CN110903546A - A kind of flame retardant polymer material and its preparation method and application - Google Patents
A kind of flame retardant polymer material and its preparation method and application Download PDFInfo
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- CN110903546A CN110903546A CN201911095243.7A CN201911095243A CN110903546A CN 110903546 A CN110903546 A CN 110903546A CN 201911095243 A CN201911095243 A CN 201911095243A CN 110903546 A CN110903546 A CN 110903546A
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- 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 51
- 239000003063 flame retardant Substances 0.000 title claims abstract description 51
- 239000002861 polymer material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- -1 polysiloxane Polymers 0.000 claims abstract description 50
- 239000004743 Polypropylene Substances 0.000 claims abstract description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 27
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 23
- 229920001155 polypropylene Polymers 0.000 claims abstract description 21
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000012188 paraffin wax Substances 0.000 claims abstract description 15
- 239000000347 magnesium hydroxide Substances 0.000 claims abstract description 12
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims abstract description 12
- 239000004114 Ammonium polyphosphate Substances 0.000 claims abstract description 11
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 11
- 229920001276 ammonium polyphosphate Polymers 0.000 claims abstract description 11
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims abstract description 11
- 239000004014 plasticizer Substances 0.000 claims abstract description 11
- 239000003381 stabilizer Substances 0.000 claims abstract description 11
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 8
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 12
- 230000002829 reductive effect Effects 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 9
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 claims description 7
- 229920002401 polyacrylamide Polymers 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 claims description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 229910000077 silane Inorganic materials 0.000 claims description 5
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000005336 cracking Methods 0.000 claims description 4
- 125000005442 diisocyanate group Chemical group 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 3
- ICFCQEJDICSLOV-UHFFFAOYSA-N diisocyanato(dimethyl)silane Chemical compound O=C=N[Si](C)(C)N=C=O ICFCQEJDICSLOV-UHFFFAOYSA-N 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 239000004575 stone Substances 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 2
- 239000012943 hotmelt Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 230000002087 whitening effect Effects 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims 3
- 229910052739 hydrogen Inorganic materials 0.000 claims 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 150000008064 anhydrides Chemical class 0.000 claims 1
- 239000008187 granular material Substances 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 8
- 239000000779 smoke Substances 0.000 abstract description 3
- 150000001408 amides Chemical class 0.000 abstract 1
- 238000000576 coating method Methods 0.000 description 15
- 238000012360 testing method Methods 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 10
- 239000007789 gas Substances 0.000 description 8
- 229920001843 polymethylhydrosiloxane Polymers 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- LIYKJALVRPGQTR-UHFFFAOYSA-M oxostibanylium;chloride Chemical compound [Cl-].[Sb+]=O LIYKJALVRPGQTR-UHFFFAOYSA-M 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000004108 freeze drying Methods 0.000 description 3
- 230000000670 limiting effect Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- DAMJCWMGELCIMI-UHFFFAOYSA-N benzyl n-(2-oxopyrrolidin-3-yl)carbamate Chemical compound C=1C=CC=CC=1COC(=O)NC1CCNC1=O DAMJCWMGELCIMI-UHFFFAOYSA-N 0.000 description 2
- 238000005282 brightening Methods 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002341 toxic gas Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- 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
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
-
- 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
- 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
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- 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)
- Fireproofing Substances (AREA)
Abstract
本发明公开了一种阻燃型高分子材料及其制备方法和应用，涉及高分子防火材料技术领域，该材料的原料以重量份计，包括以下组分：聚丙烯80‑120份、聚丙烯酰胺10‑15份、聚硅氧烷10‑40份、聚磷酸铵15‑25份、三聚氰胺7‑9份、氯化石蜡1‑5份、石墨烯9‑13份、纳米氢氧化镁12‑16份、纳米氢氧化铝4‑9份、三氧化二锑2‑8份、塑化剂10‑20份、稳定剂3‑5份。该材料具有优异阻燃性能，克服了现有技术中聚丙烯材料易燃、产生烟雾等缺点，为聚丙烯材料提供了更为广泛的应用空间。The invention discloses a flame retardant polymer material, a preparation method and application thereof, and relates to the technical field of polymer fireproof materials. 10-15 parts of amide, 10-40 parts of polysiloxane, 15-25 parts of ammonium polyphosphate, 7-9 parts of melamine, 1-5 parts of chlorinated paraffin, 9-13 parts of graphene, 12- parts of nano magnesium hydroxide 16 parts, 4-9 parts of nano aluminum hydroxide, 2-8 parts of antimony trioxide, 10-20 parts of plasticizer, and 3-5 parts of stabilizer. The material has excellent flame retardant performance, overcomes the shortcomings of polypropylene materials in the prior art, such as being inflammable and generating smoke, and provides a wider application space for polypropylene materials.
