CN116285143B - Flame-retardant foamed polystyrene composite material for storage and transportation box and preparation method thereof - Google Patents
Flame-retardant foamed polystyrene composite material for storage and transportation box and preparation method thereof Download PDFInfo
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- CN116285143B CN116285143B CN202310579419.6A CN202310579419A CN116285143B CN 116285143 B CN116285143 B CN 116285143B CN 202310579419 A CN202310579419 A CN 202310579419A CN 116285143 B CN116285143 B CN 116285143B
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- China
- Prior art keywords
- parts
- flame
- retardant
- foaming
- expanded polystyrene
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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 169
- 239000003063 flame retardant Substances 0.000 title claims abstract description 167
- 239000002131 composite material Substances 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 238000003860 storage Methods 0.000 title claims abstract description 24
- 229920006248 expandable polystyrene Polymers 0.000 title abstract description 18
- 239000000779 smoke Substances 0.000 claims abstract description 72
- 239000004794 expanded polystyrene Substances 0.000 claims abstract description 69
- 238000005187 foaming Methods 0.000 claims abstract description 61
- 239000000463 material Substances 0.000 claims abstract description 60
- 239000004088 foaming agent Substances 0.000 claims abstract description 48
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 44
- UBIJTWDKTYCPMQ-UHFFFAOYSA-N hexachlorophosphazene Chemical compound ClP1(Cl)=NP(Cl)(Cl)=NP(Cl)(Cl)=N1 UBIJTWDKTYCPMQ-UHFFFAOYSA-N 0.000 claims abstract description 40
- YVBOZGOAVJZITM-UHFFFAOYSA-P ammonium phosphomolybdate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])=O.[O-][Mo]([O-])(=O)=O YVBOZGOAVJZITM-UHFFFAOYSA-P 0.000 claims abstract description 39
- 239000004793 Polystyrene Substances 0.000 claims abstract description 33
- 229920002223 polystyrene Polymers 0.000 claims abstract description 32
- 239000000126 substance Substances 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 5
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 claims description 16
- 239000003086 colorant Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 13
- 239000004156 Azodicarbonamide Substances 0.000 claims description 12
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 claims description 12
- 235000019399 azodicarbonamide Nutrition 0.000 claims description 12
- 239000003365 glass fiber Substances 0.000 claims description 11
- VETPHHXZEJAYOB-UHFFFAOYSA-N 1-n,4-n-dinaphthalen-2-ylbenzene-1,4-diamine Chemical compound C1=CC=CC2=CC(NC=3C=CC(NC=4C=C5C=CC=CC5=CC=4)=CC=3)=CC=C21 VETPHHXZEJAYOB-UHFFFAOYSA-N 0.000 claims description 10
- 235000021355 Stearic acid Nutrition 0.000 claims description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- 239000004202 carbamide Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 10
- 239000008117 stearic acid Substances 0.000 claims description 10
- 239000003963 antioxidant agent Substances 0.000 claims description 9
- 230000003078 antioxidant effect Effects 0.000 claims description 9
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 8
- 239000004604 Blowing Agent Substances 0.000 claims description 7
- 239000012783 reinforcing fiber Substances 0.000 claims description 7
- 239000012745 toughening agent Substances 0.000 claims description 7
- 239000000314 lubricant Substances 0.000 claims description 6
- 239000002666 chemical blowing agent Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- NPNPZTNLOVBDOC-UHFFFAOYSA-N 1,1-difluoroethane Chemical compound CC(F)F NPNPZTNLOVBDOC-UHFFFAOYSA-N 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 2
- 239000004760 aramid Substances 0.000 claims description 2
- 229920006231 aramid fiber Polymers 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 238000004898 kneading Methods 0.000 claims description 2
- 239000004209 oxidized polyethylene wax Substances 0.000 claims description 2
- 235000013873 oxidized polyethylene wax Nutrition 0.000 claims description 2
- -1 polyethylene Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 abstract description 16
- 230000007797 corrosion Effects 0.000 abstract description 15
- 238000009413 insulation Methods 0.000 abstract description 4
- 230000007774 longterm Effects 0.000 abstract description 4
- 238000012423 maintenance Methods 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 31
- 150000003839 salts Chemical class 0.000 description 15
- 239000007921 spray Substances 0.000 description 13
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 12
- 230000007547 defect Effects 0.000 description 9
- 239000011148 porous material Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000002845 discoloration Methods 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 230000002195 synergetic effect Effects 0.000 description 6
- 238000007789 sealing Methods 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000006004 Quartz sand Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004595 color masterbatch Substances 0.000 description 1
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical group BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 150000005828 hydrofluoroalkanes Chemical group 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000013385 inorganic framework Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0038—Use of organic additives containing phosphorus
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0066—Use of inorganic compounding ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0085—Use of fibrous compounding ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
- C08J9/103—Azodicarbonamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/143—Halogen containing compounds
- C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
- C08J9/146—Halogen containing compounds containing carbon, halogen and hydrogen only only fluorine as halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/16—Unsaturated hydrocarbons
- C08J2203/162—Halogenated unsaturated hydrocarbons, e.g. H2C=CF2
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/18—Binary blends of expanding agents
- C08J2203/184—Binary blends of expanding agents of chemical foaming agent and physical blowing agent, e.g. azodicarbonamide and fluorocarbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/04—Homopolymers or copolymers of styrene
- C08J2325/06—Polystyrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2453/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
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- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/80—Packaging reuse or recycling, e.g. of multilayer packaging
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a flame-retardant expanded polystyrene composite material for a storage and transportation box and a preparation method thereof, wherein the flame-retardant expanded polystyrene composite material comprises the following raw materials in parts by mass: 100 parts of polystyrene, 10-30 parts of flame-retardant smoke suppressant, 0.5-5 parts of chemical foaming agent, 2-10 parts of physical foaming agent and 0.5-2 parts of foaming auxiliary agent; the flame-retardant smoke suppressant is a combination of graphene oxide, ammonium phosphomolybdate and hexachlorocyclotriphosphazene. The invention adopts a composite foaming system consisting of a chemical foaming agent and a physical foaming agent, and compounds the composite foaming system with a flame-retardant smoke suppressant of specific components, so that the flame-retardant foamed polystyrene material has a uniform and compact porous structure, low density, light weight and good heat insulation performance, has excellent flame-retardant smoke suppressant performance, corrosion resistance and mechanical strength, can be used as a material of a storage and transportation box, and meets the requirements of long-term stable use and no frequent maintenance of the material in a marine high-salt fog state.
