CN106750174A - A kind of fire-retardant phase-change energy-storing heat preservation heat-barrier material and preparation method thereof - Google Patents
A kind of fire-retardant phase-change energy-storing heat preservation heat-barrier material and preparation method thereof Download PDFInfo
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- CN106750174A CN106750174A CN201710037699.2A CN201710037699A CN106750174A CN 106750174 A CN106750174 A CN 106750174A CN 201710037699 A CN201710037699 A CN 201710037699A CN 106750174 A CN106750174 A CN 106750174A
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- fire
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- barrier material
- phase
- heat preservation
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- 239000000463 material Substances 0.000 title claims abstract description 60
- 239000003063 flame retardant Substances 0.000 title claims abstract description 47
- 238000004321 preservation Methods 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 37
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229920000570 polyether Polymers 0.000 claims abstract description 37
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 21
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 21
- 229910019213 POCl3 Inorganic materials 0.000 claims abstract description 18
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000009825 accumulation Methods 0.000 claims abstract description 13
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229940043237 diethanolamine Drugs 0.000 claims abstract description 11
- 229920002545 silicone oil Polymers 0.000 claims abstract description 11
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 10
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000012948 isocyanate Substances 0.000 claims abstract description 8
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000007822 coupling agent Substances 0.000 claims abstract description 7
- -1 polymethylene Polymers 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 35
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 20
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000012263 liquid product Substances 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 101000598921 Homo sapiens Orexin Proteins 0.000 claims description 9
- 101001123245 Homo sapiens Protoporphyrinogen oxidase Proteins 0.000 claims description 9
- 102100029028 Protoporphyrinogen oxidase Human genes 0.000 claims description 9
- 239000006260 foam Substances 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 238000005187 foaming Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 239000008118 PEG 6000 Substances 0.000 claims description 2
- 229920002584 Polyethylene Glycol 6000 Polymers 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 claims 1
- 150000002170 ethers Chemical class 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims 1
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 claims 1
- 229920000137 polyphosphoric acid Polymers 0.000 claims 1
- 238000004134 energy conservation Methods 0.000 abstract description 4
- 238000004079 fireproofing Methods 0.000 abstract description 3
- 230000001737 promoting effect Effects 0.000 abstract description 3
- 230000009466 transformation Effects 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 2
- 238000004146 energy storage Methods 0.000 description 22
- 239000011232 storage material Substances 0.000 description 13
- 229920001451 polypropylene glycol Polymers 0.000 description 11
- 239000000779 smoke Substances 0.000 description 10
- 230000008859 change Effects 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 229920005830 Polyurethane Foam Polymers 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical class [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 6
- 239000011810 insulating material Substances 0.000 description 6
- 229920005862 polyol Polymers 0.000 description 6
- 150000003077 polyols Chemical class 0.000 description 6
- 239000011496 polyurethane foam Substances 0.000 description 6
- 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 description 5
- 239000004254 Ammonium phosphate Substances 0.000 description 4
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 description 4
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 4
- 235000019289 ammonium phosphates Nutrition 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 3
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- 235000011187 glycerol Nutrition 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
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- 239000003610 charcoal Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000012774 insulation material Substances 0.000 description 2
- 229940057847 polyethylene glycol 600 Drugs 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
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- 230000006835 compression Effects 0.000 description 1
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- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000012782 phase change material Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
- C08G18/3275—Hydroxyamines containing two hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6461—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having phosphorus
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6523—Compounds of group C08G18/3225 or C08G18/3271 or polyamines of C08G18/38
- C08G18/6535—Compounds of group C08G18/3271
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
- C08G65/327—Polymers modified by chemical after-treatment with inorganic compounds containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
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- 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
- C08J9/141—Hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34922—Melamine; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
- C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2101/00—Manufacture of cellular products
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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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
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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
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a kind of fire-retardant phase-change energy-storing heat preservation heat-barrier material and preparation method thereof.The material is composed of the following components：Modified polyether polylol, polymethylene multi-phenenyl isocyanate, diethanol amine, triethylene diamine, stannous octoate, silicone oil, n-hexane, water, APP and melamine；Wherein modified polyether polylol is to be grafted phase transformation ergastic substances polyethylene glycol as coupling agent by POCl3 to be prepared to PPG, and phase-change accumulation energy material has been reacted on PPG completely by bonded form.Fire-retardant phase-change energy-storing heat preservation heat-barrier material prepared by the present invention, except possessing while thermal and insulating performance, fire resistance is also equipped with, for the heat-insulated security of building exterior wall heat preserving provides greatly support, to promoting the progress of China's energy conservation project fireproofing technique and developing significant.
