CN106633189A - High-efficiency water-resistant intumescent flame retardant and application thereof in polypropylene - Google Patents
High-efficiency water-resistant intumescent flame retardant and application thereof in polypropylene Download PDFInfo
- Publication number
- CN106633189A CN106633189A CN201611242768.5A CN201611242768A CN106633189A CN 106633189 A CN106633189 A CN 106633189A CN 201611242768 A CN201611242768 A CN 201611242768A CN 106633189 A CN106633189 A CN 106633189A
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- Prior art keywords
- tgic
- dopo
- flame
- polypropylene
- retardant
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 67
- -1 polypropylene Polymers 0.000 title claims abstract description 59
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 52
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 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 28
- 229920001276 ammonium polyphosphate Polymers 0.000 claims abstract description 47
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims abstract description 35
- 239000002131 composite material Substances 0.000 claims abstract description 31
- 239000004114 Ammonium polyphosphate Substances 0.000 claims abstract description 15
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 38
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 36
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims description 18
- 238000002347 injection Methods 0.000 claims description 16
- 239000007924 injection Substances 0.000 claims description 16
- 239000012043 crude product Substances 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 239000007822 coupling agent Substances 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 9
- 239000003610 charcoal Substances 0.000 claims description 9
- 239000012467 final product Substances 0.000 claims description 9
- 125000005842 heteroatom Chemical group 0.000 claims description 9
- 229910000077 silane Inorganic materials 0.000 claims description 9
- 238000005453 pelletization Methods 0.000 claims description 8
- 239000001993 wax Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 238000002604 ultrasonography Methods 0.000 claims description 7
- 238000005292 vacuum distillation Methods 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 150000004645 aluminates Chemical class 0.000 claims description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003963 antioxidant agent Substances 0.000 claims description 4
- 230000003078 antioxidant effect Effects 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000314 lubricant Substances 0.000 claims description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052599 brucite Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 2
- 239000003599 detergent Substances 0.000 claims description 2
- 150000004816 dichlorobenzenes Chemical class 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 229940035429 isobutyl alcohol Drugs 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 229920000137 polyphosphoric acid Polymers 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 229910052757 nitrogen Inorganic materials 0.000 abstract 1
- 229910052698 phosphorus Inorganic materials 0.000 abstract 1
- 239000011574 phosphorus Substances 0.000 abstract 1
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 36
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 26
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000007599 discharging Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 3
- 230000000979 retarding effect Effects 0.000 description 3
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- DJOWTWWHMWQATC-KYHIUUMWSA-N Karpoxanthin Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1(O)C(C)(C)CC(O)CC1(C)O)C=CC=C(/C)C=CC2=C(C)CC(O)CC2(C)C DJOWTWWHMWQATC-KYHIUUMWSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001853 inorganic hydroxide Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- HLOLETUOZGAKMT-UHFFFAOYSA-N trimethoxysilyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)OC(=O)C(C)=C HLOLETUOZGAKMT-UHFFFAOYSA-N 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/387—Borates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention belongs to the field of materials, and discloses a high-efficiency water-resistant flame retardant and application thereof in a polypropylene composite material. The ternary integrated intumescent flame retardant with high phosphorus and nitrogen contents is prepared by coating ammonium polyphosphate with TGIC-DOPO; the compatibility of the flame retardant and polypropylene, the water resistance and the heat resistance are remarkably improved while the flame-retardant efficiency is improved; in order to further improve the flame-retardant efficiency and reduce the adding amount, a carbon formation accelerant is further preferred, thus further improving the comprehensive performance of the polypropylene composite material; when the adding amount of the intumescent flame retardant provided by the invention is less than 25% (the adding amount of a traditional intumescent flame retardant is 30%, and 1.6mm flame retardance V-0 is reached), the polypropylene composite material can pass UL-94 V-0 (1.6mm).
Description
Technical field
The invention belongs to Material Field, more particularly to a kind of efficiently water-fast sex flame retardant and its in PP composite material
Application.
Background technology
Polypropylene (PP), due to its excellent thermal stability, chemical stability, is electrically insulated as a kind of polymeric material
Property and weatherability etc. are widely used in daily life.Can with injection, extrusion molding, be blow molded, reel off raw silk from cocoons etc. method carry out plus
Work.The various electric components of suitable for making, television set and radio receiver shell, anti-corrosion pipeline, sheet material, automobile component, Turnover Box, establishment
Packaging bag, packing film Strapping Material, various containers, various clothing articles, artificial lawn etc..
But PP easily burns, belong to combustible material, substantial amounts of heat and flue gas can be discharged in combustion and occurs melting drop
Phenomenon, easily ignite surrounding objects, once there is fire, fire-propagation speed is fast, and large area burning is easily caused in the short time,
Come unfavorable to rescue belts, significantly limit the application of PP.