Description
Technical Field
The invention belongs to the technical field of polymer materials and processing, and particularly relates to a flame-retardant foamed polystyrene composite material for a storage and transportation box and a preparation method thereof.
Background
The early weapon storage and transportation box adopts a military wooden storage and transportation box, the inside of the wooden box envelope package is high-grade anti-corrosion and sealing package, the strength, the sealing performance, the moisture resistance and the wading performance of the box body are poor, the box body is easy to rot in natural environment, and the long-term storage performance is poor. The metal container storage and transportation box has the characteristics of high strength, and is widely applied at present, but the metal container storage and transportation box has high density, high quality, high cost and poor corrosion resistance. The composite material is light in weight, corrosion-resistant and good in designability, and along with the continuous improvement of the requirements of weapon equipment on packaging, the problems of corrosion resistance, moisture resistance, sealing and the like are effectively solved by using the composite material storage and transportation box, so that the composite material storage and transportation box has wider application in the packaging of various weapons. The polystyrene can be used as a sandwich material of the composite material storage and transportation box, so that the heat preservation, heat insulation and rigidity performances of the storage and transportation box can be effectively improved, and the weight of a product can be remarkably reduced.
Extruded polystyrene (XPS) is a heat insulating material successfully developed in the 60 th century, and the preparation process is to continuously extrude and foam-mold Polystyrene (PS) resin, a foaming agent and related auxiliary agents through an extruder, and the XPS has a closed-pore foam structure, so that the heat insulating material has the characteristics of good heat insulating performance, durability, lower water absorption, good dimensional stability, good steam permeability resistance, high compressive strength and the like, has excellent comprehensive performance, and is widely applied to various fields. However, XPS is a typical polymer material that burns upon contact with a flame, and burns upon removal of the fire source, and is also fuming, exothermic, and emits toxic gases. Therefore, when XPS is applied to products having fire safety requirements, a fire retardant treatment must be performed.
The addition of flame retardant to XPS is a common practice in the industry to promote XPS flame retardancy, for example, CN112321959A discloses a flame retardant XPS extruded sheet comprising the following components in parts by weight: 900-950 parts of polystyrene, 20-40 parts of flame retardant, 16-28 parts of nucleating agent, 20-30 parts of color master batch, 30-50 parts of foaming agent, 10-16 parts of aluminum oxide and 14-19 parts of quartz sand; wherein the flame retardant is decabromodiphenyl ether. CN112852015a discloses a composite brominated flame retardant, which consists of a mixture of one or both of brominated SBS and methyl octabromoether, a heat stabilizer, a hydrogen bromide absorbent and an antioxidant, and has good thermal stability, and the composite flame retardant is melt-blended with polystyrene and added with a foaming agent to be extruded into foaming XPS, so that higher flame retardant performance can be realized. Although XPS with certain flame retardance is disclosed in the prior art, the production of XPS materials with high flame retardance level has higher technical difficulty, the flame retardant with higher decomposition temperature must be selected, and the dispersibility of the flame retardant is good; in addition, after a large amount of flame retardant is added to meet the requirement of high flame retardance, adverse effects are brought to the extrusion foaming process of XPS, the surface of the obtained XPS board is easy to deform and crack, the corrosion resistance is reduced, the service performance of the XPS board is seriously influenced, and the performance requirements in the application fields of storage and transportation boxes and the like cannot be met.
Therefore, how to obtain polystyrene materials with excellent flame retardance, foaming performance and corrosion resistance at the same time, so that the polystyrene materials meet the performance requirements of storage and transportation tanks is the focus of research in the field.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to solve the problem that the flame retardance, the foaming performance, the corrosion resistance and the like of the foaming polystyrene are difficult to obtain simultaneously, and the invention aims to provide the flame retardance foaming polystyrene composite material for the storage and transportation box and the preparation method thereof.
In order to achieve the purpose of the invention, the following technical scheme is adopted:
in a first aspect, the invention provides a flame-retardant expanded polystyrene composite material, which comprises the following raw materials in parts by mass:
100 parts of polystyrene
10-30 parts of flame-retardant smoke suppressant
0.5-5 parts of chemical foaming agent
2-10 parts of physical foaming agent
0.5-2 parts of foaming auxiliary agent;
the flame-retardant smoke suppressant is a combination of graphene oxide, ammonium phosphomolybdate and hexachlorocyclotriphosphazene.