Description
Technical field
Present invention design heat preserving and insulating material, a kind of fire-retardant phase-change energy-storing heat preservation heat-barrier material of specific design and its preparation side
Method.The fire-retardant phase-change energy-storing heat preservation heat-barrier material of the present invention possesses incubation and thermal insulation function, anti-flaming function, energy-storage function in one,
There is very big prospect in the application of the outer enclosed structure of building energy conservation.
Background technology
Polyurethane foam plastics is a kind of new high molecular synthetic material, and it is by isocyanates and polyol reaction system
Into a kind of polymer with carbamate segment constitutional repeating unit.At present, hard polyurethane foams are mainly used in building
Build the fields such as industry, refrigeration plant, furniture industry, household electrical appliance.
At this stage, hard polyurethane foams are most often used as external-wall heat-insulation material, how to improve its thermal and insulating performance one
It is directly problem that people are thought deeply；Absorbed in phase transition process using material or released the phase change energy storage technology of latent heat of phase change also by
The visual field of people is gradually entered, so-called phase-changing energy storage material can be just that the temperature of itself is maintained in specific range of temperatures not
Become, by changing the material that own physical state is stored or discharges heat；In the rigid polyurethane foam as external-wall heat-insulation material
Phase-changing energy storage material is added in foam, the thermal conductivity factor of material can be reduced, improve the heat insulating effect of material, but phase transformation is stored up
The addition of energy material causes that the fire risk of hard polyurethane material is greatly improved, therefore, needing one kind badly is not reducing material
On the premise of itself thermal and insulating performance even increases, the novel high polymer material that fire resistance is also improved.
The content of the invention
In view of the deficiencies in the prior art part, a kind of fire-retardant phase-change energy-storing heat preservation heat-barrier material of present invention offer and its preparation
Method.The material is using the modified phosphorous polyether polyol flame retardant with energy-storage function and mutual with the material such as isocyanates
Effect prepares fire-retardant phase-changing energy storage material, and it is also equipped with energy storage, resistance while keeping even improving thermal and insulating performance
Combustion performance, and with good compression strength and dimensional stability, for the heat-insulated security of building exterior wall heat preserving provides pole
Big support, to promoting the progress of China's Energy Conservation Project in Construction fireproofing technique and developing significant.
Technical proposal that the invention solves the above-mentioned problems is as follows, there is provided a kind of fire-retardant phase-change energy-storing heat preservation heat-barrier material, bag
Include the component of following weight portion：
The modified polyether polylol is prepared by the following method and obtains：With POCl3 as coupling agent, by phase-change accumulation energy
Material polyethylene glycol is keyed on PPG, is prepared.
Beneficial effects of the present invention are：Had with other using the phosphorus-containing polyol for being linked with phase-change accumulation energy material polyethylene glycol
The material for having certain content mutually acts synergistically, and the phosphorous polyether polyol flame retardant with phase change energy storage function, the material is obtained
Material can still keep the essence of low thermal conductivity organic polymer foams, and its phase change energy storage function causes that it can be used as a kind of " intelligence
The feature of energy " heat preserving and insulating material, absorption heat, the energy of storage are undergone phase transition when comfort temperature of the indoor temperature higher than human body
Amount is discharged when temperature is relatively low indoors, and makes the indoor temperature long period constant in human body optimal comfort temperature range.