Therefore PP is carried out flame-retardant modified, improves its fire safety in use so as to industry needed for meeting
Flame-retardancy requirements are extremely important.
Currently used for the fire-retardant mainly halogenated flame retardants of PP.The flame retardant effect of this based flame retardant is excellent, but by Europe
The restriction of RoHS bills.Therefore the Non-halogen Flame Retardant Technology that exploitation highly effective flame-retardant, high security, low cigarette, low toxic gas are generated is
It is the development trend of flame retardant area in recent years.
In the middle of Non-halogen Flame Retardant Technology, inorganic hydroxide fire retardant have non-volatile, effect persistently, be not likely to produce corrosion
The advantages of property gas, good nontoxic, heat stability, low production cost, but it is different from the two-phase interface polarity of PP matrixes due to it, and
And addition is big (sometime up to 50～60wt%), causes material mechanical properties decrease itself, so as to limit the flame-retarded technology
Application.
At present in PP halogen-free flame-retardant systems, expandable flame retardant technology is less due to addition, and with nontoxic and Halogen
The advantages of, receive more and more attention.But it is low that existing polypropylene expanding fire retardant still suffers from flame retarding efficiency, poor water resistance,
It is easy to the problems such as separating out.
The content of the invention
In order to overcome the shortcoming and deficiency of above-mentioned prior art, the primary and foremost purpose of the present invention is to provide a kind of efficiently water-fast
Property expansibility flame-proof agent.
Another object of the present invention is the application for providing above-mentioned polypropylene expanding fire retardant in PP composite material.
The purpose of the present invention is realized by following proposal：
A kind of efficient resistance to water expansibility flame-proof agent, it is mainly prepared by following methods：
(1) by isocyanuric acid three-glycidyl ester (TGIC) and the phospho hetero phenanthrene -10- oxides of -9 oxa- of 9,10- dihydros -10
(DOPO) it is added in reaction dissolvent, keeps reaction temperature to react 1h at 100～130 DEG C, obtains TGIC-DOPO pre-polymerization liquid；
Reaction dissolvent used is dichloromethane, dichloroethanes, sym-tetrachloroethane, chloroform, carbon tetrachloride, first in step (1)
One kind in benzene, chlorobenzene, dimethylbenzene, dichloro-benzenes；
Isocyanuric acid three-glycidyl ester (TGIC) used in step (1) and the phospho hetero phenanthrene of-9 oxa- of 9,10- dihydros-10-
The mol ratio of 10- oxides (DOPO) is 1:(3～6)；The amount of reaction dissolvent used is isocyanuric acid three-glycidyl ester
(TGIC) 6～10 times of quality.
(2) APP is added in reaction dissolvent, stirs under ultrasound condition and add catalyst after 0.5h, added
The TGIC-DOPO pre-polymerization liquid prepared in step (1), rises high-temperature, keeps reaction temperature at 110～150 DEG C, stirring condition
3～10h of lower reaction, reaction terminate after by reactant liquor purification obtain final product TGIC-DOPO coated ammonium polyphosphates；
Reaction dissolvent used is consistent with reaction dissolvent used in step (1) in step (2)；
Catalyst used is cetyl trimethylammonium bromide in step (2)；
The quality of APP used is isocyanuric acid three-glycidyl ester (TGIC) matter in step (1) in step (2)
4～10 times of amount；The amount of reaction dissolvent used is isocyanuric acid three-glycidyl ester (TGIC) in step (1) in step (2)
6～10 times of quality；The amount of catalyst used is isocyanuric acid three-glycidyl ester (TGIC) in step (1) in step (2)
The 1% of quality；
Purification described in step (2) refers to gained reactant liquor vacuum distillation, removes reaction dissolvent therein and obtain TGIC-
DOPO coated ammonium polyphosphate crude products, are then added to TGIC-DOPO coated ammonium polyphosphate crude products in cleaning solvent 30
～150 DEG C are followed by stirring and washing 0.1～0.5h, are subsequently cooled to room temperature, staticly settle, and filter, and gained is precipitated into drying
TGIC-DOPO coated ammonium polyphosphates；
Described cleaning solvent is the one kind in ethanol, Hexalin, glycerol, Propylene Glycol, isopropanol, isobutyl alcohol.
The consumption of detergent used is 1～20 times of isocyanuric acid three-glycidyl ester (TGIC) quality in step (1)；
(3) it is added in high mixer by the TGIC-DOPO coated ammonium polyphosphates of gained in step (2) and into charcoal accelerator,
Discharge after 10～20min of mixed at high speed, obtain final product efficient resistance to water expanding fire retardant.
In step (3) it is used into charcoal accelerator be Firebrake ZB, boric acid, manganese dioxide, silicon dioxide, lanthanum oxide, oxygen
Change zinc, antimony trioxide, zirconium dioxide, molybdenum oxide, magnesium hydroxide, aluminium hydroxide, brucite, layered hydroxide, nanometer and cover de-
One or more mixture in soil, 4A molecular sieves.
