CN109467845B - Flame-retardant smoke-suppression PVC composite material and preparation method thereof - Google Patents
Flame-retardant smoke-suppression PVC composite material and preparation method thereof Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 69
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000002131 composite material Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000000779 smoke Substances 0.000 claims abstract description 44
- QLZHNIAADXEJJP-UHFFFAOYSA-L dioxido-oxo-phenyl-$l^{5}-phosphane Chemical compound [O-]P([O-])(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-L 0.000 claims abstract description 28
- 239000003381 stabilizer Substances 0.000 claims abstract description 13
- 239000000314 lubricant Substances 0.000 claims abstract description 11
- 239000004014 plasticizer Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000011347 resin Substances 0.000 claims abstract description 8
- 229920005989 resin Polymers 0.000 claims abstract description 8
- 230000002401 inhibitory effect Effects 0.000 claims abstract description 7
- 239000003112 inhibitor Substances 0.000 claims abstract description 3
- 239000000047 product Substances 0.000 claims description 14
- YWTJALLQFVWSDI-UHFFFAOYSA-N C1(=CC=CC=C1)OP(OC1=CC=CC=C1)=O.[Co] Chemical compound C1(=CC=CC=C1)OP(OC1=CC=CC=C1)=O.[Co] YWTJALLQFVWSDI-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- SPOIGTPLXYZKBM-UHFFFAOYSA-N [Zn].O=P(OC1=CC=CC=C1)OC1=CC=CC=C1 Chemical compound [Zn].O=P(OC1=CC=CC=C1)OC1=CC=CC=C1 SPOIGTPLXYZKBM-UHFFFAOYSA-N 0.000 claims description 10
- CDXVUROVRIFQMV-UHFFFAOYSA-N oxo(diphenoxy)phosphanium Chemical compound C=1C=CC=CC=1O[P+](=O)OC1=CC=CC=C1 CDXVUROVRIFQMV-UHFFFAOYSA-N 0.000 claims description 10
- 239000012047 saturated solution Substances 0.000 claims description 10
- 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 9
- UMKARVFXJJITLN-UHFFFAOYSA-N lead;phosphorous acid Chemical compound [Pb].OP(O)O UMKARVFXJJITLN-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- VTZBTZSRBYKHDV-UHFFFAOYSA-N P(OC1=CC=CC=C1)(OC1=CC=CC=C1)=O.[Ni] Chemical compound P(OC1=CC=CC=C1)(OC1=CC=CC=C1)=O.[Ni] VTZBTZSRBYKHDV-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- -1 iron diphenylphosphonate Chemical compound 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical class OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 claims description 4
- 230000001629 suppression Effects 0.000 claims description 4
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 3
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical group CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000007731 hot pressing Methods 0.000 claims description 3
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical group [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 11
- 150000003839 salts Chemical class 0.000 abstract description 5
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 229910052736 halogen Inorganic materials 0.000 abstract description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 76
- 229920000915 polyvinyl chloride Polymers 0.000 description 74
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 238000002485 combustion reaction Methods 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000004786 cone calorimetry Methods 0.000 description 7
- 238000013329 compounding Methods 0.000 description 4
- BEQVQKJCLJBTKZ-UHFFFAOYSA-M diphenylphosphinate Chemical compound C=1C=CC=CC=1P(=O)([O-])C1=CC=CC=C1 BEQVQKJCLJBTKZ-UHFFFAOYSA-M 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GSOLWAFGMNOBSY-UHFFFAOYSA-N cobalt Chemical compound [Co][Co][Co][Co][Co][Co][Co][Co] GSOLWAFGMNOBSY-UHFFFAOYSA-N 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- WNVHHKBEWRPOHX-UHFFFAOYSA-L cobalt(2+);dioxido-oxo-phenyl-$l^{5}-phosphane Chemical compound [Co+2].[O-]P([O-])(=O)C1=CC=CC=C1 WNVHHKBEWRPOHX-UHFFFAOYSA-L 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- GEWUHQYATMHBRI-UHFFFAOYSA-L diphenylphosphinate;iron(2+) Chemical compound [Fe+2].C=1C=CC=CC=1P(=O)([O-])C1=CC=CC=C1.C=1C=CC=CC=1P(=O)([O-])C1=CC=CC=C1 GEWUHQYATMHBRI-UHFFFAOYSA-L 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- 238000011173 large scale experimental method Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 230000036284 oxygen consumption Effects 0.000 description 1
- OGBPILLJZSJJRC-UHFFFAOYSA-N phenoxyphosphonoyloxybenzene Chemical compound C=1C=CC=CC=1OP(=O)OC1=CC=CC=C1 OGBPILLJZSJJRC-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 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 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
-
- 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
- C08K3/30—Sulfur-, selenium- or tellurium-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
