CN117362754A - Efficient flame-retardant smoke suppressant, composite material containing efficient flame-retardant smoke suppressant and preparation method of composite material - Google Patents
Efficient flame-retardant smoke suppressant, composite material containing efficient flame-retardant smoke suppressant and preparation method of composite material Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 85
- 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 82
- 239000000779 smoke Substances 0.000 title claims abstract description 79
- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000013173 zeolitic imidazolate framework-9 Substances 0.000 claims abstract description 11
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229960003638 dopamine Drugs 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 35
- 239000000243 solution Substances 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 14
- 239000011218 binary composite Substances 0.000 claims description 12
- 239000004014 plasticizer Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 10
- 239000006077 pvc stabilizer Substances 0.000 claims description 9
- 239000011347 resin Substances 0.000 claims description 9
- 229920005989 resin Polymers 0.000 claims description 9
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims description 9
- 229910021645 metal ion Inorganic materials 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000007731 hot pressing Methods 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000006174 pH buffer Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical group OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 2
- SEQKRHFRPICQDD-UHFFFAOYSA-N N-tris(hydroxymethyl)methylglycine Chemical compound OCC(CO)(CO)[NH2+]CC([O-])=O SEQKRHFRPICQDD-UHFFFAOYSA-N 0.000 claims description 2
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 2
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 claims description 2
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 claims description 2
- FTXJFNVGIDRLEM-UHFFFAOYSA-N copper;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O FTXJFNVGIDRLEM-UHFFFAOYSA-N 0.000 claims description 2
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 claims description 2
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 claims description 2
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 12
- 230000001629 suppression Effects 0.000 abstract description 8
- XZXAIFLKPKVPLO-UHFFFAOYSA-N cobalt(2+);dinitrate;hydrate Chemical compound O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XZXAIFLKPKVPLO-UHFFFAOYSA-N 0.000 abstract description 7
- 230000002195 synergetic effect Effects 0.000 abstract description 7
- 239000000178 monomer Substances 0.000 abstract description 3
- 238000013329 compounding Methods 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- 231100000252 nontoxic Toxicity 0.000 abstract 1
- 230000003000 nontoxic effect Effects 0.000 abstract 1
- 239000004800 polyvinyl chloride Substances 0.000 description 62
- 229920000915 polyvinyl chloride Polymers 0.000 description 61
- 238000002485 combustion reaction Methods 0.000 description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 231100000331 toxic Toxicity 0.000 description 5
- 230000002588 toxic effect Effects 0.000 description 5
- 241000282414 Homo sapiens Species 0.000 description 4
- 229910052787 antimony Inorganic materials 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000006378 damage Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003517 fume Substances 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 206010000369 Accident Diseases 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical group [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000006084 composite stabilizer Substances 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003000 extruded plastic Substances 0.000 description 1
- -1 flame retardant compound Chemical class 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000002991 molded plastic Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001690 polydopamine Polymers 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- JNXDCMUUZNIWPQ-UHFFFAOYSA-N trioctyl benzene-1,2,4-tricarboxylate Chemical group CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C(C(=O)OCCCCCCCC)=C1 JNXDCMUUZNIWPQ-UHFFFAOYSA-N 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
-
- 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
- C08K3/2279—Oxides; Hydroxides of metals of antimony
-
- 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
- C08K3/38—Boron-containing compounds
-
- 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
- C08K3/38—Boron-containing compounds
- C08K2003/387—Borates
-
- 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 provides a high-efficiency flame-retardant smoke suppressant, a composite material containing the high-efficiency flame-retardant smoke suppressant and a preparation method thereof, wherein the high-efficiency flame-retardant smoke suppressant is prepared by compounding ZB, PDA and ZIF-9, and the preparation method comprises the following steps: firstly introducing dopamine monomer into ZB dispersion liquid to prepare PDA@ZB, and then adding the PDA@ZB into ethanol solution of cobalt nitrate hydrate and benzimidazole to obtain ZIF-9@PDA@ZB high-efficiency flame-retardant smoke suppressant; the high-efficiency flame-retardant smoke suppressant prepared by the method is halogen-free and nontoxic, can play a synergistic flame-retardant role with antimony trioxide, has an obvious smoke suppression effect, is uniformly dispersed in a polymer, and can be added into the polymer to prepare a composite material containing the high-efficiency flame-retardant smoke suppressant.