TGIC-DOPO coated ammonium polyphosphates used and the amount into charcoal accelerator are that TGIC-DOPO claddings are poly- in step (3)
Ammonium phosphate accounts for TGIC-DOPO coated ammonium polyphosphates and into the 95～99% of charcoal accelerator gross mass.
Application of the above-mentioned efficient resistance to water expansibility flame-proof agent in polypropylene composite.
A kind of flame-retardant polypropylene composite material prepared by above-mentioned efficient resistance to water expansibility flame-proof agent, it includes
The composition of following percentage by weight：
Described polypropylene is one or more mixture in HOPP, COPP.
Described lubricant is one or more mixture in PE waxes, stearic acid, silicone powder.
Described coupling agent is the one kind in silane coupler, aluminate coupling agent, titanate coupling agent；
Described silane coupler is silane coupler commonly used in the art, preferably methacryloxy front three
At least one in TMOS, 3- glycidyl ether oxygen propyl trimethoxy silicanes, Y- aminopropyl triethoxysilanes；It is described
Aluminate coupling agent be aluminate coupling agent commonly used in the art, preferably distearyl acyl-oxygen isopropyl Aluminate；Institute
The titanate coupling agent stated is titanate coupling agent commonly used in the art, preferably monoalkoxytitanates, pyrophosphate
At least one in titanate esters, monoalkoxy unsaturated fatty acid titanate esters.
Described antioxidant is one or more mixture in 1010,1076,168.
A kind of preparation method of above-mentioned flame-retardant polypropylene composite material, specifically includes following steps：At room temperature, will be upper
The resistance to water expanding fire retardant stated and coupling agent are added in high-speed mixer, in 1000r/min～2000r/min mixing
3min, then adds polypropylene, lubricant and antioxidant, then in 1000r/min～2000r/min mixing 10min, must mix
Material, by gained compound double screw extruder in 160 DEG C～180 DEG C extruding pelletizations, is then molded with injection machine at 180 DEG C,
Obtain anti-flaming polypropylene composite.
The present invention has the following advantages and beneficial effect relative to prior art：
(1) present invention is obtained the three-in-one expanding fire retardant of high phosphorus nitrogen content with TGIC-DOPO coated ammonium polyphosphates,
While flame retarding efficiency is improved fire retardant can be significantly improved with the polyacrylic compatibility, resistance to water, thermostability；
(2) in order to further improve flame retarding efficiency, reduce addition, the present invention further preferably into charcoal accelerator, so as to enter
One step improves the combination property of composite：In addition, less than 25%, (conventional expanded fire retardant needs 30%, reaches 1.6mm resistances
Combustion V-0), composite can just pass through UL-94V-0 (1.6mm).
Specific embodiment
With reference to embodiment, the present invention is described in further detail, but embodiments of the present invention not limited to this.
Reagent used can routinely be buied if no special instructions from market in embodiment.APP used in embodiment
Polymerization degree n >=1000.
Embodiment 1
The efficiently preparation of resistance to water expanding fire retardant：
(1) by isocyanuric acid three-glycidyl ester (TGIC) and the phospho hetero phenanthrene -10- oxides of -9 oxa- of 9,10- dihydros -10
DOPO is 1 according to mol ratio:3 are added in dichloromethane, and the consumption of dichloromethane is 10 times of TGIC mass used, keep anti-
Answer temperature to react 1h at 130 DEG C, obtain TGIC-DOPO pre-polymerization liquid standby；
(2) APP is added in dichloromethane, the consumption of dichloromethane is 10 of TGIC mass used in step (1)
Times, APP consumption is 4 times of TGIC mass used in step (1), and 0.5h is stirred under ultrasound condition, adds hexadecane
Base trimethylammonium bromide, consumption is the 1% of TGIC mass used in step (1).It is subsequently adding (1) gained TGIC-DOPO pre-
Poly- liquid, rises high-temperature, keeps reaction temperature at 110 DEG C, and under stirring condition 10h is reacted；
(3) vacuum distillation removes dichloromethane, obtains TGIC-DOPO coated ammonium polyphosphate crude products；
(4) TGIC-DOPO coated ammonium polyphosphate crude products are added in ethanol, the consumption of solvent contracts for isocyanuric acid three
10 times of water glyceride quality, maintain the temperature at 50 DEG C, and agitator treating is cooled to room temperature, staticly settles, and obtain after filtering drying
Product TGIC-DOPO coated ammonium polyphosphates；
(5) the TGIC-DOPO coated ammonium polyphosphates that mass fraction is 95% and the Firebrake ZB that mass fraction is 5% are added
In high mixer, at a high speed mixed 20min, discharging, obtain final product efficient resistance to water expanding fire retardant a.