Description
Technical Field
The invention relates to the technical field of high polymer fireproof materials, in particular to a flame-retardant high polymer material and a preparation method and application thereof.
Background
Polypropylene, a widely used thermoplastic polymer material, is extremely flammable, and once ignited, releases a large amount of heat in a short time, and also releases a large amount of smoke and toxic gases, so that it is important to reduce the flammability of PP.
At present, the common method for improving the flame retardance of the high polymer material is to prepare the flame-retardant high polymer material. Generally, the preparation method of the flame retardant polymer material mainly comprises the following three steps: (1) preparing an intrinsic flame-retardant high polymer material; (2) an additive flame-retardant polymer material; (3) the flame-retardant coating is a flame-retardant high polymer material. The flame-retardant coating flame-retardant polymer material is a novel method with good application prospect, and is a method for obtaining the flame-retardant polymer material by firstly preparing flame-retardant slurry (comprising a flame retardant, an auxiliary agent, a solvent and the like) and then coating the flame-retardant slurry on the surface of a substrate in a certain mode (such as a pulling method, a spraying method, a blade coating method, a hot pressing method and the like). The coating not only can endow the substrate with good comprehensive properties without influencing the mechanical properties of the substrate, so that the improvement of the flame retardance of the polymer substrate through the coating is the most promising flame retardance way.
Since the first full introduction of intumescent coatings in 1971 by HL Vandersall, intumescent coatings have evolved rapidly, with intumescent flame retardant coatings being commonly used to improve the flame retardancy of metals, wood and fabrics, whereas intumescent flame retardant coatings are less used to improve the flame retardancy of PP, mainly for several reasons: (1) the weak adhesion to the flame retardant coating makes it difficult to apply the coating to the surface of PP; (2) a greater thickness to obtain good flame retardancy limits the use of PP in certain fields; (3) the coating lacks toughness and easily falls off when the PP is deformed. Therefore, in order to introduce a flame retardant coating to the surface of PP to reduce the fire risk of PP, an effective way to solve the above problems has to be sought.
Disclosure of Invention
The invention aims to provide a flame-retardant high polymer material, a preparation method and application thereof, and aims to solve the technical problem of application of the intumescent coating on the aspect of polypropylene materials.
According to one technical scheme, the flame-retardant high polymer material comprises the following raw materials in parts by weight:
80-120 parts of polypropylene, 10-15 parts of polyacrylamide, 10-40 parts of polysiloxane, 15-25 parts of ammonium polyphosphate, 7-9 parts of melamine, 1-5 parts of chlorinated paraffin, 9-13 parts of graphene, 12-16 parts of nano magnesium hydroxide, 4-9 parts of nano aluminum hydroxide, 2-8 parts of antimony trioxide, 10-20 parts of plasticizer and 3-5 parts of stabilizer.
Preferably, the polysiloxane is obtained by taking polymethylhydrosiloxane, allyl glycidyl ether, dimethyl diisocyanate silane and metaphosphoric acid as raw materials and absolute ethyl alcohol as a solvent through reduced pressure distillation under the action of a catalyst; the mass ratio of the polymethylhydrosiloxane, the allyl glycidyl ether, the dimethyl diisocyanate silane and the metaphosphoric acid is 1: 5: 2: 5, and the catalyst is a Speier catalyst.