- C08K3/32—Phosphorus-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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
-
- 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
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
-
- 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 Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention relates to the technical field of PVC material preparation, in particular to a flame-retardant smoke-inhibiting PVC composite material and a preparation method thereof, wherein the composite material comprises the following raw materials in parts by weight: 95-110 parts of PVC resin, 35-45 parts of plasticizer, 3-6 parts of stabilizer, 0.2-0.8 part of lubricant and 4-8 parts of flame-retardant smoke inhibitor; the flame-retardant smoke suppressant consists of phenylphosphonate and antimony trioxide, wherein the mass ratio of the phenylphosphonate to the antimony trioxide is 1: 3. The flame-retardant smoke-suppression PVC composite material provided by the invention is prepared by replacing antimony trioxide with phenylphosphonate, and the salt not only has the flame-retardant smoke-suppression performance of metal salt, but also increases the compatibility with PVC, and simultaneously can play a phosphorus-halogen synergistic flame-retardant effect, so that the prepared PVC composite material has better flame-retardant smoke-suppression performance and mechanical property.
Description
Technical Field
The invention relates to the technical field of PVC material preparation, in particular to a flame-retardant smoke-suppression PVC composite material and a preparation method thereof.
Background
Polyvinyl chloride (PVC) plastic is widely applied to various departments such as industry, agriculture, mining industry, chemical industry, electronic and electric products, building industry and the like due to the advantages of excellent electrical property, chemical corrosion resistance, simple processing, low price, easy modification and the like. PVC can be divided into two main types of hard PVC and soft PVC, and hard PVC products are widely applied in the world, but soft PVC is widely applied in China. Most of the soft PVC products are applied to the production process of electronic and electric appliances, wires and cables and building materials, and because the materials have higher requirements on flame retardant property, the flame retardant treatment of the soft PVC is necessary.
The flame retardants currently used in PVC mainly include halogen-antimony synergistic flame retardants, phosphate flame retardants, inorganic flame retardants, and the like. Wherein, the antimony compound in the halogen-antimony synergistic flame retardant is mainly antimony trioxide, and the single use of the antimony trioxide enhances the flame retardant effect and increases the smoke generation amount, and the price is higher.
Some people use zinc borate to partially replace antimony trioxide, and obtain better flame-retardant smoke-eliminating effect. It has been found by Shixi Chang, Lattimer, R.P., flood bin, Linanlian et al that the transition metal oxides and other metal oxides such as zinc oxide, copper oxide, cuprous oxide, iron oxide, vanadium pentoxide, titanium dioxide, cobalt oxide, molybdenum oxide, manganese dioxide, etc. in the inorganic substances have flame retardant and smoke abatement effects on PVC, and the main effect is that PVC is earlier separated from HCl during degradation, so that the PVC reacts with the transition metal elements to generate stronger Lewis acid, the PVC is catalyzed to crosslink into carbon, the volatilization of combustible gas and aromatic products is reduced, and the flammability is reduced to achieve the purpose of flame retardant and smoke abatement. But the inorganic metal salt has poor compatibility with the polymer, so that the mechanical property of the PVC is greatly influenced. Therefore, the important significance is to find a novel additive which has flame-retardant smoke-eliminating performance and small influence on the mechanical properties of the material.
Disclosure of Invention
The invention aims to solve the technical problems and provides a flame-retardant smoke-inhibiting PVC composite material and a preparation method thereof.
The invention comprises the following technical scheme:
in a first aspect, the invention provides a flame-retardant smoke-inhibiting PVC composite material, which comprises the following raw materials in parts by weight:
95-110 parts of PVC resin, 35-45 parts of plasticizer, 3-6 parts of stabilizer, 0.2-0.8 part of lubricant and 4-8 parts of flame-retardant smoke inhibitor; the flame-retardant smoke suppressant consists of phenylphosphonate and antimony trioxide, wherein the mass ratio of the phenylphosphonate to the antimony trioxide is 1: 3.