The preparation of anti-flaming polypropylene composite：
(1) by efficient resistance to water expanding fire retardant 220g and 10g methacryloxy trimethoxy manufactured in the present embodiment
Base silane add high mixer in, under room temperature, speed be 2000r/min mixing 3min, then by 780gZ30S polypropylene,
10gH108PE waxes, 3g1010 are added in high mixer, and speed is 2000r/min mixed at high speed 10min.
(2) by material double screw extruder mixed above in 160 DEG C～180 DEG C extruding pelletizations, then with injection machine 180
DEG C injection, obtain anti-flaming polypropylene composite A.
Embodiment 2
The efficiently preparation of resistance to water expanding fire retardant：
(1) by isocyanuric acid three-glycidyl ester (TGIC) and the phospho hetero phenanthrene -10- oxides of -9 oxa- of 9,10- dihydros -10
DOPO is 1 according to mol ratio:6 add in dichloromethane, and the consumption of dichloromethane is 6 times of TGIC mass used, keep reaction
Temperature reacts 1h at 100 DEG C, obtains TGIC-DOPO pre-polymerization liquid standby；
(2) APP is added in dichloromethane, the consumption of dichloromethane is TGIC mass used in step (1)
6 times, APP consumption is 10 times of TGIC mass used in step (1), and 0.5h is stirred under ultrasound condition, adds 16
Alkyl trimethyl ammonium bromide, consumption is the 1% of TGIC mass used in step (1).It is subsequently adding (1) gained TGIC-DOPO
Pre-polymerization liquid, rises high-temperature, keeps reaction temperature at 120 DEG C, and under stirring condition 10h is reacted；
(3) vacuum distillation removes dichloromethane and obtains TGIC-DOPO coated ammonium polyphosphate crude products；
(4) TGIC-DOPO coated ammonium polyphosphate crude products are added in ethanol, the consumption of solvent is the 10 of TGIC mass
Times, 60 DEG C are maintained the temperature at, agitator treating is cooled to room temperature, staticly settles, and product TGIC-DOPO bags are obtained after filtering drying
Cover APP.
(5) the TGIC-DOPO coated ammonium polyphosphates that mass fraction is 95% and the Zinc Oxide that mass fraction is 5% are added
In high mixer, at a high speed mixed 10min, discharging, obtain final product efficient resistance to water expanding fire retardant b.
The preparation of anti-flaming polypropylene composite：
(1) by efficient resistance to water expanding fire retardant 220g and 10g methacryloxy trimethoxy manufactured in the present embodiment
Base silane add high mixer in, under room temperature, speed be 2000r/min mixing 3min, then by 780gZ30S polypropylene,
10gH108PE waxes, 3g1010 are added in high mixer, and speed is 2000r/min mixed at high speed 10min.
(2) by material double screw extruder mixed above in 160 DEG C～180 DEG C extruding pelletizations, then with injection machine 180
DEG C injection, obtain anti-flaming polypropylene composite B.
Embodiment 3
The efficiently preparation of resistance to water expanding fire retardant：
(1) by isocyanuric acid three-glycidyl ester (TGIC) and the phospho hetero phenanthrene -10- oxides of -9 oxa- of 9,10- dihydros -10
DOPO is 1 according to mol ratio:5 add chlorobenzene, and the consumption of chlorobenzene is 10 times of TGIC mass used, keep reaction temperature 110
DEG C reaction 1h, obtain TGIC-DOPO pre-polymerization liquid standby；
(2) APP is added in (1) described chlorobenzene, the consumption of chlorobenzene is the 6 of TGIC mass used in step (1)
Times, APP consumption is 8 times of TGIC mass used in step (1), and 0.5h is stirred under ultrasound condition, adds hexadecane
Base trimethylammonium bromide, consumption is the 1% of TGIC mass used in step (1).It is subsequently adding (1) gained TGIC-DOPO pre-
Poly- liquid, rises high-temperature, keeps reaction temperature at 130 DEG C, and under stirring condition 10h is reacted；
(3) vacuum distillation removes reaction dissolvent and obtains TGIC-DOPO coated ammonium polyphosphate crude products；
(4) TGIC-DOPO coated ammonium polyphosphate crude products are added in ethanol, the consumption of solvent is the 10 of TGIC mass
Times, 60 DEG C are maintained the temperature at, agitator treating is cooled to room temperature, staticly settles, and product TGIC-DOPO bags are obtained after filtering drying
Cover APP.
(5) the TGIC-DOPO coated ammonium polyphosphates that mass fraction is 97% and the Firebrake ZB that mass fraction is 3% are added
In high mixer, at a high speed mixed 15min, discharging, obtain final product efficient resistance to water expanding fire retardant c.