Preferably, the preparation method of the polysiloxane comprises the following steps: dissolving polymethylhydrosiloxane and a catalyst in a solvent, heating to 75 ℃, stirring at a constant temperature for 30min, continuously heating to 100 ℃, dropwise adding an absolute ethyl alcohol solution dissolved with dimethyl diisocyanate silane into a reaction vessel, reacting at a constant temperature for 8h, dropwise adding an absolute ethyl alcohol solution dissolved with allyl glycidyl ether into the reaction vessel, reacting at a constant temperature for 8h, adding metaphosphoric acid, continuously stirring, introducing nitrogen, reacting at a constant temperature of 100 ℃ for 12h, distilling under reduced pressure, washing, and drying to obtain the product polysiloxane.
Preferably, the graphene is reduced graphene oxide, and is specifically prepared by the following steps: dissolving graphene oxide prepared by a Hummers method in water, performing ultrasonic dispersion, placing in a water bath environment at 100 ℃, dropwise adding hydrazine hydrate, mechanically stirring for reaction for 2 hours, filtering, washing with water, and performing freeze drying to obtain reduced graphene oxide.
Preferably, the average grain diameter of the nano aluminum hydroxide and the nano magnesium hydroxide is less than or equal to 100 nm.
Preferably, the plasticizer is stone powder, a dispersant, a cracking catalyst, a brightening agent, glyoxylic acid, maleic anhydride, glutaric anhydride, starch and paraffin wax, and the weight ratio of the stone powder to the dispersant to the cracking catalyst to the brightening agent is 2: 6: 4: 3: 3: 3: 7: 1: 5 by mass ratio.
Preferably, the stabilizer is organic tin or organic antimony which is mixed according to the weight ratio of 3: 2, and mixing the components in a mass ratio.
According to a second technical scheme of the invention, the preparation method of the flame-retardant polymer material comprises the following steps: heating polypropylene to 110-120 ℃, respectively adding polyacrylamide, polysiloxane, ammonium polyphosphate, melamine, chlorinated paraffin and graphene under the stirring condition, heating to 130-145 ℃, stirring at the speed of 50-75r/min for 1-1.5h, naturally cooling to 70-80 ℃, adding nano magnesium hydroxide, nano aluminum hydroxide, antimony trioxide, plasticizer and stabilizer, stirring at the speed of 80-100r/min for 1-1.5h, placing in a double-screw extruder, carrying out hot melting, granulating in a granulator, and then cooling with cold water to obtain the flame-retardant polymer material.
Preferably, the hot melt temperature is 130-.
According to the third technical scheme, the flame-retardant high polymer material is applied to a fireproof material.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
the flame-retardant high polymer material prepared by the invention takes polypropylene as a base material, a certain amount of polyacrylamide, polysiloxane, ammonium polyphosphate, melamine, chlorinated paraffin, graphene, nano magnesium hydroxide, nano aluminum hydroxide, antimony trioxide, a plasticizer and a stabilizer are added, and the mixture is uniformly mixed under a certain condition, then is subjected to hot melting and extrusion granulation to prepare the high polymer material with excellent flame-retardant property, so that the defects of flammability, smoke generation and the like of the polypropylene material in the prior art are overcome, and a wider application space is provided for the polypropylene material.
The flame-retardant mechanism of the flame-retardant polymer material of the invention is as follows:
the invention creatively introduces an acid source, a carbon source and a gas source of an expansion type flame retardant system with excellent flame retardant property into the preparation process of a polypropylene material, when a polymer is burnt under heat, a large amount of non-combustible gas can be generated, so that the concentration of combustible gas and oxygen is diluted and the heat is taken away, meanwhile, polysiloxane is a macromolecule taking a silicon-oxygen bond (-Si-O-Si-) as a main chain and silicon atoms are connected with various organic groups, the polysiloxane has good thermal stability, excellent aging resistance and good biocompatibility, when the polysiloxane meets the fire, the polysiloxane can form a silicon dioxide protective layer to reduce the exchange of the heat and the combustible gas and play a role in improving the flame retardant property of a matrix, and the polysiloxane prepared by the method contains a large amount of rich-Si-O-CH2CH3The hydrophobic polysiloxane of the group can carry out surface modification on the ammonium polyphosphate in the melt blending process so as to improve the compatibility of the ammonium polyphosphate and the polypropylene, thereby playing a role in synergy with the ammonium polyphosphate and greatly improving the flame retardance of the polypropylene material.