The flame-retardant foamed polystyrene material provided by the invention adopts a composite foaming system formed by combining a chemical foaming agent and a physical foaming agent, and is cooperated with a specific flame-retardant smoke suppressant, on one hand, hexachlorocyclotriphosphazene in the flame-retardant smoke suppressant) The flame-retardant foamed polystyrene material contains P-Cl bonds, can perform nucleophilic substitution reaction with functional groups (such as hydroxyl groups) on the surface of graphene oxide in the preparation process of the flame-retardant foamed polystyrene material, and the product obtained by the reaction contains P=N inorganic frameworks, so that the flame-retardant foamed polystyrene material has an improvement effect on the thermal stability of the graphene oxide and the flame-retardant smoke suppression performance of the flame-retardant foamed polystyrene material. On the other hand, the flame-retardant smoke suppressant can improve the melt elasticity of polystyrene, and is mutually cooperated with a composite foaming system, so that uniform and compact cells can be generated, cell nucleation is promoted, and cell rupture and fusion in the foaming process are effectively inhibited, so that the foamed polystyrene material has a uniform and compact closed cell structure, and is low in density, light in weight and good in heat insulation performance. The flame-retardant foamed polystyrene material has excellent flame retardance and foaming performance, good appearance, no defects, excellent corrosion resistance and mechanical strength through the design and mutual cooperation of a composite foaming system consisting of a chemical foaming agent and a physical foaming agent and a flame-retardant smoke suppressant, can be used as a material of a storage and transportation box, and meets the requirements of long-term stable use and no need of frequent maintenance under the offshore high-salt fog state.
In the invention, the flame-retardant smoke suppressant is 10-30 parts by weight based on 100 parts of polystyrene, and for example, 11 parts, 13 parts, 15 parts, 17 parts, 19 parts, 20 parts, 21 parts, 23 parts, 25 parts, 27 parts or 29 parts and the like can be used.
The chemical foaming agent is 0.5-5 parts, for example, 0.8 parts, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts or 4.5 parts, etc.
The physical foaming agent is 2-10 parts, for example, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts and the like.
The foaming auxiliary is 0.5-2 parts, for example, 0.8 parts, 1 part, 1.2 parts, 1.5 parts or 1.8 parts, etc.
Preferably, the mass ratio of graphene oxide, ammonium phosphomolybdate and hexachlorocyclotriphosphazene in the flame-retardant smoke suppressant is 1 (3-8) (0.5-2), and more preferably 1 (4-6) (0.7-1.5).
Wherein, the mass ratio of graphene oxide to ammonium phosphomolybdate in the flame-retardant smoke suppressant is 1 (3-8), for example, 1:3.5, 1:4, 1:4.5, 1:5, 1:5.5, 1:6, 1:6.5, 1:7, 1:7.5 and the like, and further preferably 1 (4-6); the mass ratio of graphene oxide to hexachlorocyclotriphosphazene is 1 (0.5-2), and may be, for example, 1:0.6, 1:0.8, 1:1, 1:1.2, 1:1.5, 1:1.8, etc., and further preferably 1 (0.7-1.5).
As a preferable technical scheme of the invention, the graphene oxide, the ammonium phosphomolybdate and the hexachlorocyclotriphosphazene are compounded according to the mass ratio of 1 (3-8) (0.5-2), and more preferably 1 (4-6) (0.7-1.5), on one hand, the three are mutually cooperated, so that the flame retardance of the flame retardant expanded polystyrene material can be improved, and the smoke density can be reduced; on the other hand, the flame-retardant foamed polystyrene material interacts with a composite foaming system, can improve the foaming uniformity, forms a compact and uniform porous structure in the flame-retardant foamed polystyrene material, has good corrosion resistance and salt spray resistance, and has good mechanical properties.
Preferably, the chemical foaming agent is an azo-based foaming agent.
Preferably, the physical blowing agent is a hydrofluoroalkane.
Preferably, the chemical blowing agent comprises azodicarbonamide and/or azodiisobutyronitrile.
Preferably, the physical blowing agent comprises difluoroethane (HFC-152A) and/or tetrafluoroethane (HFC-134A).
Preferably, the mass ratio of the chemical foaming agent to the physical foaming agent is 1 (1.2-6), for example, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:5.5, and the like, and further preferably 1 (1.5-5).
As a preferable technical scheme of the invention, the mass ratio of the chemical foaming agent to the physical foaming agent is 1 (1.2-6), and more preferably 1 (1.5-5), and the composite foaming system formed by the chemical foaming agent and the physical foaming agent is mutually cooperated with the flame-retardant smoke suppressant, so that compact and uniform foam holes can be formed in the foamed polystyrene material. If the mass ratio of the two is outside the preferred range of the present invention, the uniformity of cells is affected, the cells in the material are fused or broken, apparent defects are generated in the material, and the corrosion resistance of the material is affected.
Preferably, the foaming aid comprises urea and/or stearate.
Preferably, the stearate comprises zinc stearate and/or calcium stearate.
Preferably, the flame retardant expanded polystyrene material further comprises the following raw materials in parts by mass:
5-40 parts of reinforcing fiber
10-30 parts of toughening agent
0.5-2 parts of lubricant
0.5-2 parts of antioxidant
1-5 parts of a colorant.
The reinforcing fiber is 5 to 40 parts by weight based on 100 parts of polystyrene, and may be 8 parts, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, 28 parts, 30 parts, 32 parts, 35 parts, 38 parts, or the like, for example.
The toughening agent is 10-30 parts, and for example, 11 parts, 13 parts, 15 parts, 17 parts, 19 parts, 20 parts, 21 parts, 23 parts, 25 parts, 27 parts or 29 parts and the like can be used.
The lubricant is 0.5 to 2 parts, and for example, may be 0.8 parts, 1 part, 1.2 parts, 1.5 parts, 1.8 parts, or the like.
The antioxidant is 0.5-2 parts, for example, 0.8 parts, 1 part, 1.2 parts, 1.5 parts or 1.8 parts, etc.