The preparation of anti-flaming polypropylene composite：
(1) by efficient resistance to water expanding fire retardant 220g and 10g methacryloxy trimethoxy manufactured in the present embodiment
Base silane add high mixer in, under room temperature, speed be 2000r/min mixing 3min, then by 780gZ30S polypropylene,
10gH108PE waxes, 3g1010 are added in high mixer, and speed is 2000r/min mixed at high speed 10min.
(2) by material double screw extruder mixed above in 160 DEG C～180 DEG C extruding pelletizations, then with injection machine 180
DEG C injection, obtain anti-flaming polypropylene composite C.
Embodiment 4
The efficiently preparation of resistance to water expanding fire retardant：
(1) by isocyanuric acid three-glycidyl ester (TGIC) and the phospho hetero phenanthrene -10- oxides of -9 oxa- of 9,10- dihydros -10
DOPO is 1 according to mol ratio:4 add chlorobenzene, and the consumption of chlorobenzene is 10 times of TGIC mass used, keep reaction temperature 110
DEG C reaction 1h, obtain TGIC-DOPO pre-polymerization liquid standby；
(2) APP is added in (1) described chlorobenzene, the consumption of chlorobenzene is the 6 of TGIC mass used in step (1)
Times, APP consumption is 9 times of TGIC mass used in step (1), and 0.5h is stirred under ultrasound condition, adds hexadecane
Base trimethylammonium bromide, consumption is the 1% of TGIC mass used in step (1).It is subsequently adding (1) gained TGIC-DOPO pre-
Poly- liquid, rises high-temperature, keeps reaction temperature at 130 DEG C, and under stirring condition 10h is reacted；
(3) vacuum distillation removes reaction dissolvent and obtains TGIC-DOPO coated ammonium polyphosphate crude products；
(4) TGIC-DOPO coated ammonium polyphosphate crude products are added in isopropanol, the consumption of isopropanol is TGIC mass
10 times, maintain the temperature at 60 DEG C, agitator treating is cooled to room temperature, staticly settles, after filtering drying obtain product TGIC-
DOPO coated ammonium polyphosphates.
(5) the TGIC-DOPO coated ammonium polyphosphates that mass fraction is 97% and the brucite that mass fraction is 3% are added
In high mixer, at a high speed mixed 10min, discharging, obtain final product efficient resistance to water expanding fire retardant d.
The preparation of anti-flaming polypropylene composite：
(1) by efficient resistance to water expanding fire retardant 220g and 10g methacryloxy trimethoxy manufactured in the present embodiment
Base silane add high mixer in, under room temperature, speed be 2000r/min mixing 3min, then by 780gZ30S polypropylene,
10gH108PE waxes, 3g1010 are added in high mixer, and speed is 2000r/min mixed at high speed 10min.
(2) by material double screw extruder mixed above in 160 DEG C of -180 DEG C of extruding pelletizations, then with injection machine 180
DEG C injection, obtain anti-flaming polypropylene composite D.
Embodiment 5
The efficiently preparation of resistance to water expanding fire retardant：
(1) by isocyanuric acid three-glycidyl ester (TGIC) and the phospho hetero phenanthrene -10- oxides of -9 oxa- of 9,10- dihydros -10
DOPO is 1 according to mol ratio:3 add chlorobenzene, and the consumption of chlorobenzene is 10 times of TGIC mass used, keep reaction temperature 110
DEG C reaction 1h, obtain TGIC-DOPO pre-polymerization liquid standby；
(2) APP is added in (1) described chlorobenzene, the consumption of chlorobenzene is the 6 of TGIC mass used in step (1)
Times, APP consumption is 6 times of TGIC mass used in step (1), and 0.5h is stirred under ultrasound condition, adds hexadecane
Base trimethylammonium bromide, consumption is the 1% of TGIC mass used in step (1).It is subsequently adding (1) gained TGIC-DOPO pre-
Poly- liquid, rises high-temperature, keeps reaction temperature at 130 DEG C, and under stirring condition 10h is reacted；
(3) vacuum distillation removes reaction dissolvent and obtains TGIC-DOPO coated ammonium polyphosphate crude products；
(4) TGIC-DOPO coated ammonium polyphosphate crude products are added in isopropanol, the consumption of isopropanol is TGIC mass
10 times, maintain the temperature at 60 DEG C, agitator treating is cooled to room temperature, staticly settles, after filtering drying obtain product TGIC-
DOPO coated ammonium polyphosphates.
(5) the TGIC-DOPO coated ammonium polyphosphates that mass fraction is 97% and the 4A molecular sieves that mass fraction is 3% are added
In entering high mixer, at a high speed mixed 10min, discharging, obtain final product efficient resistance to water expanding fire retardant e.
The preparation of anti-flaming polypropylene composite：
(1) by efficient resistance to water expanding fire retardant 220g and 10g methacryloxy trimethoxy manufactured in the present embodiment
Base silane add high mixer in, under room temperature, speed be 2000r/min mixing 3min, then by 780gZ30S polypropylene,
10gH108PE waxes, 3g1010 are added in high mixer, and speed is 2000r/min mixed at high speed 10min.