The invention also introduces graphene into the polymer material, the graphene can not only improve the electromagnetic shielding performance of the polymer composite material, the specific 2D layered structure can also effectively improve the thermal stability and the flame retardant property of the polymer, in the combustion process, the layered graphene has good shielding effect, can isolate an external heat source and combustible substances, meanwhile, the release of toxic gas is reduced, but the strong pi-pi action among the sheet layers enables the graphene to easily agglomerate in a polymer matrix, the flame retardant effect can not be fully exerted, therefore, the reduced graphene oxide is prepared and added into the polypropylene raw material in the form of raw material, through heating and melting, the surface of the reduced graphene oxide is grafted to polypropylene molecules, so that the problem of agglomeration of graphene is avoided, and the compatibility of a matrix is further improved. Meanwhile, when the matrix is heated, silicon dioxide generated by polysiloxane is loaded on the surface of grapheneFormation of GO/SiO2The combination of the microspheres and the polypropylene also obviously improves the flame retardance and the thermal stability of the polymer material.
When the chlorinated paraffin is heated to a certain temperature (usually 120 ℃), the chlorinated paraffin is decomposed slowly and releases hydrogen chloride gas, so that when the high polymer is decomposed, the chlorinated paraffin also starts to be decomposed, and can capture free radicals when the high polymer material is decomposed, thereby delaying or inhibiting the reaction of a combustion chain, and simultaneously the released hydrogen chloride is a flame-retardant gas which can cover the surface of the material and play a role in blocking and diluting the oxygen concentration. Meanwhile, the chlorinated paraffin and the antimony trioxide are compounded for use, the flame retardant effect is obviously improved through the coordination effect, hydrogen chloride and the antimony trioxide react to generate antimony trichloride and antimony oxychloride during combustion in the presence of halide, the antimony oxychloride is heated and endothermically decomposed to continuously generate the antimony trichloride, the generated antimony halides such as the antimony chloride and the like have large relative densities and cover the surface of a polymer, and the antimony oxychloride also has the function of capturing free radicals in a gaseous state, and the reaction of the antimony oxychloride not only inhibits the generation of open fire but also reduces the concentration of HCl, i.e. asphyxiant gas.
The nanometer magnesium hydroxide and the nanometer aluminum hydroxide release crystal water when being heated and decomposed, thereby absorbing a large amount of heat, inhibiting the temperature rise of the polymer material, delaying the heating and decomposition of the polymer material and reducing the combustion speed of the material, diluting the concentration of combustible gas and other substances in a gas-phase combustion area by water vapor generated by decomposition, simultaneously playing a certain physical heat insulation role by magnesium oxide and aluminum oxide generated by decomposition, and being beneficial to forming a surface carbonization layer to prevent the heat and oxygen from entering.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The specification and examples are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
The "parts" in the present invention are all parts by mass unless otherwise specified.
Example 1
Preparing a graphene raw material: mixing 5g of natural graphite and 2g of NaNO3Mixing, adding into a three-neck flask, placing in an ice-water bath, slowly adding 120mL concentrated sulfuric acid, mechanically stirring for 30min, and adding 20g KMnO in several times4Reacting for 60min, raising the temperature to 40 ℃, continuing to react for 4H, then slowly adding 230mL of deionized water, transferring the three-neck flask into a water bath with the temperature of 98 ℃ raised in advance, stirring for 5min, and adding a proper amount of H2O2Until no bubbles are generated, the system is formed by dark brownThe color turned to bright yellow. And then washing the product for multiple times by using deionized water and dilute hydrochloric acid, and dialyzing the product until the product is neutral, and freeze-drying the product for 36 hours to obtain GO. 2g of graphene oxide was dissolved in 500mL of water, ultrasonically dispersed for 1h, then transferred into a flask and placed in a water bath at 100 ℃, 10mL of hydrazine hydrate was added dropwise, mechanically stirred and reacted for 2 h. And after the reaction is finished, filtering while the reaction is hot, washing the reaction product for multiple times by using deionized water, and freeze-drying the product for 36 hours to obtain the reduced graphene oxide RGO.