The colorant is 1 to 5 parts, and for example, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, or the like can be used.
Preferably, the reinforcing fibers comprise any one or a combination of at least two of glass fibers, carbon fibers, aramid fibers.
Preferably, the toughening agent includes any one or a combination of at least two of SBS (styrene-butadiene-styrene block copolymer), SBR (styrene butadiene rubber), SEBS (hydrogenated styrene-butadiene block copolymer).
Preferably, the lubricant comprises any one or a combination of at least two of stearic acid, polyethylene wax, oxidized polyethylene wax.
Preferably, the antioxidant comprises any one or a combination of at least two of antioxidant 1010, antioxidant 168, antioxidant DNP and antioxidant TNP.
Preferably, the colorant is carbon black.
In a second aspect, the present invention provides a method for preparing the flame retardant expanded polystyrene composite according to the first aspect, the method comprising:
first mixing the components except the physical foaming agent to obtain a first mixture;
and (3) placing the first mixture into an extruder, heating to 180-200 ℃ (182 ℃, 185 ℃, 188 ℃, 190 ℃, 192 ℃, 195 ℃ or 198 ℃ and the like), adding a physical foaming agent into the mixture, and then performing melt mixing foaming and extrusion to obtain the flame retardant foaming polystyrene material.
Preferably, the first mixed material comprises polystyrene, flame retardant smoke suppressant, chemical blowing agent, foaming aid, optionally reinforcing fiber, optionally toughening agent, optionally lubricant, optionally antioxidant and optionally colorant.
Preferably, the temperature of the first mixture is 180-200deg.C, such as 182 deg.C, 185 deg.C, 188 deg.C, 190 deg.C, 192 deg.C, 195 deg.C or 198 deg.C.
Preferably, the first mixing is performed in a mixer.
Preferably, the extruder is a twin screw extruder.
Preferably, the temperature of the melt-kneading and foaming is 180 to 200 ℃, and may be 182 ℃, 185 ℃, 188 ℃, 190 ℃, 192 ℃, 195 ℃, 198 ℃ or the like, for example.
Specifically, the preparation method comprises the following steps:
(1) Placing all components except the physical foaming agent into a mixer, and carrying out melt mixing at 180-200 ℃ to obtain a first mixture;
(2) And (3) placing the first mixture obtained in the step (1) into a double-screw extruder, heating to 180-200 ℃, adding a physical foaming agent into a mixing section of the double-screw extruder, and extruding the obtained material through a die head after melting, mixing and foaming to obtain the flame-retardant foaming polystyrene material.
In another aspect, the present invention provides a storage and transportation tank, the material of the storage and transportation tank comprising the flame retardant expanded polystyrene composite according to the first aspect, or the flame retardant expanded polystyrene composite prepared by the preparation method according to the second aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) The flame-retardant foamed polystyrene material provided by the invention adopts a composite foaming system consisting of the chemical foaming agent and the physical foaming agent, and is compounded and mutually cooperated with the flame-retardant smoke suppressant with specific components, so that the flame-retardant foamed polystyrene material has a uniform and compact porous structure, is low in density, light in weight and good in heat insulation performance, has excellent flame-retardant smoke suppressant performance, corrosion resistance and mechanical strength, can be used as a material of a storage and transportation tank, and meets the requirements of long-term stable use and no frequent maintenance in a marine high-salt fog state.
(2) The invention ensures that the flame retardant foaming polystyrene material has even foaming, no apparent defects such as pore, protrusion, color change and the like on the surface, smooth and good appearance, oxygen index of more than 37%, smoke density grade of less than 16 and impact strength of 3.01-3.17 kJ/m by the optimal design and the synergistic effect of the compound foaming system consisting of the chemical foaming agent and the physical foaming agent and the flame retardant smoke suppressant 2 The impact strength after salt spray test of 500 h is still 2.99-3.14 kJ/m 2 The decay rate of the mechanical property after the salt spray corrosion is less than 1 percent, and the foam material has excellent foaming property, flame-retardant smoke-suppressing property, mechanical property, corrosion resistance and salt spray resistance.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
In the following specific embodiments of the present invention, the materials involved are as follows:
(1) And (3) polystyrene.
(2) Graphene oxide: and (3) powder.
(3) Chemical foaming agent: azodicarbonamide and azobisisobutyronitrile.
(4) Physical blowing agent: difluoroethane (HFC-152A), tetrafluoroethane (HFC-134A).
(5) Reinforcing fibers: glass fibers.
(6) Toughening agent: SBS, specifically SBS4402.
(7) Coloring agent: carbon black, NC8320.
Example 1
The flame-retardant expanded polystyrene composite material comprises the following raw materials in parts by mass:
100 parts of polystyrene
20 parts of flame-retardant smoke suppressant
Azodicarbonamide 1 part
HFC-134A 3 parts
Urea 1 part
20 parts of glass fiber
SBS 20 parts
Stearic acid 1 part
Antioxidant DNP 1 part
2 parts of a colorant;
the flame-retardant smoke suppressant is a combination of graphene oxide, ammonium phosphomolybdate and hexachlorocyclotriphosphazene, and the mass ratio of the graphene oxide to the ammonium phosphomolybdate to the hexachlorocyclotriphosphazene is 1:5:1.
The preparation method of the flame-retardant expanded polystyrene material specifically comprises the following steps:
(1) Placing the components except HFC-134A into a mixer according to the formula amount, and carrying out melt mixing at 190 ℃ to obtain a first mixture;
(2) Placing the first mixture obtained in the step (1) into a double-screw extruder, heating to 185 ℃, injecting HFC-134A into the first mixture in a mixing section, uniformly mixing all components under the action of double screws, melting, mixing and foaming the materials, and extruding the materials through a die head to obtain the flame-retardant foaming polystyrene material.