(2) by material double screw extruder mixed above in 160 DEG C of -180 DEG C of extruding pelletizations, then with injection machine 180
DEG C injection, obtain anti-flaming polypropylene composite E.
Comparative example 1
Traditional expanding fire retardant 220g and 10g methacryloxy trimethoxy silane is added in high mixer, room
Under temperature, speed is 2000r/min mixing 3min, then 780gZ30S polypropylene, 10gH108PE waxes, 3g1010 is added to into height
In mixed machine, speed is 2000r/min mixed at high speed 10min.Conventional expanded fire retardant APP in mass ratio：Tripolycyanamide：
Poly- penta tetrol (Yunnan Yuntianhua Co., Ltd.)=3:1:1 mixes f.
By material double screw extruder mixed above in 160 DEG C～180 DEG C extruding pelletizations, then with injection machine at 180 DEG C
Injection, obtains anti-flaming polypropylene composite F.
The expanding fire retardant prepared in embodiment 1～5 and comparative example 1 is carried out with thermogravimetric analyzer (TGA)
Thermally-stabilised test, method of testing is：Under nitrogen atmosphere, temperature rises to 800 DEG C from room temperature, 10 DEG C/min of heating rate, gas
Rate of flow of fluid 60ml/min, 3～5mg of sample quality, when record fire retardant weightlessness is 1%, corresponding temperature is that temperature is decomposed in starting
Degree.Test result is as shown in table 1：
The thermal stability data of the expanding fire retardant prepared in the embodiment 1～5 of table 1 and comparative example 1
| Performance | a | b | c | d | e | f |
| Initial decomposition temperature DEG C | 265 | 264 | 267 | 275 | 275 | 230 |
From table 1 it follows that the heat resistance of the efficient resistance to water expanding fire retardant prepared in embodiment 1～5
Better than conventional expanded fire retardant, initial decomposition temperature rises to more than 260 DEG C by 230 DEG C of conventional expanded fire retardant.
The anti-flaming polypropylene composite that embodiment 1～5 and comparative example 1 prepare is made into test bars, then
Vertical burn test is carried out by UL-94, materials water-resistant test is carried out by UL746C, carries out oxygen index (OI) by GB/T 2408-2008
Test, carry out tensile strength test by GB/T 1040-2006.As a result it is as shown in table 2：
The properties data of prepared anti-flaming polypropylene composite in the embodiment 1～5 of table 2 and comparative example 1
From Table 2, it can be seen that with TGIC-DOPO coated ammonium polyphosphates in the embodiment of the present invention 1～5, high phosphorus nitrogen is obtained
The three-in-one expanding fire retardant of content, the resistance to water of the flame-retardant polypropylene composite material prepared using the fire retardant is better than
The flame-retardant polypropylene composite material prepared with conventional flame retardant in comparative example 1：Through UL746 water resistance tests
Afterwards, embodiment A-E can keep flame retardant rating to reach V-0, and oxygen index (OI) reduces being maintained within 1.7%, and comparative example F is then
Flame retardant rating drops to HB from V-1, and oxygen index (OI) reduces 3%.And when fire retardant addition is 22wt%, embodiment is reachable
To 1.6mm UL-94 V-0 ranks.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention not by above-described embodiment
Limit, other any spirit without departing from the present invention and the change, modification, replacement made under principle, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (9)
1. a kind of efficient resistance to water expansibility flame-proof agent, it is characterised in that prepared by following methods：
(1) isocyanuric acid three-glycidyl ester and the phospho hetero phenanthrene -10- oxides of -9 oxa- of 9,10- dihydros -10 are added to into reaction molten
In agent, keep reaction temperature to react 1h at 100～130 DEG C, obtain TGIC-DOPO pre-polymerization liquid；
(2) APP is added in reaction dissolvent, stirs under ultrasound condition and add catalyst after 0.5h, add step
(1) the TGIC-DOPO pre-polymerization liquid prepared in, rises high-temperature, keeps reaction temperature at 110～150 DEG C, anti-under stirring condition
Answer 3～10h, reaction terminate after by reactant liquor purification obtain final product TGIC-DOPO coated ammonium polyphosphates；
(3) it is added in high mixer by the TGIC-DOPO coated ammonium polyphosphates of gained in step (2) and into charcoal accelerator, at a high speed
Discharge after 10～20min of mixing, obtain final product efficient resistance to water expanding fire retardant.
2. efficient resistance to water expansibility flame-proof agent according to claim 1, it is characterised in that：
Reaction dissolvent used is dichloromethane, dichloroethanes, sym-tetrachloroethane, chloroform, carbon tetrachloride, toluene, chlorine in step (1)
One kind in benzene, dimethylbenzene, dichloro-benzenes；
Isocyanuric acid three-glycidyl ester used and the phospho hetero phenanthrene -10- oxides of -9 oxa- of 9,10- dihydros -10 in step (1)
Mol ratio is 1:(3～6)；The amount of reaction dissolvent used is 6～10 times of isocyanuric acid three-glycidyl ester quality.