Description
Technical Field
The invention relates to the technical field of flame retardance, in particular to a high-efficiency flame retardance smoke suppressant, a composite material containing the high-efficiency flame retardance smoke suppressant and a preparation method.
Background
Soft polyvinyl chloride (PVC) is widely used in the fields of construction, agriculture, automobile industry, home appliances, electronic appliances, etc. because of its advantages of good plasticity, excellent mechanical properties, good chemical resistance, weather resistance, etc. Rigid, pure PVC is inherently flame-retardant, but because of the large amount of flammable plasticizers contained in the soft PVC material, soft PVC is very flammable, and burns with large amounts of toxic, corrosive fumes, which severely limits its use in some applications.
Flame retardants currently used in flexible PVC include antimony-based, phosphorus-based, nitrogen-based, silicon-based, intumescent flame retardant systems and synergistic systems of two or more flame retardants. Among them, antimony flame retardants such as antimony trioxide exert a strong halogen-antimony synergistic flame retardant effect with chlorine element in PVC, and only a small amount of antimony trioxide is added to obviously improve the inflammability of soft PVC, but is considered as the most efficient PVC flame retardant, but the total amount of toxic smoke generated during the combustion of soft PVC cannot be reduced or even increased, once a fire disaster occurs, the life safety of human beings is seriously endangered, the ecological environment is seriously damaged by the generated toxic smoke, and the load-bearing structure such as metal is damaged by the generated corrosive smoke to further increase the disaster degree.
As disclosed in chinese patent document CN202210529920.7, a flame-retardant antistatic soft PVC material and a preparation method thereof are disclosed, wherein the flame-retardant antistatic soft PVC material comprises the following raw materials in parts by weight: 100 parts of PVC and 30-100 parts of plasticizer; 4-6 parts of stabilizer, 0.2-1 part of lubricant, 1-5 parts of processing aid, 1-8 parts of composite flame retardant, 5-40 parts of hydroxide, 5-20 parts of conductive filler, 0.1-1.5 parts of aluminate and 0.05-1 part of graphene; the composite flame retardant is a mixture of antimony trioxide and zinc borate in a mass ratio of 1:1.
The existing PVC flame retardant technology comprises the following defects: (1) Most of the existing smoke suppressants are low-efficiency inorganic matters, the addition amount of the existing smoke suppressants is often relatively large, however, the compatibility of the inorganic matters and organic PVC materials is poor, and the mechanical properties of PVC can be damaged; (2) The soft PVC is very inflammable due to the addition of a large amount of plasticizer, and generates a large amount of toxic smoke during combustion, thereby threatening the safety of human life and ecological environment; (3) the flame retardant effect of the existing flame retardant is single.
Aiming at the problems faced in the field of soft PVC flame retardance, it is necessary to develop a high-efficiency flame retardance smoke suppressant with good compatibility with a PVC resin matrix, and the technical problems are solved by matching with an antimony-based flame retardant applied to the field of soft PVC flame retardance.
Disclosure of Invention
In order to solve the defects in the prior art, the invention aims to provide the efficient flame-retardant smoke suppressant, the composite material containing the efficient flame-retardant smoke suppressant and the preparation method, and the prepared efficient flame-retardant smoke suppressant can achieve good flame retardance and smoke suppression effects, can not destroy the good mechanical properties of soft PVC, can widen the application field of the soft PVC, can be added into the PVC to prepare the composite material, can obviously inhibit smoke generated during the combustion of the PVC, and can provide more escape time for people in case of fire accidents.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a preparation method of an efficient flame-retardant smoke suppressant comprises the following steps:
(1) Dispersing Zinc Borate (ZB) in deionized water, regulating the pH value of the mixed solution to an alkaline environment by using a pH buffer, adding dopamine (PDA) after stirring, continuing stirring reaction, washing the product with water and ethanol for 3 times, and drying to obtain a PDA@ZB binary composite material;
(2) Dispersing the PDA@ZB binary composite material and metal ion salt in a solvent to obtain a solution A, stirring, then adding a solution B obtained by mixing benzimidazole, ammonia water and the solvent, continuously stirring for reaction, washing the product with ethanol and water for 3 times, and drying to obtain the efficient flame-retardant smoke suppressant ZIF-9@PDA@ZB.