The phenylphosphonate has a certain flame-retardant effect, and is mixed with Sb at a low addition amount2O3The flame retardant is compounded to be used as a flame retardant of PVC, so that a better flame retardant effect can be obtained than that of independently adding antimony trioxide; the phenylphosphonate is used as a smoke suppressant of PVC, and can play a good smoke suppression role; phenylphosphonate with Sb2O3The compound is used as a flame retardant of PVC, so that the compatibility with PVC is increased to a certain extent, and the mechanical property of a sample is improved.
Preferably, the stabilizer consists of dibasic lead phosphite and tribasic lead sulfate, and the mass ratio of the dibasic lead phosphite to the tribasic lead sulfate is 1: 1.
Preferably, the lubricant is zinc stearate.
Preferably, the plasticizer is dioctyl phthalate.
In a second aspect, the invention provides a method for preparing the flame-retardant smoke-suppression PVC composite material, which comprises the following steps:
(1) preparing raw materials according to parts by weight;
(2) uniformly mixing and stirring the plasticizer, the stabilizer, the lubricant, the flame-retardant smoke suppressant and the PVC resin by using a mixer;
(3) mixing the product obtained in the step (2) for 10min at the temperature of 155-160 ℃ by a mixer;
(4) transferring the product obtained in the step (3) into a flat vulcanizing machine, and carrying out hot pressing for 5-8 min at the temperature of 160-170 ℃ and under the pressure of 10-12 MPa;
(5) and (5) taking out the product obtained in the step (4) for natural cooling to obtain the flame-retardant smoke-suppression type PVC.
By adopting the technical scheme, the method has the following beneficial effects: the flame-retardant smoke-suppression PVC composite material provided by the invention is prepared by replacing antimony trioxide with phenylphosphonate, and the salt not only has the flame-retardant smoke-suppression performance of metal salt, but also increases the compatibility with PVC, and simultaneously can play a phosphorus-halogen synergistic flame-retardant effect, so that the prepared PVC composite material has better flame-retardant smoke-suppression performance and mechanical property.
Drawings
FIG. 1 shows pure PVC, PVC/Sb2O3, PVC/cobalt diphenylphosphinate/Sb2O3A heat release rate map of;
FIG. 2 shows pure PVC, PVC/Sb2O3, PVC/cobalt diphenylphosphinate/Sb2O3Graph of smoke release rate.
Detailed Description
The present invention will be described in further detail below with reference to specific embodiments and with reference to the attached drawings.
Example 1:
the embodiment provides a flame-retardant smoke-inhibiting PVC composite material, which comprises the following raw materials: 100 g of PVC resin, 40 g of plasticizer, 4 g of stabilizer, 0.5 g of lubricant and 6 g of flame retardant and smoke suppressant; wherein the flame-retardant smoke suppressant consists of 1.5g of phenylphosphonate and 4.5g of antimony trioxide. The stabilizer consists of dibasic lead phosphite and tribasic lead sulfate, the mass ratio of the dibasic lead phosphite to the tribasic lead sulfate is 1: 1, namely, the dibasic lead phosphite and the tribasic lead sulfate are 2 g respectively. The stabilizer consists of 2 grams of dibasic lead phosphite and 2 grams of tribasic lead sulfate. In this embodiment, preferably, the lubricant is zinc stearate and the plasticizer is dioctyl phthalate. Wherein the phenylphosphonate is one of zinc diphenylphosphonate, iron diphenylphosphonate, nickel diphenylphosphonate and cobalt diphenylphosphonate.
In addition, the embodiment provides a method for preparing the flame-retardant smoke-suppression PVC composite material, which specifically comprises the following steps:
(1) preparing the raw materials according to the parts by weight;
(2) uniformly mixing and stirring the plasticizer, the stabilizer, the lubricant, the flame-retardant smoke suppressant and the PVC resin by using a mixer;
(3) mixing the product obtained in the step (2) for 10min at the temperature of 155-160 ℃ by a mixer;
(4) transferring the product obtained in the step (3) into a flat vulcanizing machine, and carrying out hot pressing for 5-8 min at the temperature of 160-170 ℃ and under the pressure of 10-12 MPa;
(5) and (5) taking out the product obtained in the step (4) for natural cooling to obtain the flame-retardant smoke-suppression type PVC.