Example 2
The flame-retardant expanded polystyrene composite material comprises the following raw materials in parts by mass:
100 parts of polystyrene
20 parts of flame-retardant smoke suppressant
Azodicarbonamide 1 part
HFC-152A 3 parts
Urea 1 part
20 parts of glass fiber
SBS 20 parts
Stearic acid 1 part
Antioxidant DNP 1 part
2 parts of a colorant;
the flame-retardant smoke suppressant is a combination of graphene oxide, ammonium phosphomolybdate and hexachlorocyclotriphosphazene, and the mass ratio of the graphene oxide to the ammonium phosphomolybdate to the hexachlorocyclotriphosphazene is 1:5.5:0.8.
The preparation method of the flame retardant expanded polystyrene material is the same as that of example 1.
Example 3
The flame-retardant expanded polystyrene composite material comprises the following raw materials in parts by mass:
100 parts of polystyrene
20 parts of flame-retardant smoke suppressant
1.5 parts of azobisisobutyronitrile
HFC-134A 2.5 parts
Urea 1 part
20 parts of glass fiber
SBS 20 parts
Stearic acid 1 part
Antioxidant DNP 1 part
2 parts of a colorant;
the flame-retardant smoke suppressant is a combination of graphene oxide, ammonium phosphomolybdate and hexachlorocyclotriphosphazene, and the mass ratio of the graphene oxide to the ammonium phosphomolybdate to the hexachlorocyclotriphosphazene is 1:4.5:1.5.
The preparation method of the flame retardant expanded polystyrene material is the same as that of example 1.
Example 4
The flame-retardant expanded polystyrene composite material comprises the following raw materials in parts by mass:
100 parts of polystyrene
20 parts of flame-retardant smoke suppressant
0.8 part of azobisisobutyronitrile
HFC-152A 4 parts
Urea 1 part
20 parts of glass fiber
SBS 20 parts
Stearic acid 1 part
Antioxidant DNP 1 part
2 parts of a colorant;
the flame-retardant smoke suppressant is a combination of graphene oxide, ammonium phosphomolybdate and hexachlorocyclotriphosphazene, and the mass ratio of the graphene oxide to the ammonium phosphomolybdate to the hexachlorocyclotriphosphazene is 1:5:1.
The preparation method of the flame retardant expanded polystyrene material is the same as that of example 1.
Example 5
The flame-retardant expanded polystyrene composite material comprises the following raw materials in parts by mass:
100 parts of polystyrene
20 parts of flame-retardant smoke suppressant
Azodicarbonamide 2 parts
HFC-134A 2 parts
Urea 1 part
20 parts of glass fiber
SBS 20 parts
Stearic acid 1 part
Antioxidant DNP 1 part
2 parts of a colorant;
the flame-retardant smoke suppressant is a combination of graphene oxide, ammonium phosphomolybdate and hexachlorocyclotriphosphazene, and the mass ratio of the graphene oxide to the ammonium phosphomolybdate to the hexachlorocyclotriphosphazene is 1:5:1.
The preparation method of the flame retardant expanded polystyrene material is the same as that of example 1.
Example 6
The flame-retardant expanded polystyrene composite material comprises the following raw materials in parts by mass:
100 parts of polystyrene
20 parts of flame-retardant smoke suppressant
Azodicarbonamide 0.5 parts
HFC-134A 3.5 parts
Urea 1 part
20 parts of glass fiber
SBS 20 parts
Stearic acid 1 part
Antioxidant DNP 1 part
2 parts of a colorant;
the flame-retardant smoke suppressant is a combination of graphene oxide, ammonium phosphomolybdate and hexachlorocyclotriphosphazene, and the mass ratio of the graphene oxide to the ammonium phosphomolybdate to the hexachlorocyclotriphosphazene is 1:5:1.
The preparation method of the flame retardant expanded polystyrene material is the same as that of example 1.
Example 7
The flame-retardant expanded polystyrene composite material comprises the following raw materials in parts by mass:
100 parts of polystyrene
10 parts of flame-retardant smoke suppressant
Azodicarbonamide 1 part
HFC-134A 3 parts
Urea 1 part
20 parts of glass fiber
SBS 20 parts
Stearic acid 1 part
Antioxidant DNP 1 part
2 parts of a colorant;
the flame-retardant smoke suppressant is a combination of graphene oxide, ammonium phosphomolybdate and hexachlorocyclotriphosphazene, and the mass ratio of the graphene oxide to the ammonium phosphomolybdate to the hexachlorocyclotriphosphazene is 1:5:1.
The preparation method of the flame retardant expanded polystyrene material is the same as that of example 1.
Example 8
The flame-retardant expanded polystyrene composite material comprises the following raw materials in parts by mass:
100 parts of polystyrene
30 parts of flame-retardant smoke suppressant
Azodicarbonamide 1 part
HFC-134A 3 parts
Urea 1 part
20 parts of glass fiber
SBS 20 parts
Stearic acid 1 part
Antioxidant DNP 1 part
2 parts of a colorant;
the flame-retardant smoke suppressant is a combination of graphene oxide, ammonium phosphomolybdate and hexachlorocyclotriphosphazene, and the mass ratio of the graphene oxide to the ammonium phosphomolybdate to the hexachlorocyclotriphosphazene is 1:5:1.
The preparation method of the flame retardant expanded polystyrene material is the same as that of example 1.