Preferably, in the step (1), the weight-volume ratio of zinc borate, dopamine and deionized water is 1-5 g: 0.2-1 g:200mL of zinc borate with the particle size of 0.1-5 μm and one or more of spherical, rod-like and sheet-like shapes.
Preferably, in the step (1), stirring is carried out for 30-60 min under the stirring condition of 500-900 r/min, and stirring is carried out for 12-24 h under the stirring reaction condition of 500-900 r/min; the drying condition is that the drying is carried out for 12 to 24 hours at the temperature of 60 to 70 ℃.
Preferably, in the step (1), the pH buffer is tris (hydroxymethyl) aminomethane and/or N-tris (hydroxymethyl) methylglycine, and the pH of the alkaline environment is 8-9.5.
Preferably, in the step (2), in the solution A, the weight-volume ratio of the PDA@ZB binary composite material, the metal ion salt and the solvent is 1-6 g:0.5 g to 2g:50mL; in the solution B, the weight volume ratio of benzimidazole, ammonia water and solvent is 0.1-2 g:0.2 to 0.9g:20mL.
Preferably, in the step (2), the stirring condition of the solution A is 300-500 r/min for 30min; stirring the mixture for 6 to 24 hours at normal temperature; the drying condition is that the drying is carried out for 12 to 24 hours at the temperature of 60 to 70 ℃.
Preferably, in step (2), the metal ion salt is one or more of zinc nitrate hexahydrate, nickel nitrate hexahydrate, copper nitrate hexahydrate, magnesium nitrate hexahydrate, cobalt nitrate hexahydrate, zinc acetate dihydrate, nickel acetate tetrahydrate, copper acetate monohydrate, cobalt acetate tetrahydrate; the solvent is one or more of methanol, ethanol and N-N dimethylformamide.
The invention also discloses a high-efficiency flame-retardant smoke suppressant prepared by the preparation method.
The invention also claims a composite material containing the high-efficiency flame-retardant smoke suppressant, which is prepared from the following components in parts by weight: 70-90 parts of PVC resin, 30-40 parts of plasticizer, 4-6 parts of PVC stabilizer, 1-20 parts of antimonous oxide and 1-20 parts of efficient flame-retardant smoke suppressant.
The invention also claims a preparation method of the composite material, which comprises the following steps: uniformly mixing the raw materials by a double-roller open mill, and then performing hot press curing by a flat vulcanizing machine to prepare the PVC composite flame-retardant material; in the extrusion process, the temperature of a processing area is 160-180 ℃ and the extrusion time is 15-20 min; hot-pressing for 10-20 min at 175-185 deg.C and 20MPa by using plate vulcanization hot press.
Compared with the prior art, the invention has the following beneficial effects:
1) The invention provides a high-efficiency flame-retardant smoke suppressant, which is prepared by using low-toxicity inorganic ZB as a flame-retardant smoke suppressant substrate, then using a bio-based flame retardant PDA to carry out organic modification on ZB, and finally using metal ions with smoke suppression function and benzimidazole with flame retardant function to modify the material.
2) The invention provides a high-efficiency flame-retardant smoke suppressant, PDA can promote the generation of a compact carbon layer on the surface when a composite material is combusted, and plays a role of terminating free radicals generated during combustion, after ZB is organically modified by PDA, the dispersity of ZB in a polymer matrix can be increased, and the damage of inorganic ZB to the mechanical property of a polyvinyl chloride composite material is reduced; the rich metal ions in the high-efficiency flame-retardant smoke suppressant have the function of synergetic catalytic crosslinking to form carbon, so that a carbon layer is more compact and continuous, and oxygen and heat are prevented from being transferred into PVC; the flame-retardant smoke suppressant also contains rich nitrogen elements, and when the polyvinyl chloride composite material burns, non-combustible gas such as nitrogen can be released to dilute the concentration of oxygen and combustible gas, so that good flame-retardant and smoke suppression effects can be achieved, and the harm caused by fire disaster is reduced.