3. efficient resistance to water expansibility flame-proof agent according to claim 1, it is characterised in that：
Reaction dissolvent used is consistent with reaction dissolvent used in step (1) in step (2)；
Catalyst used is cetyl trimethylammonium bromide in step (2)；
The quality of APP used is 4～10 of isocyanuric acid three-glycidyl ester quality in step (1) in step (2)
Times；The amount of reaction dissolvent used is 6～10 times of isocyanuric acid three-glycidyl ester quality in step (1) in step (2)；Step
Suddenly the amount of catalyst used in (2) is 1% of isocyanuric acid three-glycidyl ester quality in step (1)；
Purification described in step (2) refers to gained reactant liquor vacuum distillation, removes reaction dissolvent therein and obtain TGIC-DOPO
Coated ammonium polyphosphate crude product, is then added to TGIC-DOPO coated ammonium polyphosphate crude products in cleaning solvent 30～150
DEG C 0.1～0.5h is followed by stirring and washing, is subsequently cooled to room temperature, staticly settled, filtered, gained is precipitated into drying TGIC-
DOPO coated ammonium polyphosphates.
4. efficient resistance to water expansibility flame-proof agent according to claim 3, it is characterised in that：
Described cleaning solvent is the one kind in ethanol, Hexalin, glycerol, Propylene Glycol, isopropanol, isobutyl alcohol；
The consumption of detergent used is 1～20 times of isocyanuric acid three-glycidyl ester quality in step (1).
5. efficient resistance to water expansibility flame-proof agent according to claim 1, it is characterised in that：
In step (3) it is used into charcoal accelerator be Firebrake ZB, boric acid, manganese dioxide, silicon dioxide, lanthanum oxide, Zinc Oxide,
Antimony trioxide, zirconium dioxide, molybdenum oxide, magnesium hydroxide, aluminium hydroxide, brucite, layered hydroxide, nano imvite, 4A
One or more mixture in molecular sieve；
TGIC-DOPO coated ammonium polyphosphates used and the amount into charcoal accelerator are that TGIC-DOPO coats polyphosphoric acid in step (3)
Ammonium accounts for TGIC-DOPO coated ammonium polyphosphates and into the 95～99% of charcoal accelerator gross mass.
6. the efficient resistance to water expansibility flame-proof agent according to any one of Claims 1 to 5 in polypropylene composite should
With.
7. the flame-retardant polypropylene that a kind of efficient resistance to water expansibility flame-proof agent by described in any one of Claims 1 to 5 is prepared
Alkene composite, it is characterised in that including the composition of following percentage by weight：
8. flame-retardant polypropylene composite material according to claim 7, it is characterised in that：
Described polypropylene is one or more mixture in HOPP, COPP；
Described lubricant is one or more mixture in PE waxes, stearic acid, silicone powder；
Described coupling agent is the one kind in silane coupler, aluminate coupling agent, titanate coupling agent；
Described antioxidant is one or more mixture in 1010,1076,168.
9. a kind of preparation method of the flame-retardant polypropylene composite material according to claim 7 or 8, it is characterised in that include with
Lower step：At room temperature, resistance to water expanding fire retardant and coupling agent are added in high-speed mixer, 1000r/min～
2000r/min mixing 3min, then add polypropylene, lubricant and antioxidant, then mixed in 1000r/min～2000r/min
10min is closed, compound is obtained, by gained compound double screw extruder in 160 DEG C～180 DEG C extruding pelletizations, then with injection
Machine obtains anti-flaming polypropylene composite in 180 DEG C of injections.