Example 9
The flame-retardant expanded polystyrene composite material is different from the flame-retardant expanded polystyrene composite material in example 1 only in that the flame-retardant smoke suppressant is a combination of graphene oxide, ammonium phosphomolybdate and hexachlorocyclotriphosphazene, and the mass ratio of the graphene oxide to the ammonium phosphomolybdate to the hexachlorocyclotriphosphazene is 1:3:0.5 (the total amount is 20 parts, and the flame-retardant expanded polystyrene composite material is the same as the flame-retardant expanded polystyrene composite material in example 1); the kinds, amounts and preparation methods of the other components were the same as in example 1.
Example 10
The flame-retardant expanded polystyrene composite material is different from the flame-retardant expanded polystyrene composite material in example 1 only in that the flame-retardant smoke suppressant is a combination of graphene oxide, ammonium phosphomolybdate and hexachlorocyclotriphosphazene, and the mass ratio of the three is 1:8:2 (the total amount is 20 parts, and the flame-retardant expanded polystyrene composite material is the same as the flame-retardant expanded polystyrene composite material in example 1); the kinds, amounts and preparation methods of the other components were the same as in example 1.
Example 11
A storage and transportation tank is made of the flame retardant expanded polystyrene composite materials in examples 1 to 10, respectively.
Comparative example 1
The flame-retardant expanded polystyrene material is different from the example 1 only in that the flame-retardant smoke suppressant is a combination of graphene oxide and ammonium phosphomolybdate, and the mass ratio of the graphene oxide to the ammonium phosphomolybdate is 1:5 (the total amount is 20 parts, and the flame-retardant expanded polystyrene material is the same as the example 1); the kinds, amounts and preparation methods of the other components were the same as in example 1.
Comparative example 2
The flame-retardant expanded polystyrene composite material is different from the example 1 only in that the flame-retardant smoke suppressant is a combination of graphene oxide and hexachlorocyclotriphosphazene, and the mass ratio of the graphene oxide to the hexachlorocyclotriphosphazene is 1:1 (the total amount is 20 parts, and the flame-retardant expanded polystyrene composite material is the same as the example 1); the kinds, amounts and preparation methods of the other components were the same as in example 1.
Comparative example 3
The flame-retardant expanded polystyrene composite material is different from the example 1 only in that the flame-retardant smoke suppressant is a combination of ammonium phosphomolybdate and hexachlorocyclotriphosphazene, and the mass ratio of the two is 5:1 (the total amount is 20 parts, and the same as the example 1); the kinds, amounts and preparation methods of the other components were the same as in example 1.
Comparative example 4
A flame retardant expanded polystyrene composite differing from example 1 only in that the flame retardant smoke suppressant is graphene oxide (20 parts); the kinds, amounts and preparation methods of the other components were the same as in example 1.
Comparative example 5
A flame retardant expanded polystyrene composite differing from example 1 only in that the flame retardant smoke suppressant is ammonium phosphomolybdate (20 parts); the kinds, amounts and preparation methods of the other components were the same as in example 1.
Comparative example 6
A flame retardant expanded polystyrene composite differing from example 1 only in that the flame retardant smoke suppressant is hexachlorocyclotriphosphazene (20 parts); the kinds, amounts and preparation methods of the other components were the same as in example 1.
Comparative example 7
The flame-retardant expanded polystyrene composite material is different from the flame-retardant expanded polystyrene composite material in example 1 only in that the flame-retardant smoke suppressant is a combination of graphene oxide, ammonium phosphomolybdate and hexachlorocyclotriphosphazene, and the mass ratio of the graphene oxide to the ammonium phosphomolybdate to the hexachlorocyclotriphosphazene is 1:2:0.3 (the total amount is 20 parts, and the flame-retardant expanded polystyrene composite material is the same as the flame-retardant expanded polystyrene composite material in example 1); the kinds, amounts and preparation methods of the other components were the same as in example 1.
Comparative example 8
The flame-retardant expanded polystyrene composite material is different from the flame-retardant expanded polystyrene composite material in example 1 only in that the flame-retardant smoke suppressant is a combination of graphene oxide, ammonium phosphomolybdate and hexachlorocyclotriphosphazene, and the mass ratio of the three is 1:10:3 (the total amount is 20 parts, and the flame-retardant expanded polystyrene composite material is the same as the flame-retardant expanded polystyrene composite material in example 1); the kinds, amounts and preparation methods of the other components were the same as in example 1.
Comparative example 9
The flame-retardant expanded polystyrene composite material is different from the flame-retardant expanded polystyrene composite material in example 1 only in that the flame-retardant smoke suppressant is a combination of graphene oxide, ammonium phosphomolybdate and hexaphenoxy cyclotriphosphazene, and the mass ratio of the three is 1:5:1 (the total amount is 20 parts, and the flame-retardant expanded polystyrene composite material is the same as the example 1); the kinds, amounts and preparation methods of the other components were the same as in example 1.
Comparative example 10
A flame retardant expanded polystyrene composite differing from example 1 only in that azodicarbonamide was not added, HFC-134A was 4 parts; the kinds, amounts and preparation methods of the other components were the same as in example 1.
Comparative example 11
A flame retardant expanded polystyrene composite differing from example 1 only in that HFC-134A was not added and azodicarbonamide was 4 parts; the kinds, amounts and preparation methods of the other components were the same as in example 1.
Comparative example 12
A flame retardant expanded polystyrene composite differing from example 1 only in that no flame retardant smoke suppressant was added; the kinds, amounts and preparation methods of the other components were the same as in example 1.