Polysiloxane preparation: weighing raw materials according to the mass ratio of polymethylhydrosiloxane, allyl glycidyl ether, dimethyl diisocyanato silane and metaphosphoric acid of 1: 5: 2: 5, respectively dissolving the raw materials in a proper amount of absolute ethyl alcohol solvent, adding a Speier catalyst (80ppm) into the polymethylhydrosiloxane solution, heating to 75 ℃, stirring at constant temperature for 30min to activate the catalyst, heating to 100 ℃, dropwise adding the absolute ethyl alcohol solution of dimethyl diisocyanato silane into a flask within 3h, continuously reacting for 8h, dropwise adding the absolute ethyl alcohol solution dissolved with the allyl glycidyl ether into the flask within 2h, reacting for 8h at constant temperature, adding metaphosphoric acid, continuously stirring and introducing nitrogen, reacting for 12h at constant temperature of 100 ℃, and removing the solvent by rotary evaporation. And washing the obtained powder with absolute ethyl alcohol for multiple times, washing with deionized water for multiple times, and drying the solid powder obtained by suction filtration in an oven at 85 ℃ for 12 hours to obtain the polysiloxane.
Respectively weighing 120 parts of polypropylene, 15 parts of polyacrylamide, 40 parts of polysiloxane, 25 parts of ammonium polyphosphate, 9 parts of melamine, 5 parts of chlorinated paraffin, 13 parts of graphene, 16 parts of nano magnesium hydroxide, 9 parts of nano aluminum hydroxide, 8 parts of antimony trioxide, 20 parts of plasticizer and 5 parts of stabilizer for later use, wherein the average particle size of the nano aluminum hydroxide and the nano magnesium hydroxide is less than or equal to 100nm, and the plasticizer is prepared by mixing mountain flour, a dispersing agent, a cracking catalyst, a whitening agent, glyoxylic acid, maleic anhydride, glutaric anhydride, starch and paraffin according to a ratio of 2: 6: 4: 3: 3: 3: 7: 1: 5, and the stabilizer is prepared by mixing organic tin and organic antimony according to the mass ratio of 3: 2, and mixing the components in a mass ratio.
Heating polypropylene to 110-120 ℃, respectively adding polyacrylamide, polysiloxane, ammonium polyphosphate, melamine, chlorinated paraffin and graphene under the stirring condition, heating to 145 ℃, stirring at the speed of 65r/min for 1.5h, naturally cooling to 80 ℃, adding nano magnesium hydroxide, nano aluminum hydroxide, antimony trioxide, plasticizer and stabilizer, stirring at the speed of 100r/min for 1.5h, placing in a double-screw extruder, carrying out hot melting and extrusion, entering a granulator for granulation, and then cooling with water to obtain the flame-retardant polymer material.
Example 2
The method steps are the same as example 1, except that the graphene used is common graphene oxide.
Example 3
The process steps are the same as in example 1, except that the polysiloxane is polymethylhydrosiloxane.
Examples 4 to 11
The procedure is as in example 1, except that the amounts of the components are shown in Table 1
The following tests were carried out on the polymeric materials prepared in examples 1 to 10 and the ordinary PP materials:
limiting oxygen index test (LOI, vol.%), test standard ASTM D2863-10;
vertical burning test (UL-94), test standard ASTM D3801-10;
tensile property test, the test standard is ASTM D638-10;
and (3) testing the impact performance, wherein the test standard is ASTM D256-10, and the test result is shown in Table 2.
TABLE 2
As can be seen from table 2, the flame retardant polymer material prepared by the method of the present invention significantly improves the flame retardant property of the polypropylene material without significantly affecting the mechanical properties of the polypropylene material.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (10)
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