On the basis of above-mentioned technical proposal, the present invention can also do following improvement：
A kind of fire-retardant phase-change energy-storing heat preservation heat-barrier material, including following weight portion component：
Further, the specific preparation method of the modified polyether polylol is：
(1) polyethylene glycol is added in tetrahydrofuran, stirring is completely dissolved polyethylene glycol, obtains solution A；
(2) POCl3 is added in n-hexane, stirring is completely dissolved POCl3, obtains solution B；
(3) at 40-50 DEG C, solution B is added in solution A, is reacted 1~1.5 hour, revolving obtains liquid product
C；
(4) liquid product C is heated to 90-100 DEG C, PPG is added dropwise, reacted 1~1.5 hour, obtained final product modified poly-
Ethoxylated polyhydric alcohol；
Further, the PPG is glycerine base PPOX ether, trimethylolpropane PPOX ether
And any one in pentaerythrite PPOX ether.
Beneficial effects of the present invention are：When POCl3 is added drop-wise in polyglycol solution, P-Cl keys can rapidly with it is poly-
The hydroxyl of ethylene glycol end reacts and generates P-O-C keys and accessory substance HCl gases, when certain P-Cl key of POCl3 is bonded
After upper peg molecule, the reactivity of remaining P-Cl can be reduced because of space steric effect, and the present invention is by controlling poly- second
The addition of glycol, and then the POCl3-polyethylene glycol compound containing P-Cl keys is obtained.
During the phosphorous PPG with phase-change accumulation energy segment is prepared, polyethylene glycol and POCl3Reaction ten
Divide violent, it is easy to generate other products, introduce tetrahydrofuran as solvent, the n-hexane of polyethylene glycol as POCl3It is dilute
Agent is released, reaction rate, another aspect n-hexane and tetrahydrofuran azeotropic on the one hand can be effectively controlled, general 50 DEG C or so are rotated
Can just steam together；
Simultaneously as embedded in poly- second two by way of block in the phosphorous PPG with phase-change accumulation energy segment
Alcohol, theoretical according to block macromolecular, the block in block macromolecular can keep independence on crystal property, therefore, poly- second
The crystallinity of glycol can keep independence, so that the function of PPG phase-change accumulation energy is assigned, also, PPG knot
The network confinement effect of the skeleton function and polyurethane three-dimensional net structure of structure unit and MDI construction units so that even if poly-
There is melt phase change and also do not flow in ethylene glycol；Simultaneously as coupling agent POCl3 introduces halogen-free flameproof element P elements,
Be heated Shi Qike with tertiary charcoal, phenyl ring in catalytic cpd etc. into carbon structure unit into charcoal, rise heat-insulated oxygen barrier and hinder cohesion
Mutually transmitted with the material of gas phase and play fire retardation.
Further, the weight ratio of the polyethylene glycol, POCl3 and PPG is 1~3：1~1.15：2~7；
The polyethylene glycol is 1.5~3 with the mass volume ratio of tetrahydrofuran：3~7；
The POCl3 is 1~1.15 with the mass volume ratio of n-hexane：2~4.
Further, the polyethylene glycol is polyethylene glycol -600, PEG-8 00 or PEG-6000.
Further, in step (3), at 45 DEG C, solution B is slowly dropped in solution A, is reacted 1 hour, obtain liquid
Product C.
Further, in step (4), liquid product C is heated to 90 DEG C, quick stirring is lower to be added dropwise PPG, reaction 1
Hour, obtain modified polyether polylol.
The preparation method of above-mentioned fire-retardant phase-change energy-storing heat preservation heat-barrier material, including：
Add diethanolamine solution in modified polyether polylol, stirring reaction 20~30 minutes, adjusting its acid number is
0.03~0.05mgKOH/g, the modified polyether polylol needed for being foamed；
It is modified polyether polylol, stannous octoate, silicone oil needed for weighing foaming obtained above, poly- according to formula rate
The mixing of ammonium phosphate, melamine and water, after stirring 10~15 minutes, is subsequently adding n-hexane, stirs 1~2 minute, adds many
Polymethylene polyphenyl isocyanates and triethylene diamine, quickly stirring are foamed for 8~10 seconds, and the foam that will be obtained is in 100-
Cured 2-3 hours at 120 DEG C, obtain fire-retardant phase-change energy-storing heat preservation heat-barrier material.