3) The invention provides a polyvinyl chloride composite material containing a high-efficiency flame-retardant smoke suppressant, which can effectively catalyze PVC to be degraded in advance in the initial stage of combustion, generates hydrogen chloride (HCl) gas with high density to cover the surface of a polymer, isolates oxygen with low density to prevent the polymer from further combustion, and can help the PVC composite material to form more complete, compact and carbon residue capable of effectively isolating heat, combustible matters and oxygen when being completely combusted; meanwhile, the efficient flame-retardant smoke suppressant ZIF-9@PDA@ZB provided by the invention can also effectively cooperate with antimony trioxide to play a role in synergistic flame retardance and smoke suppression on soft PVC.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart of the preparation of ZIF-9@PDA@ZB flame-retardant smoke-suppressing material in examples 1 and 2 of the invention;
FIG. 2 is a scanning electron microscope image (SEM) of a flame retardant, smoke suppressant composite of example 1 of the present invention;
FIG. 3 is a scanning electron microscope image of a flame retardant, smoke suppressant composite of example 2 of the present invention;
FIG. 4 is a graph of total smoke produced from combustion of the soft PVC composite of all examples and comparative examples;
FIG. 5 is a graph of total heat release from combustion for all of the example and comparative soft PVC composites;
FIG. 6 is a graph of thermal weight loss of all examples and comparative soft PVC composites;
FIG. 7 is a graph of carbon residue from complete combustion of all the example and comparative soft PVC composites.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the following examples. Of course, the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Unless otherwise specified, both chemical reagents and materials in the present invention are purchased through a market route or synthesized from raw materials purchased through a market route.
PVC is purchased from Weifang Langtai chemical Co., ltd, model SG-5;
the PVC stabilizer is a calcium-zinc composite stabilizer, and the model is LY21;
the plasticizer is trioctyl trimellitate.
The invention will be further illustrated by the following examples.
Preparation example 1
A preparation method of an efficient flame-retardant smoke suppressant comprises the following steps:
(1) Dispersing 5g of ZB ultrasonic wave in 200mL of water solution by stirring, regulating the pH value of the mixed solution to 8.5 by using tris (hydroxymethyl) aminomethane, magnetically stirring at 600r/min for 30min, adding 0.3g of dopamine monomer, magnetically stirring at 600r/min for reaction for 24h, washing the product with anhydrous and ethanol for 3 times, and finally drying at 65 ℃ for 18h to obtain the PDA@ZB binary composite material;
(2) Taking 5g of PDA@ZB binary composite material and 0.5g of cobalt nitrate hydrate, stirring and dispersing the binary composite material and the cobalt nitrate hydrate in 50mL of ethanol to obtain a solution A, stirring the solution A at a stirring speed of 300r/min for 30min, then adding a solution B obtained by mixing 0.1g of benzimidazole, 0.6g of ammonia water (10 wt%) and 20mL of ethanol, continuing stirring and reacting for 24h at normal temperature, washing the product with ethanol and water for 3 times, and drying at 65 ℃ for 12h to obtain the high-efficiency flame-retardant smoke suppressant, which is recorded as ZIF-9@PDA@ZB.
Preparation example 2
A preparation method of an efficient flame-retardant smoke suppressant comprises the following steps:
(1) 3g of ZB ultrasonic wave is taken, stirred and dispersed in 200mL of aqueous solution, the pH value of the mixed solution is regulated to 8 by using tris (hydroxymethyl) aminomethane, 0.2g of dopamine monomer is added after magnetic stirring for 35min at the rotating speed of 700r/min, then magnetic stirring is carried out for 24h at the rotating speed of 800r/min, the product is washed 3 times by using anhydrous and ethanol, and finally the product is dried for 12h at the temperature of 65 ℃ to obtain the PDA@ZB binary composite material;
(2) Taking 6g of PDA@ZB binary composite material and 1.48g of cobalt nitrate hydrate, stirring and dispersing the binary composite material and 1.48g of cobalt nitrate hydrate in 50mL of ethanol to obtain a solution A, stirring the solution A at a stirring speed of 300r/min for 30min, then adding a solution B obtained by mixing 0.1g of benzimidazole, 0.6g of ammonia water (10 wt%) and 20mL of ethanol, continuing stirring and reacting for 24h at normal temperature, washing the product with ethanol and water for 3 times, and drying at 65 ℃ for 12h to obtain the high-efficiency flame-retardant smoke suppressant, which is recorded as ZIF-9@PDA@ZB.