The following performance tests were performed on the flame retardant expanded polystyrene composite provided in examples 1 to 10 and comparative examples 1 to 12:
(1) Oxygen index: testing by using a method in a standard GB/T2406.2-2009;
(2) Smoke density rating: testing by adopting a method in a standard GB/T8323.1-2008;
(3) Surface morphology: visual observation of the appearance of the flame retardant foamed polystyrene material to be tested is used for evaluating the foaming performance; and (2) the following steps: no pores, protrusions or discoloration are observed on the surface, the surface is defect-free, the appearance is smooth and good, and the foaming performance is excellent; and ∈: the surface has one of pores, protrusions and discoloration, and at 100 cm 2 The number of defects (pores, protrusions and discoloration) in the range is less than or equal to 1, the smoothness and appearance are good, and the foaming performance is good; delta: at least one of pores, protrusions, discoloration are present on the surface, and at 100 cm 2 The number of defects (voids, protrusions and discoloration) in the range is 2 to 4, the smoothness and appearance are poor, and the foaming property is poor; x: at least one of pores, protrusions, discoloration are present on the surface, and at 100 cm 2 The number of defects (pores, protrusions and discoloration) in the range is more than or equal to 5, the smoothness and appearance are poor, and the foaming performance is poor;
(4) Salt spray resistance: testing by adopting a method in a standard GB/T1771-2007, wherein the testing time is 500 h, and respectively inspecting the impact strength before and after salt spray resistance testing and 500 h;
(5) Impact strength: the notched Izod impact strength was tested using the method in Standard GB/T1843-2008.
The test results are shown in table 1:
table 1 results of performance testing of materials
| Oxygen index (%) | Smoke density grade | Apparent morphology | Impact strength (kJ/m) 2 ） | Impact resistance (kJ/m) after 500. 500 h salt spray resistance test 2 ） | |
| Example 1 | 38.5 | 14.7 | 〇 | 3.15 | 3.14 |
| Example 2 | 38.1 | 15.3 | 〇 | 3.08 | 3.06 |
| Example 3 | 37.9 | 15.7 | 〇 | 3.17 | 3.16 |
| Example 4 | 37.8 | 15.6 | 〇 | 3.02 | 2.99 |
| Example 5 | 37.6 | 15.1 | □ | 3.16 | 3.11 |
| Example 6 | 37.7 | 15.0 | □ | 3.01 | 2.96 |
| Example 7 | 37.1 | 15.8 | 〇 | 3.13 | 3.09 |
| Example 8 | 38.7 | 14.5 | 〇 | 3.08 | 3.06 |
| Example 9 | 37.4 | 15.6 | □ | 3.18 | 3.12 |
| Example 10 | 38.2 | 14.8 | □ | 3.09 | 3.05 |
| Comparative example 1 | 32.2 | 32.5 | △ | 3.13 | 2.96 |
| Comparative example 2 | 32.4 | 36.9 | △ | 3.16 | 3.02 |
| Comparative example 3 | 31.8 | 30.2 | × | 2.31 | 2.03 |
| Comparative example 4 | 30.6 | 58.5 | × | 3.08 | 2.88 |
| Comparative example 5 | 29.2 | 46.2 | × | 2.28 | 1.95 |
| Comparative example 6 | 29.8 | 71.3 | × | 2.26 | 1.94 |
| Comparative example 7 | 33.1 | 17.7 | △ | 3.17 | 2.98 |
| Comparative example 8 | 34.5 | 15.9 | △ | 2.89 | 2.62 |
| Comparative example 9 | 35.2 | 15.5 | △ | 3.05 | 2.9 |
| Comparative example 10 | 37.8 | 16.1 | × | 2.88 | 2.68 |
| Comparative example 11 | 36.4 | 17.3 | × | 2.96 | 2.73 |
| Comparative example 12 | 25.2 | 78.6 | △ | 2.76 | 2.25 |
According to the performance test results in Table 1, the invention adopts a composite foaming system composed of a chemical foaming agent and a physical foaming agent, and the composite foaming system is mutually cooperated with a flame-retardant smoke suppressant with specific components, so that the flame-retardant foaming polystyrene material has excellent foaming performance, forms a uniform and compact porous structure, has no defects of pores, protrusions, color change and the like on the surface, has smooth and good appearance, has excellent flame-retardant smoke suppressant performance and salt fog resistance, has an oxygen index of more than 37%, and has a smoke density grade of less than 16. Wherein, in the flame retardant expanded polystyrene material provided in examples 1-4 and 7-8, the oxygen index is 37.1-38.5%, the smoke density grade is 14.5-15.8, and the impact strength is 3.01-3.17 kJ/m by the optimization and synergistic effect of the composite foaming system consisting of the chemical foaming agent and the physical foaming agent and the flame retardant smoke suppressant 2 The impact strength after salt spray test of 500 h is still 2.99-3.14 kJ/m 2 The decay proportion of the mechanical property is less than 1 percent, and the salt spray corrosion resistance is excellent.
Comparing examples 1-4 with examples 5-6, it is known that the chemical foaming agent and the physical foaming agent are compounded according to the mass ratio of 1 (1.2-6), so that compact and uniform cells can be formed in the foamed polystyrene material, and the apparent morphology is better; the amount of azodicarbonamide used as the chemical blowing agent in example 5 was large, and the amount of HFC-134A used as the physical blowing agent in example 6 was large, resulting in a slight decrease in the uniformity of foaming and a slight defect in appearance.
As is clear from comparison of example 1 with examples 7 to 8, as the amount of the flame retardant smoke suppressant increases from 10 parts to 20 parts to 30 parts, the oxygen index of the flame retardant expanded polystyrene material increases, the smoke density decreases, and the flame retardant and smoke suppressing effects are more excellent, but the flame retardancy of the flame retardant expanded polystyrene material increases less when the amount is 30 parts than when it is 20 parts, and the amount of the flame retardant smoke suppressant is preferably 20 parts from the viewpoint of cost.