The invention has the advantages that：
1) the obtained fire-retardant phase-change energy-storing heat preservation heat-barrier material of the present invention has good in the presence of inorganic fire-retarded element P
Flame retardant effect, while causing heat preserving and insulating material to be led using the introducing that the energy storage capacity of phase-change accumulation energy material compensate for P element
Hot coefficient increase so that the thermal and insulating performance of heat preserving and insulating material is not reduced or even increased, while effectively reducing
The fire risk of heat preserving and insulating material, for the heat-insulated security of building exterior wall heat preserving provides technical support, to promoting China
The development of Energy Conservation Project in Construction fireproofing technique is significant.
2) present invention will be embedded in polyethylene glycol by way of block in PPG so that its crystal property keeps
Independence, so that with good phase change energy storage function, meanwhile, then P elements are introduced wherein, make it while having good
Continue fire resistance.
3) that the present invention is provided is phosphorous cheap and easy to get with phase-change accumulation energy segment polyether polyols raw polyol, without halogen, ring
Protect nontoxic, fire-retardant poly- ammonia can be prepared with poly methylene poly phenyl poly isocyanate reaction containing the reactive hydroxyl end groups of more than 2
Ester phase-changing energy storage material, both overcome physics additive flame retardant in polyurethane system bad dispersibility, be easily reduced material thing
The defect of rationality energy, thermal and insulating performance reduction caused by the addition of P elements is solved further through the addition of phase-changing energy storage material
Problem.
Brief description of the drawings
The DSC figures that Fig. 1 is determined for the differential scanning calorimeter of pure sample polyurethane foam；
Fig. 2 is the DSC figures of the differential scanning calorimeter measure of fire-retardant phase-change energy-storing heat preservation heat-barrier material of the invention；
Fig. 3 is the smoke density analysis chart of fire-retardant phase-change energy-storing heat preservation heat-barrier material of the invention.
Specific embodiment
Principle of the invention and feature are described below in conjunction with accompanying drawing, example is served only for explaining the present invention, and
It is non-for limiting the scope of the present invention.
Embodiment 1：
A kind of fire-retardant phase-changing energy storage material, including following weight portion component：
100 parts of modified polyether polylol, 20 parts of diethanol amine, 150 parts of polymethylene multi-phenenyl isocyanate, triethylene two
2 parts of 2.0 parts of amine, 0.3 part of stannous octoate, 2.0 parts of silicone oil, 15 parts of n-hexane, 10 parts of APP, 10 parts of melamine and water.
The preparation process of the modified polyether polylol is：With POCl3 as coupling agent, by filling for its P-Cl key and OH
Divide reaction, phase-change accumulation energy material polyethylene glycol is keyed on glycerine base PPOX ether；
Specifically include following steps：
(1) 30ml tetrahydrofurans are added in three neck round bottom flask, 15g PEG-8s 00, normal temperature is then slowly added into
Lower quick stirring, obtains solution A after dissolving；
(2) under normal temperature, 10.00g POCl3s are added in 20ml n-hexanes and are configured to solution B, be subsequently poured into constant pressure
Funnel, at 45 DEG C, quick stirring is slowly dropped in solution A, and tear drop is finished, and is reacted 1 hour, and revolving obtains liquid product
C；
(3) liquid product C is to slowly warm up to 90 DEG C, 85g glycerine bases polyoxygenated third is slowly added dropwise under fast stirring
Alkene ether, tear drop is finished, and is reacted 1 hour, obtains modified polyether polylol.
The preparation method of above-mentioned fire-retardant phase-changing energy storage material is：
Each component is weighed according to formula rate, diethanolamine solution, stirring reaction 20 are added in modified polyether polylol
Minute, its acid number is adjusted for 0.03~0.05mgKOH/g, the modified polyether polylol needed for being foamed；
It is modified polyether polylol, stannous octoate, silicone oil needed for weighing foaming obtained above, poly- according to formula rate
The mixing of ammonium phosphate, melamine and water, after stirring 10~15 minutes, is subsequently adding n-hexane, stirs 1~2 minute, adds many
Polymethylene polyphenyl isocyanates and triethylene diamine, quickly stirring are foamed for 8~10 seconds, and well mixed foam is poured into
In the mould got ready, it is put in baking oven and is cured 2 hours in 120 DEG C, the demoulding obtains fire-retardant phase-change energy-storing heat preservation heat-barrier material.