Preparation example 3
A preparation method of a flame-retardant smoke suppressant comprises the following steps:
taking 5g of zinc borate and 0.5g of cobalt nitrate hydrate, ultrasonically stirring and dispersing the zinc borate and the 0.5g of cobalt nitrate hydrate in 50mL of ethanol to obtain a solution A, stirring the solution A at a stirring speed of 300r/min for 30min, then adding a solution B obtained by mixing 0.1g of benzimidazole, 0.6g of ammonia (10wt%) and 20mL of ethanol, continuously stirring and reacting for 24h at normal temperature, washing the product with ethanol and water for 3 times, and drying at 65 ℃ for 12h to obtain the flame-retardant smoke suppressant, namely ZIF-9@ZB.
Example 1
A preparation method of a composite material containing a high-efficiency flame-retardant smoke suppressant comprises the following steps:
70g of PVC resin, 30g of plasticizer, 4g of PVC stabilizer, 3g of antimonous oxide and 5g of efficient flame-retardant smoke suppressant prepared in preparation example 1 are weighed, the materials are uniformly mixed at 180 ℃ by a two-roll open mill, and then are subjected to hot pressing for 10min at 20Mpa and 180 ℃ by a flat vulcanizing machine, and then are cooled and solidified, so that the polyvinyl chloride composite material containing the efficient flame-retardant smoke suppressant is prepared.
Example 2
A preparation method of a composite material containing a high-efficiency flame-retardant smoke suppressant comprises the following steps:
80g of PVC resin, 34g of plasticizer, 4.5g of PVC stabilizer, 3.4g of antimonous oxide and 5.7g of efficient flame-retardant smoke suppressant prepared in preparation example 2 are weighed, the materials are uniformly mixed by a two-roll open mill at 180 ℃, and then are subjected to hot pressing for 10min at 20Mpa and 180 ℃ by a flat vulcanizing machine, and then cooled and solidified, so that the polyvinyl chloride composite material containing the efficient flame-retardant smoke suppressant is prepared.
Example 3
A preparation method of a composite material containing a high-efficiency flame-retardant smoke suppressant comprises the following steps:
90g of PVC resin, 38.4g of plasticizer, 5.1g of PVC stabilizer, 3.8g of antimonous oxide and 7.7g of efficient flame-retardant smoke suppressant prepared in preparation example 2 are weighed, the materials are uniformly mixed at 180 ℃ through a two-roll open mill, and then are subjected to hot pressing for 10min at 20Mpa and 180 ℃ through a flat vulcanizing machine, and then cooled and solidified, so that the polyvinyl chloride composite material containing the efficient flame-retardant smoke suppressant is prepared.
Example 4
A preparation method of a composite material containing a high-efficiency flame-retardant smoke suppressant comprises the following steps:
90g of PVC resin, 38.4g of plasticizer, 5.1g of PVC stabilizer, 3.8g of antimonous oxide and 9g of efficient flame-retardant smoke suppressant prepared in preparation example 2 are weighed, the materials are uniformly mixed by a two-roll open mill at 180 ℃, and then are subjected to hot pressing for 10min at 20Mpa and 180 ℃ by a flat vulcanizing machine, and then cooled and solidified, so that the polyvinyl chloride composite material containing the efficient flame-retardant smoke suppressant is prepared.
Comparative example 1
A method of preparing a composite material comprising the steps of:
70g of PVC resin, 30g of plasticizer, 4g of PVC stabilizer and 3g of antimonous oxide are weighed, the materials are uniformly mixed by a double-roller open mill at 180 ℃, and then are hot-pressed for 10min at 20Mpa and 180 ℃ by a flat vulcanizing machine, and then cooled and solidified, so that the polyvinyl chloride composite material is prepared.