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| CN110591150A (en) * | 2019-07-29 | 2019-12-20 | 浙江大学宁波理工学院 | Cerium-phosphorus complex flame retardant, cerium-phosphorus complex flame-retardant polycarbonate composite material and preparation methods of cerium-phosphorus complex flame retardant and cerium-phosphorus complex flame-retardant polycarbonate composite material |
| CN112175294A (en) * | 2020-10-26 | 2021-01-05 | 江苏昊晟塑业科技有限公司 | Flame-retardant foamed polypropylene and preparation method thereof |
| CN112321945A (en) * | 2020-11-23 | 2021-02-05 | 江苏金发科技新材料有限公司 | Precipitation-resistant halogen-free flame-retardant polypropylene composite material and preparation method thereof |
| CN112480505A (en) * | 2020-11-05 | 2021-03-12 | 安徽红桥金属制造有限公司 | High-flame-retardant and aging-resistant air spring |
| CN113045800A (en) * | 2021-04-06 | 2021-06-29 | 什邡市太丰新型阻燃剂有限责任公司 | Novel flame retardant based on APP and DOPO and preparation method thereof |
| CN115161036A (en) * | 2022-06-28 | 2022-10-11 | 苏州世名科技股份有限公司 | Environment-friendly flame retardant, preparation method and environment-friendly flame-retardant viscose fiber |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103554999A (en) * | 2013-11-06 | 2014-02-05 | 四川大学 | Modified ammonium polyphosphate as well as preparation method and use thereof |
| CN104448560A (en) * | 2014-12-01 | 2015-03-25 | 黑龙江省润特科技有限公司 | Polypropylene halogen-free intumescent flame retardant |
| CN104449766A (en) * | 2014-11-19 | 2015-03-25 | 太原理工大学 | Benzene-ring-containing hydrophobic organic ammonium polyphosphate fire retardant and preparation method thereof |
-
2016
- 2016-12-29 CN CN201611242768.5A patent/CN106633189B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103554999A (en) * | 2013-11-06 | 2014-02-05 | 四川大学 | Modified ammonium polyphosphate as well as preparation method and use thereof |
| CN104449766A (en) * | 2014-11-19 | 2015-03-25 | 太原理工大学 | Benzene-ring-containing hydrophobic organic ammonium polyphosphate fire retardant and preparation method thereof |
| CN104448560A (en) * | 2014-12-01 | 2015-03-25 | 黑龙江省润特科技有限公司 | Polypropylene halogen-free intumescent flame retardant |
Non-Patent Citations (1)
| Title |
|---|
| 张金凯: ""DOPO功能化的新型疏水聚磷酸铵的制备及在PP中的引用"", 《中国优选硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
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| CN107602839A (en) * | 2017-10-16 | 2018-01-19 | 中山康诺德新材料有限公司 | A kind of water resistance halogen-free expansion fire retardant and preparation method thereof |
| CN107604457A (en) * | 2017-10-18 | 2018-01-19 | 温州市赢创新材料技术有限公司 | A kind of flame-retardant polypropylene long filament and preparation method thereof |
| CN107652469A (en) * | 2017-10-18 | 2018-02-02 | 合肥华顺阻燃新材料科技有限公司 | A kind of PP flame-retardant additives |
| CN109575361A (en) * | 2018-11-23 | 2019-04-05 | 洛阳赛图新材料科技有限公司 | A kind of preparation method of the cladded type fire retardant of excellent electrical properties |
| CN109575361B (en) * | 2018-11-23 | 2021-06-29 | 洛阳赛图新材料科技有限公司 | Preparation method of coated flame retardant with excellent electrical property |
| CN110591150B (en) * | 2019-07-29 | 2021-05-07 | 浙江大学宁波理工学院 | Cerium-phosphorus complex flame retardant, cerium-phosphorus complex flame-retardant polycarbonate composite material and preparation methods of cerium-phosphorus complex flame retardant and cerium-phosphorus complex flame-retardant polycarbonate composite material |
| CN110591150A (en) * | 2019-07-29 | 2019-12-20 | 浙江大学宁波理工学院 | Cerium-phosphorus complex flame retardant, cerium-phosphorus complex flame-retardant polycarbonate composite material and preparation methods of cerium-phosphorus complex flame retardant and cerium-phosphorus complex flame-retardant polycarbonate composite material |
| CN110577716A (en) * | 2019-09-23 | 2019-12-17 | 南通伟越电器有限公司 | Preparation method of high-impact-resistance polystyrene special material for television shell |
| CN112175294A (en) * | 2020-10-26 | 2021-01-05 | 江苏昊晟塑业科技有限公司 | Flame-retardant foamed polypropylene and preparation method thereof |
| CN112480505A (en) * | 2020-11-05 | 2021-03-12 | 安徽红桥金属制造有限公司 | High-flame-retardant and aging-resistant air spring |
| CN112480505B (en) * | 2020-11-05 | 2023-08-01 | 安徽红桥金属制造有限公司 | High flame-retardant ageing-resistant air spring |
| CN112321945A (en) * | 2020-11-23 | 2021-02-05 | 江苏金发科技新材料有限公司 | Precipitation-resistant halogen-free flame-retardant polypropylene composite material and preparation method thereof |
| CN113045800A (en) * | 2021-04-06 | 2021-06-29 | 什邡市太丰新型阻燃剂有限责任公司 | Novel flame retardant based on APP and DOPO and preparation method thereof |
| CN115161036A (en) * | 2022-06-28 | 2022-10-11 | 苏州世名科技股份有限公司 | Environment-friendly flame retardant, preparation method and environment-friendly flame-retardant viscose fiber |
| CN115161036B (en) * | 2022-06-28 | 2024-02-02 | 苏州世名科技股份有限公司 | Environment-friendly flame retardant, preparation method and environment-friendly flame retardant viscose fiber |
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