Wherein, if the phenylphosphonate adopts zinc diphenylphosphonate, the preparation method comprises the following steps: respectively preparing saturated solutions of zinc sulfate and diphenylphosphonic acid by using deionized water and ethanol, pouring the two saturated solutions into a 100/ml beaker, stirring for 3 minutes by using a glass rod, filtering, and drying the obtained precipitate in an oven for 20 minutes to obtain the zinc diphenylphosphonate.
If the phenylphosphonate adopts iron diphenylphosphonate, the preparation method comprises the following steps: and (2) preparing saturated solutions of ferric trichloride and diphenyl phosphonic acid by using deionized water and ethanol respectively, pouring the two solutions into a 100/ml beaker, stirring for 3 minutes by using a glass rod, filtering, and drying the obtained precipitate in an oven for 20 minutes to obtain the ferric diphenyl phosphonate.
If the phenylphosphonate adopts nickel diphenylphosphonate, the preparation method comprises the following steps: respectively preparing saturated solutions of nickel sulfate and diphenylphosphonic acid by using deionized water and ethanol, pouring the two saturated solutions into a 100/ml beaker, stirring for 3 minutes by using a glass rod, filtering, and drying the obtained precipitate in an oven for 20 minutes to obtain nickel diphenylphosphonate;
if the phenylphosphonate adopts cobalt diphenylphosphonate, the preparation method comprises the following steps: and (3) respectively preparing saturated solutions of cobalt chloride and diphenyl phosphonic acid by using deionized water and ethanol, pouring the two saturated solutions into a 100/ml beaker, stirring for 3 minutes by using a glass rod, filtering, and drying the obtained precipitate in an oven for 20 minutes to obtain the cobalt diphenyl phosphonate.
Comparative example 1:
this example provides a comparative experiment to verify the flame retardant and smoke suppressant properties of a PVC composite prepared with a phenylphosphonate moiety instead of antimony trioxide. The experimental instruments adopted by the comparison experiment comprise an oxygen index instrument with the model of JF-3 and a smoke density instrument with the model of JCY-2. The experimental data are as follows:
TABLE 1 addition of phenylphosphonate/Sb2O3Oxygen index and smoke density comparison table of PVC sample
As can be seen from Table 1, from the results of the above oxygen index (LOI) tests, the pure PVC has an oxygen index of 28.5, and Sb is added alone2O3Oxygen index at time 34.1; at an addition amount of 1.5g, the oxygen index of each group is changed in a range that: diphenylphosphonate/Sb in constant total amount2O3The oxygen index is 34.5-35.3, and the oxygen index is higher than that of Sb added separately in an amount of 1.5g2O3The oxygen index of (c). According to the analysis, the phenylphosphonate has a certain flame retardant effect, and the phenylphosphonate reacts with Sb at a low addition level2O3The flame retardant is compounded to be used as a flame retardant of PVC, so that a better flame retardant effect can be obtained than that of independently adding antimony trioxide.
As can be seen from the smoke density data in Table 1, the maximum smoke density and smoke density rating of the samples were lower than that of the PVC without smoke suppression and the PVC sample with antimony trioxide alone when the phenylphosphonate was added at 1.5 g. When the adding amount of the phenylphosphonate is 1.5g, the maximum smoke density value is reduced to different degrees compared with the PVC sample which is not treated by the smoke-inhibiting phenylphosphonate, and a good smoke inhibiting effect is achieved.
Comparative example 2:
this example provides a comparative experiment to verify the mechanical properties of PVC composites prepared with phenylphosphonate moieties instead of antimony trioxide.
Tensile strength is the stress at which the material undergoes maximum uniform plastic deformation, i.e., the ability to resist tensile deformation, and is commonly used to characterize the mechanical properties of the material. Including tensile strength, tensile strain at break, tensile strength tensile strain, tensile yield stress, and tensile elastic modulus.