Comparative example 2
A preparation method of a composite material containing a flame-retardant smoke suppressant comprises the following steps:
70g of PVC resin, 30g of plasticizer, 4g of PVC stabilizer, 3g of antimonous oxide and 5g of flame-retardant smoke suppressant prepared in preparation example 3 are weighed, the materials are uniformly mixed by a double-roller open mill at 180 ℃, and then are subjected to hot pressing for 10min at 20Mpa and 180 ℃ by a flat vulcanizing machine, and then are cooled and solidified, so that the polyvinyl chloride composite material containing the flame-retardant smoke suppressant is prepared.
The composite materials prepared in examples 1 to 4 and comparative examples 1 to 2 were subjected to performance test, and reference was made to GB/T1040.2-2022 "determination of Plastic tensile Properties part 2: test conditions for molded and extruded plastics the elongation at break and the tensile strength were tested; the carbon residue of the material at 800℃was measured with a thermogravimetric analyzer (STA 2500Regulus, heating rate 20 ℃/min, initial sample weight 18 mg); limiting Oxygen Index (LOI) test was performed with an oxygen index meter (FTT 0077, UK) with sample sizes of 10cm 1cm (based on standard ASTM D2863), and 10 sets of parallel tests were averaged; the total smoke release during the combustion phase and the total smoke release during the ignition phase were measured with a Cone Calorimeter (Cone Calorimeter, instrument model TTech-GBT 16172) with reference to ISO5660, and the results are shown in Table 1.
TABLE 1 Performance test results
Note that: LOI is limiting oxygen index, TSR (flag) is total smoke release during combustion, and TSR (non-flag) is total smoke release during ignition.
From the table, it can be seen that examples 1 to 4 are excellent in flame retardance, smoke suppression and mechanical properties.
In the prior art, a certain flame retardant property is usually given to the soft PVC material in a flame retardant blending mode, but the addition amount of the flame retardant is usually large, and the mechanical property of the PVC material is adversely affected. In the invention, the inventor adopts the bio-based flame retardant compound polydopamine and ZIF-9 as the surface modifier with the smoke suppression function to carry out surface organic modification on the inorganic ZB, the modification can improve the compatibility of the ZB in PVC, and the mechanical property data of comparative example 2 and examples 1-4 show that the ZB can not cause obvious damage to the mechanical property of the PVC after modification, and the ZB can be dispersed in the PVC more uniformly after surface modification, thereby being beneficial to fully playing the smoke suppression performance of the ZB. It can be noted that the high-efficiency flame-retardant smoke suppressant provided by the invention can generate obvious synergistic flame-retardant effect with the antimonous oxide, so that the oxygen index of the soft PVC is improved, and the flame retardance of the material is improved.
The intense and massive heat release associated with combustion with the generation of large amounts of toxic and hazardous fumes is often one of the most threatening reasons for the greatest injury to human life safety and environmental pollution in the event of polymer combustion or fire. As shown in fig. 4, fig. 5 and table 1, the total smoke emission (TSR) of the 6 PVC composite materials prepared in comparative examples 1 and 2 and examples 1 to 4 can be obviously reduced when the ZB is surface-modified, and the total heat emission of the composite PVC material is obviously reduced as the content of the composite material is increased, so that the composite material of the present invention is safer in use and can provide more escape time for human beings when a fire disaster occurs. It is well known that the combustion of polymers produces a stable carbon layer that can coat the surface of the unburned polymer to isolate the combustible gaseous volatiles from contact with oxygen, thereby increasing the flame retardancy of the polymer. As is apparent from the data of fig. 6 and table 1, the high-efficiency flame-retardant smoke suppressant prepared by the present invention can effectively catalyze PVC to be degraded in advance in the initial stage of combustion to generate hydrogen chloride (HCl) gas with high density to cover the surface of the polymer to isolate oxygen with low density to flame-retardant the polymer for further combustion and form more