reducing the smoke.
Examples 12 to 14 and comparative example 5
The smoke suppressant A1 and EVA were added to an internal mixer, and mixed at 150 ℃ followed by vulcanization (150 ℃) in a press vulcanizer to obtain an EVA composite material. The amounts of EVA and smoke suppressant A1 are shown in Table 5, and the properties of the EVA composites are shown in Table 5.
TABLE 5
As can be seen from table 5: the smoke suppressant can obtain excellent flame-retardant and smoke-suppressing properties when applied to the EVA material, and improves the mechanical properties of the EVA material.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. A smoke suppressant is characterized in that: the smoke suppressant comprises an inorganic flame retardant and metal organic framework particles loaded on the inorganic flame retardant; the metal organic framework particles are formed by self-assembling organic ligands and metal ions through the metal ions as connection points;
the metal ion is at least one selected from transition metal ions.
2. The smoke suppressant of claim 1, wherein: the metal ion is selected from Zr 4+ 、Zn 2+ 、Fe 3+ 、Ni 2+ 、Co 2+ 、Mo 3+ 、Sn 4+ 、Sb 5+ And Mn 2+ At least one of (a); preferably Zr 4+ 、Zn 2+ 、Ni 2+ And Co 2+ At least one of;
preferably, the inorganic flame retardant is at least one selected from boehmite, hydrotalcite, attapulgite, magnesium oxide, aluminum oxide and hydroxide;
preferably, the organic ligand is selected from at least one of terephthalic acid and its derivatives, trimellitic acid, 2-aminoterephthalic acid, 2-methylimidazole and benzimidazole;
preferably, the mass ratio of the inorganic flame retardant to the metal-organic framework particles is (1-10): 1, preferably (4-8): 1.
3. A method of preparing a smoke suppressant, comprising: the method comprises the following steps: in the presence of a solvent, mixing an inorganic flame retardant, an organic ligand and a transition metal salt, and then transferring a mixed system obtained by mixing into a reaction kettle for reaction to obtain the smoke suppressant.
4. The method of claim 3, wherein: the inorganic flame retardant is selected from at least one of boehmite, hydrotalcite, attapulgite, magnesium oxide, aluminum oxide and hydroxide;
preferably, the organic ligand is selected from at least one of terephthalic acid and its derivatives, trimellitic acid, 2-aminoterephthalic acid, 2-methylimidazole and benzimidazole;
preferably, the transition metal salt is a soluble transition metal salt, preferably at least one of zirconium salt, zinc salt, iron salt, nickel salt, cobalt salt, molybdenum salt, tin salt, antimony salt and manganese salt; further preferably at least one of a zirconium salt, a zinc salt, a nickel salt and a cobalt salt.
5. The method according to claim 3 or 4, characterized in that: the molar ratio of the organic ligand to the transition metal salt is 1 (0.5-10);
preferably, the conditions of the reaction include: the temperature is 120-140 ℃ and the time is 12-96h.
6. A smoke suppressant prepared according to the process of any one of claims 3 to 5.
7. A polymer composite characterized by: comprising a polymer matrix and the smoke suppressant of claim 1 or 6.
8. The polymer composite of claim 7, wherein: the polymer matrix is selected from at least one of polyvinyl chloride, polypropylene, polyethylene, polystyrene, polyphenyl ether, polyamide, polycarbonate, epoxy resin, polyurethane, acrylic resin, polyacrylonitrile resin, polyvinyl alcohol resin, bismaleimide resin, polyimide resin, cyanate resin, silicon rubber and copolymers thereof.
9. The polymer composite according to claim 7 or 8, characterized in that: the amount of the smoke suppressant is 5-80 parts, preferably 10-50 parts, based on 100 parts of the total weight of the polymer composite.
10. The polymer composite according to any one of claims 7 to 9, wherein: the polymer composite material also contains at least one of a plasticizer, a stabilizer and a lubricant;
preferably, the plasticizer is selected from at least one of trioctyl trimellitate, dioctyl terephthalate, dioctyl oxalate and tricresyl phosphate;
preferably, the stabilizer is selected from at least one of zinc calcium stabilizer, bisphenol a, tribasic lead sulfate, lead stearate and organotin compound;
preferably, the lubricant is selected from at least one of calcium stearate, liquid paraffin, stearic acid, and silicone oil.
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