In order to study the influence of antimony trioxide and the addition of phenylphosphonate and antimony trioxide on the mechanical properties of PVC, tests for measuring the tensile properties of PVC, pure PVC and PVC treated by compounding zinc diphenylphosphonate, iron diphenylphosphonate, cobalt diphenylphosphonate and nickel diphenylphosphonate with antimony trioxide in an amount of 1.5g were performed. The test results were as follows:
table 2 shows the mechanical properties of antimony trioxide and the PVC obtained by compounding the phenylphosphonate and antimony trioxide
As can be seen from the mechanical property data in Table 8, with the addition of zinc diphenylphosphonate, when the addition amount is 1.5, the tensile strength of the sample shows a tendency of decreasing with the increase of the addition amount, and the tensile strength of the sample is not higher than that of untreated PVC and Sb is added separately2O3The tensile strength of the sample indicates that zinc diphenylphosphonate cannot improve the mechanical property of PVC well, but ratherHas great influence on the mechanical property. When the addition amount of iron diphenylphosphinate was 1.5g, the tensile strength reached a maximum of 23.5MPa, the tensile yield stress and the elastic modulus also reached a maximum at this addition amount, and the elongation at break reached 310%. The ferric diphenylphosphinate is added as a PVC flame-retardant smoke suppressant and also improves the mechanical property of a sample. With the addition of cobalt diphenylphosphonate, when the addition amount is 1.5g, the tensile strength of the sample is higher than that of untreated PVC and Sb is added separately2O3The tensile strength of the sample. The elongation at break of the drawn sample reaches 332%. With the addition of nickel diphenylphosphonate, when the addition amount is 1.5g, the tensile strength of the sample is higher than that of untreated PVC and Sb is added separately2O3The tensile strength of the sample reaches 21.4MPa, and the tensile yield stress is increased at the addition amount. The addition of nickel diphenylphosphonate improves the mechanical properties of the PVC sample to a certain extent.
Comparative example 3:
in this comparative example, Sb was added alone to investigate pure PVC2O3The smoke production rate of the samples of (a) and the samples with the added phenylphosphonate salt provides the following comparative experiments. The instrument used in the experiment was a cone calorimeter, model PX-07-007.
CONE Calorimetry (CONE) is an instrument used to test the combustion performance of a sample based on the principle of oxygen consumption. The CONE can simultaneously measure various parameters of the material in the actual combustion process, and the combustion performance of the polymer material can be evaluated from different aspects by using the parameters.
The CONE can simulate various fire intensities by changing the heat radiation intensity of the radiation CONE, and various combustion parameters provided by experiments can evaluate the combustibility and the flame retardance of the polymer material from different aspects, the test result is stable, and the correlation with data obtained by large-scale experiments is relatively good, so that the CONE is widely applied in recent years. At present, the flame retardant material is widely applied to various fields such as plastic products, building materials, electronic and electric appliances and the like, and is used for carrying out multi-aspect evaluation on the combustion performance of a test material and researching the combustion performance and the flame retardant mechanism of various flame retardant materials.
In the experiment, zinc diphenylphosphonate, nickel diphenylphosphonate and cobalt diphenylphosphonate are added into PVC respectively in an adding amount of 1.5g and a sample obtained by compounding 4.5g of antimony trioxide, and pure PVC and Sb are separately added2O3The samples of (a) were tested for comparison.
The heat release rate refers to the rate at which a unit area of a sample releases heat when burned. The curve of HRR (Rockwell Rate) change along with time of a sample in the combustion process can be obtained through CONE (flame ionization event) test, pure PVC (polyvinyl chloride) and Sb added independently2O3The results of the heat release rate experiments for the sample of (1) and the sample compounded with 1.5g of cobalt phenylphosphonate and 4.5g of antimony trioxide are shown in FIG. 1.
Various parameters of the heat release rate change of each sample can be obtained from the heat release rate chart of the sample:
(1)PVC/Sb2O3cobalt diphenylphosphonate/Sb2O3The heat release rate is reduced compared to pure PVC, which is the most important reason for the flame retardant to function. Wherein, PVC/Sb2O3Peak heat release rate (45 kW/m)2) Compared with the peak value (113 kW/m) of PVC without flame retardant treatment2) The reduction is 60 percent, and the diphenyl cobalt phosphonate is 1.5g/Sb2O3Peak Heat Release Rate (40 kW/m) for 4.5g of sample2) The peak value is reduced by 65 percent compared with the PVC without flame retardant treatment; addition of Sb alone2O3The exothermic peak of the sample is much lower than that of a pure PVC sample, and after the cobalt diphenylphosphonate is added, the heat release rate of the sample is lower than that of the sample with Sb added separately2O3Sample of (5), indicating that the addition of cobalt diphenylphosphonate caused Sb2O3The flame retardant effect of (2) is increased.