carbon residue when the soft PVC composite material is completely combusted, and as is apparent from fig. 7, the carbon residue after complete combustion of the soft PVC composite material prepared by the present invention is more complete and compact compared with the comparative example, and has good expansion degree, so that the soft PVC composite material prepared by the present invention generates more carbon residue when being combusted, and the carbon residue is complete and compact to increase the flame-retardant effect of the polymer by effectively isolating heat, combustible and oxygen transfer. From all test data, the ZIF-9@PDA@ZB efficient flame-retardant smoke-suppressing agent prepared by the invention can effectively cooperate with antimony trioxide to play a synergistic flame-retardant and smoke-suppressing role on soft PVC.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (10)
1. The preparation method of the efficient flame-retardant smoke suppressant is characterized by comprising the following steps of:
(1) Dispersing Zinc Borate (ZB) in deionized water, regulating the pH value of the mixed solution to an alkaline environment by using a pH buffer, adding dopamine (PDA) after stirring, continuing stirring reaction, washing the product with water and ethanol for 3 times, and drying to obtain a PDA@ZB binary composite material;
(2) Dispersing the PDA@ZB binary composite material and metal ion salt in a solvent to obtain a solution A, stirring, then adding a solution B obtained by mixing benzimidazole, ammonia water and the solvent, continuously stirring for reaction, washing the product with ethanol and water for 3 times, and drying to obtain the efficient flame-retardant smoke suppressant ZIF-9@PDA@ZB.
2. The preparation method of claim 1, wherein in the step (1), the weight-volume ratio of zinc borate, dopamine and deionized water is 1-5 g: 0.2-1 g:200mL of zinc borate with the particle size of 0.1-5 μm and one or more of spherical, rod-like and sheet-like shapes.
3. The preparation method according to claim 1, wherein in the step (1), stirring is performed for 30-60 min under the stirring condition of 500-900 r/min, and stirring is performed for 12-24 h under the continuous stirring reaction condition of 500-900 r/min; and drying at the temperature of 60-70 ℃ for 12-24 hours.
4. The method according to claim 1, wherein in the step (1), the pH buffer is tris (hydroxymethyl) aminomethane and/or N-tris (hydroxymethyl) methylglycine, and the pH of the alkaline environment is 8 to 9.5.
5. The preparation method of claim 1, wherein in the step (2), in the solution A, the weight-volume ratio of the PDA@ZB binary composite material, the metal ion salt and the solvent is 1-6 g: 0.5-2 g:50mL; in the solution B, the weight volume ratio of benzimidazole, ammonia water and solvent is 0.1-2 g: 0.2-0.9 g:20mL.
6. The preparation method according to claim 1, wherein in the step (2), the solution A is stirred for 30min under the stirring condition of 300-500 r/min; stirring the mixture for 6 to 24 hours at normal temperature; and drying at the temperature of 60-70 ℃ for 12-24 hours.
7. The method according to claim 1, wherein in the step (2), the metal ion salt is one or more of zinc nitrate hexahydrate, nickel nitrate hexahydrate, copper nitrate hexahydrate, magnesium nitrate hexahydrate, cobalt nitrate hexahydrate, zinc acetate dihydrate, nickel acetate tetrahydrate, copper acetate monohydrate, cobalt acetate tetrahydrate; the solvent is one or more of methanol, ethanol and N-N dimethylformamide.
8. An efficient flame-retardant smoke suppressant prepared by the preparation method of any one of claims 1-7.
9. A composite material containing the high-efficiency flame-retardant smoke suppressant according to claim 8, which is characterized by comprising the following components in parts by weight: 70-90 parts of PVC resin, 30-40 parts of plasticizer, 4-6 parts of PVC stabilizer, 1-20 parts of antimony trioxide and 1-20 parts of efficient flame-retardant smoke suppressant.
10. A method of preparing the composite material of claim 9, comprising the steps of: uniformly mixing the raw materials by a double-roller open mill, and then performing hot press curing by a flat vulcanizing machine to prepare the PVC composite flame-retardant material; in the extrusion process, the temperature of a processing area is 160-180 ℃, and the extrusion time is 15-20 min; and hot-pressing for 10-20 min at 175-185 ℃ under 20MPa by using a flat vulcanizing hot press.
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