Embodiment 2：
A kind of fire-retardant phase-changing energy storage material, including following weight portion component：
120 parts of modified polyether polylol, 25 parts of diethanol amine, 146 parts of polymethylene multi-phenenyl isocyanate, triethylene two
2.5 parts of amine, 0.5 part of stannous octoate, 3.0 parts of silicone oil, 10 parts of n-hexane, 30 parts of APP, 30 parts of melamine and water 1.5
Part.
The preparation process of the modified polyether polylol is：With POCl3 as coupling agent, by filling for its P-Cl key and OH
Divide reaction, phase-change accumulation energy material polyethylene glycol is keyed on trimethylolpropane PPOX ether；
Specifically include following steps：
(1) 50ml tetrahydrofurans are added in three neck round bottom flask, 25g PEG-8s 00, normal temperature is then slowly added into
Lower quick stirring, obtains solution A after dissolving；
(2) under normal temperature, 11.50g POCl3s are added in 40ml n-hexanes and are configured to solution B, be subsequently poured into constant pressure
Funnel, at 50 DEG C, quick stirring is slowly dropped in solution A, and tear drop is finished, and is reacted 1.5 hours, revolving, obtains liquid product
Thing C；
(3) liquid product C is to slowly warm up to 100 DEG C, 75g trimethylolpropanes base is slowly added dropwise under fast stirring and is gathered
Propylene oxide ether, tear drop is finished, and is reacted 1.5 hours, obtains phosphorous and phase-change accumulation energy segment modified polyether polylol.
The preparation method of above-mentioned fire-retardant phase-changing energy storage material is：
Each component is weighed according to formula rate, diethanolamine solution, stirring reaction 20 are added in modified polyether polylol
Minute, its acid number is adjusted for 0.03~0.05mgKOH/g, the modified polyether polylol needed for being foamed；
It is modified polyether polylol, stannous octoate, silicone oil needed for weighing foaming obtained above, poly- according to formula rate
The mixing of ammonium phosphate, melamine and water, after stirring 10~15 minutes, is subsequently adding n-hexane, stirs 1~2 minute, adds many
Polymethylene polyphenyl isocyanates and triethylene diamine, quickly stirring are foamed for 8~10 seconds, and well mixed foam is poured into
In the mould got ready, it is put in baking oven and is cured 2 hours in 120 DEG C, the demoulding obtains fire-retardant phase-change energy-storing heat preservation heat-barrier material.
Embodiment 3：
A kind of fire-retardant phase-changing energy storage material, including following weight portion component：
80 parts of modified polyether polylol, 23 parts of diethanol amine, 153 parts of polymethylene multi-phenenyl isocyanate, triethylene two
1.8 parts of 2.3 parts of amine, 0.4 part of stannous octoate, 2.5 parts of silicone oil, 13 parts of n-hexane and water.
The preparation process of the modified polyether polylol is：With POCl3 as coupling agent, by filling for its P-Cl key and OH
Divide reaction, phase-change accumulation energy material polyethylene glycol is keyed on pentaerythrite base PPOX ether；
Specifically include following steps：
(1) 70ml tetrahydrofurans are added in three neck round bottom flask, 30g polyethylene glycol -600, normal temperature are then slowly added into
Lower quick stirring, obtains solution A after dissolving；
(2) under normal temperature, 11.50g POCl3s are added in 40ml n-hexanes and are configured to solution B, be subsequently poured into constant pressure
Funnel, at 40 DEG C, quick stirring is slowly dropped in solution A, and tear drop is finished, and is reacted 1.5 hours, revolving, obtains liquid product
Thing C；
(3) liquid product C is to slowly warm up to 95 DEG C, 70g pentaerythrite base polyoxygenateds is slowly added dropwise under fast stirring
Propylene ether, tear drop is finished, and is reacted 1 hour, obtains modified polyether polylol.