(2)PVC/Sb2O3Diphenylphosphonic acid/Sb2O3The peak value of the heat release rate of the sample is backward shifted to different degrees compared with the appearance time of pure PVC, the appearance time of the heat release peak is prolonged, the heat generated during the combustion of the material is favorably diffused in time, the rise of the temperature of the sample is inhibited, and the pyrolysis speed is further reduced, so that the combustion of the sample is delayed.
Pure PVC, separately added Sb2O3Sample (2)And the results of the smoke generation rate test data of the sample added with 1.5g of cobalt diphenylphosphonate are shown in figure 2:
as can be seen from FIG. 2, Sb was added alone2O3The sample of (A) has a lower smoke production rate than pure PVC, indicating that Sb is2O3Flame retardant PVC and slow down the smoke release rate of the sample, and the smoke generation rate of the sample added with 1.5g of cobalt diphenylphosphonate is higher than that of the sample added with Sb alone2O3The sample of (2) is further reduced, indicating that certain amounts of diphenylphosphonic acid and Sb are added2O3The smoke suppression effect of the PVC is obviously improved by compounding.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. The flame-retardant smoke-inhibiting PVC composite material is characterized by comprising the following raw materials in parts by weight:
95-110 parts of PVC resin, 35-45 parts of plasticizer, 3-6 parts of stabilizer, 0.2-0.8 part of lubricant and 4-8 parts of flame-retardant smoke inhibitor; the flame-retardant smoke suppressant consists of phenylphosphonate and antimony trioxide, wherein the mass ratio of the phenylphosphonate to the antimony trioxide is 1: 3; the phenylphosphonate is one of zinc diphenylphosphonate, iron diphenylphosphonate, nickel diphenylphosphonate and cobalt diphenylphosphonate.
2. The flame-retardant smoke-suppressing PVC composite material according to claim 1, wherein the stabilizer consists of dibasic lead phosphite and tribasic lead sulfate, and the mass ratio of the dibasic lead phosphite to the tribasic lead sulfate is 1: 1.
3. The flame-retardant smoke-suppressing PVC composite material according to claim 1, which is characterized by comprising the following raw materials in parts by weight:
100 parts of PVC resin, 40 parts of plasticizer, 4 parts of stabilizer, 0.5 part of lubricant and 6 parts of flame-retardant smoke suppressant; wherein the flame-retardant smoke suppressant consists of 1.5 parts of phenylphosphonate and 4.5 parts of antimony trioxide.
4. A fire-retardant smoke-suppressing PVC composite as claimed in claim 3, characterized in that said stabilizer consists of 2 parts of dibasic lead phosphite and 2 parts of tribasic lead sulfate.
5. The flame and smoke retardant PVC composite of claim 1, wherein the lubricant is zinc stearate.
6. The flame retardant smoke suppression PVC composite of claim 1, wherein said plasticizer is dioctyl phthalate.
7. A process for the preparation of a flame retardant, smoke suppressant PVC composite as defined in any one of claims 1 to 6 comprising the steps of:
(1) preparing raw materials according to parts by weight;
(2) uniformly mixing and stirring the plasticizer, the stabilizer, the lubricant, the flame-retardant smoke suppressant and the PVC resin by using a mixer;
(3) mixing the product obtained in the step (2) for 10min at the temperature of 155-160 ℃ by a mixer;
(4) transferring the product obtained in the step (3) into a flat vulcanizing machine, and carrying out hot pressing for 5-8 min at the temperature of 160-170 ℃ and under the pressure of 10-12 MPa;
(5) and (5) taking out the product obtained in the step (4) for natural cooling to obtain the flame-retardant smoke-suppression type PVC.
8. The method of claim 7, wherein the phenylphosphonate salt is zinc diphenylphosphonate prepared by: respectively preparing saturated solutions of zinc sulfate and diphenylphosphonic acid by using deionized water and ethanol, pouring the two saturated solutions into a 100/ml beaker, stirring for 3 minutes by using a glass rod, filtering, and drying the obtained precipitate in an oven for 20 minutes to obtain the zinc diphenylphosphonate.
9. The method according to claim 7, wherein the phenylphosphonate is iron diphenylphosphonate, and is prepared by: and (2) preparing saturated solutions of ferric trichloride and diphenyl phosphonic acid by using deionized water and ethanol respectively, pouring the two solutions into a 100/ml beaker, stirring for 3 minutes by using a glass rod, filtering, and drying the obtained precipitate in an oven for 20 minutes to obtain the ferric diphenyl phosphonate.
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