As can be seen from comparison of examples 1-4 and examples 9-10, in the flame-retardant smoke suppressant, when the mass ratio of graphene oxide to ammonium phosphomolybdate to hexachlorocyclotriphosphazene is 1 (4-6) (0.7-1.5), the three are mutually cooperated, so that the optimal balance effect in the aspects of flame retardance, foaming performance and corrosion resistance of the flame-retardant foaming polystyrene material is achieved.
Compared with comparative example 12 without flame-retardant smoke suppressant, the invention adopts the combination of graphene oxide, ammonium phosphomolybdate and hexachlorocyclotriphosphazene as the flame-retardant smoke suppressant, and the three are synergistic and coactive, thus improving the flame retardance of the material, reducing the smoke density, simultaneously being capable of being mutually synergistic with a composite foaming system, improving the foaming uniformity of the foaming material and improving the salt fog resistance of the material.
Comparing example 1 with comparative examples 1-6, comparative example 9, it is known that if the flame retardant smoke suppressant is not a combination of graphene oxide, ammonium phosphomolybdate and hexachlorocyclotriphosphazene, the absence of either component affects the foaming properties, flame retardant smoke suppressant properties and salt spray resistance of the material. If hexachlorocyclotriphosphazene is replaced by hexaphenoxy cyclotriphosphazene (comparative example 9), interaction with graphene oxide cannot be performed, so that the flame retardant property of the material is reduced, and the foaming uniformity and salt spray resistance are also insufficient.
As can be seen from comparison of example 1 with comparative examples 7 to 8, if the mass ratio of graphene oxide, ammonium phosphomolybdate and hexachlorocyclotriphosphazene in the flame retardant smoke suppressant exceeds the range of 1 (3 to 8): (0.5 to 2), too low or too high content of ammonium phosphomolybdate and hexachlorocyclotriphosphazene not only affects the synergistic flame retardance of the three but also cannot effectively promote cell nucleation, and has a certain adverse effect on foaming performance, apparent morphology and salt spray resistance.
As can be seen from comparison of example 1 and comparative examples 10 to 11, the present invention adopts a composite foaming system of a chemical foaming agent and a physical foaming agent, and obtains excellent foaming performance under the synergistic effect of flame retardant smoke suppressant, and the foaming effect of a single physical foaming agent or a single chemical foaming agent is poor, and the salt spray resistance is also insufficient.
The applicant states that the flame retardant expanded polystyrene material of the present invention, and the preparation method and application thereof, are illustrated by the above examples, but the present invention is not limited to the above examples, i.e., it does not mean that the present invention must be practiced by relying on the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (8)
1. The flame-retardant expanded polystyrene composite material is characterized by comprising the following raw materials in parts by mass:
100 parts of polystyrene
10-30 parts of flame-retardant smoke suppressant
0.5-5 parts of chemical foaming agent
2-10 parts of physical foaming agent
0.5-2 parts of foaming auxiliary agent;
the flame-retardant smoke suppressant is a combination of graphene oxide, ammonium phosphomolybdate and hexachlorocyclotriphosphazene;
the mass ratio of graphene oxide to ammonium phosphomolybdate to hexachlorocyclotriphosphazene in the flame-retardant smoke suppressant is 1 (3-8) (0.5-2);
the mass ratio of the chemical foaming agent to the physical foaming agent is 1 (1.2-6);
the flame-retardant expanded polystyrene composite material comprises the following raw materials in parts by mass:
5-40 parts of reinforcing fiber
10-30 parts of toughening agent
0.5-2 parts of lubricant
0.5-2 parts of antioxidant
1-5 parts of a colorant.
2. The flame retardant expanded polystyrene composite according to claim 1, wherein said chemical blowing agent is an azo-based blowing agent and said physical blowing agent is a hydrogenated fluoroalkane.
3. The flame retardant expanded polystyrene composite according to claim 1, wherein said chemical blowing agent comprises azodicarbonamide and/or azodiisobutyronitrile; the physical blowing agent comprises difluoroethane and/or tetrafluoroethane.
4. The flame retardant expanded polystyrene composite of claim 1, wherein said foaming aid comprises urea and/or stearate.
5. The flame retardant expanded polystyrene composite according to claim 1, wherein said reinforcing fibers comprise any one or a combination of at least two of glass fibers, carbon fibers, aramid fibers;
the toughening agent comprises any one or a combination of at least two of SBS, SBR, SEBS;
the lubricant comprises any one or a combination of at least two of stearic acid, polyethylene wax and oxidized polyethylene wax;
the antioxidant comprises any one or a combination of at least two of antioxidant 1010, antioxidant 168, antioxidant DNP and antioxidant TNP;
the colorant is carbon black.
6. A method of preparing a flame retardant expanded polystyrene composite according to any one of claims 1 to 5, comprising:
firstly mixing polystyrene, a flame-retardant smoke suppressant, a chemical foaming agent and a foaming auxiliary agent to obtain a first mixture;
and placing the first mixture into an extruder, heating to 180-200 ℃, adding a physical foaming agent into the mixture, and then performing melt mixing foaming and extrusion to obtain the flame-retardant foaming polystyrene composite material.
7. The method according to claim 6, wherein the temperature of the first mixing is 180 to 200 ℃, and the temperature of the melt-kneading foaming is 180 to 200 ℃.
8. A storage and transportation tank, wherein the material of the storage and transportation tank comprises the flame retardant expanded polystyrene composite material according to any one of claims 1 to 5, or the flame retardant expanded polystyrene composite material prepared by the preparation method according to claim 6 or 7.
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