The preparation method of above-mentioned fire-retardant phase-changing energy storage material is：
Each component is weighed according to formula rate, diethanolamine solution, stirring reaction 20 are added in modified polyether polylol
Minute, its acid number is adjusted for 0.03~0.05mgKOH/g, the modified polyether polylol needed for being foamed；
It is modified polyether polylol, stannous octoate, silicone oil needed for weighing foaming obtained above, poly- according to formula rate
The mixing of ammonium phosphate, melamine and water, after stirring 10~15 minutes, is subsequently adding n-hexane, stirs 1~2 minute, adds many
Polymethylene polyphenyl isocyanates and triethylene diamine, quickly stirring are foamed for 8~10 seconds, and well mixed foam is poured into
In the mould got ready, it is put in baking oven and is cured 2 hours in 120 DEG C, the demoulding obtains fire-retardant phase-change energy-storing heat preservation heat-barrier material.
Test example：
Fire-retardant phase-changing energy storage material obtained in the embodiment of the present invention 1 is respectively adopted differential scanning calorimeter and smoke density is surveyed
Examination instrument determines its performance respectively, specific as follows：
Fig. 1 is that the PPG that could be used without before modified foam the differential scanning of the polyurethane foam for preparing
The DSC figures that calorimeter is determined, Fig. 2 is that the differential scanning calorimeter of fire-retardant phase-change energy-storing heat preservation heat-barrier material of the invention is determined
DSC schemes；Be can see from the contrast of two figures, the obtained fire-retardant phase-change energy-storing heat preservation heat-barrier material of the present invention has obvious phase
Become peak, the generation at the phase transformation peak and the temperature range at peak are 21.2~41.5 DEG C, be 27.23KJ/ (kgk), symbol than thermal change
Its demand as heat preserving and insulating material is closed, possesses the performance of insulation.
Its fire resistance is carried out using oxygen index method GB/T2406-93 and horizontal vertical combustion method GB/T2408-2008
Determine, result is：The oxygen index (OI) of the fire-retardant phase-changing energy storage material be 30.3, and oxygen index (OI) between 27-60 when, material is in air
In just being capable of self-extinguishment；The horizontal firing grade of the material is FH-1, and vertical combustion grade is FV-0, it is seen that the anti-flammability of the material
Can be good.
Fig. 3 is the smoke density analysis chart of fire-retardant phase-change energy-storing heat preservation heat-barrier material of the invention；Smoke density refers to material in rule
Fixed experimental condition issues measuring for smoke, and it is described with the light intensity decays amount through cigarette.The bigger material of smoke density
Material, evacuates personnel during to fire and fire extinguishing is more unfavorable.The fire-retardant foamed material of common use additive flame retardant, its smoke density
Grade can become much larger, reach more than 50, and new phase change materials for heat energy storage of the invention passes through being introduced into for halogen-free flameproof element P
Row is fire-retardant, and smoke density grade (SDR) is relatively low, and only 24.59, maximum smoke density (MSD) also only reaches 32, is not increasing smoke density
While reached the demand of fire-protection rating.
The foregoing is only presently preferred embodiments of the present invention, be not intended to limit the invention, it is all it is of the invention spirit and
Within principle, any modification, equivalent substitution and improvements made etc. should be included within the scope of the present invention.
Claims (9)
1. a kind of fire-retardant phase-change energy-storing heat preservation heat-barrier material, it is characterized in that, including following weight portion component：
80~120 parts of modified polyether polylol
20~25 parts of diethanol amine
146~153 parts of polymethylene multi-phenenyl isocyanate
2.0~2.5 parts of triethylene diamine
0.3~0.5 part of stannous octoate
2.0~3.0 parts of silicone oil
10~15 parts of n-hexane
1.5~2 parts of water
0~30 part of APP
0~30 part of melamine；
The modified polyether polylol is prepared by the following method and obtains：With POCl3 as coupling agent, by phase-change accumulation energy material
Polyethylene glycol is keyed on PPG, is prepared.
2. fire-retardant phase-change energy-storing heat preservation heat-barrier material according to claim 1, it is characterized in that, including following weight portion group
Point：
100 parts of modified polyether polylol
20 parts of diethanol amine
150 parts of polymethylene multi-phenenyl isocyanate
2.0 parts of triethylene diamine
0.3 part of stannous octoate
2.0 parts of silicone oil
15 parts of n-hexane
2 parts of water
10 parts of APP
10 parts of melamine.
3. fire-retardant phase-change energy-storing heat preservation heat-barrier material according to claim 1 and 2, it is characterized in that, the modified polyether is more
The specific preparation method of first alcohol is：
(1) add polyethylene glycol, stirring polyethylene glycol to be completely dissolved in tetrahydrofuran, obtain solution A；
(2) POCl3 is added in n-hexane, stirring is completely dissolved POCl3, obtains solution B；
(3) at 40-50 DEG C, solution B is added in solution A, is reacted 1~1.5 hour, revolving obtains liquid product C；
(4) liquid product C is heated to 90-100 DEG C, PPG is added dropwise, reacted 1~1.5 hour, obtain final product modified polyether many
First alcohol.
4. fire-retardant phase-change energy-storing heat preservation heat-barrier material according to claim 3, it is characterized in that, the polyethylene glycol, trichlorine
The weight ratio of oxygen phosphorus and PPG is 1~3: 1~1.15: 2~7；
The polyethylene glycol is 1.5~3: 3~7 with the mass volume ratio of tetrahydrofuran；
The POCl3 is 1~1.15: 2~4 with the mass volume ratio of n-hexane.
5. fire-retardant phase-change energy-storing heat preservation heat-barrier material according to claim 3, it is characterized in that, the PPG is third
Any in three alcohol radical PPOX ethers, trimethylolpropane PPOX ether and pentaerythrite PPOX ether
Kind.
6. fire-retardant phase-change energy-storing heat preservation heat-barrier material according to claim 3, it is characterized in that, the polyethylene glycol is poly- second
Glycol -600, PEG-8 00 or PEG-6000.
7. fire-retardant phase-change energy-storing heat preservation heat-barrier material according to claim 3, it is characterized in that, in step (3), at 45 DEG C
Under, solution B is slowly dropped in solution A, react 1 hour, obtain liquid product C.
8. fire-retardant phase-change energy-storing heat preservation heat-barrier material according to claim 3, it is characterized in that, in step (4), liquid is produced
Thing C is heated to 90 DEG C, and quick stirring is lower to be added dropwise PPG, reacts 1 hour, obtains modified ethoxylated polyhydric alcohol.
9. the preparation method of the fire-retardant phase-change energy-storing heat preservation heat-barrier material described in any one of claim 1-8, it is characterized in that, bag
Include：
Add diethanolamine solution in modified polyether polylol, stirring reaction 20~30 minutes, adjust its acid number for 0.03~
0.05mgKOH/g, the modified polyether polylol needed for being foamed；
According to formula rate, modified polyether polylol, stannous octoate needed for weighing foaming obtained above, silicone oil, polyphosphoric acid
The mixing of ammonium, melamine and water, after stirring 10~15 minutes, is subsequently adding n-hexane, stirs 1~2 minute, adds many methylenes
Quito phenyl isocyanate and triethylene diamine, quickly stirring are foamed for 8~10 seconds, and the foam that will be obtained is in 100-120 DEG C
Lower curing 2-3 hours, obtains fire-retardant phase-change energy-storing heat preservation heat-barrier material.
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| CN108148175A (en) * | 2017-12-28 | 2018-06-12 | 长沙善道新材料科技有限公司 | A kind of fireproof heat-preservation decoration material and preparation method thereof |
| CN108484865A (en) * | 2018-04-26 | 2018-09-04 | 汤广金 | Heat-insulation and heat-preservation free-floride foamed material and preparation method thereof |
| CN108586704A (en) * | 2018-04-26 | 2018-09-28 | 汤广金 | Insulation aluminium section bar and preparation method thereof |
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| CN112358804A (en) * | 2020-11-20 | 2021-02-12 | 兰州理工大学白银新材料研究院 | Preparation method of efficient flame-retardant polyurethane material |
| CN114539764A (en) * | 2021-04-19 | 2022-05-27 | 东莞市英捷工程塑料有限公司 | Low-hardness flame-retardant high polymer material and preparation method thereof |
| CN114539764B (en) * | 2021-04-19 | 2024-04-02 | 东莞市英捷工程塑料有限公司 | Flame-retardant high polymer material with low hardness and preparation method thereof |
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