CN112480323B - Polystyrene flame-retardant material and preparation method and application thereof - Google Patents
Polystyrene flame-retardant material and preparation method and application thereof Download PDFInfo
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- CN112480323B CN112480323B CN201910857837.0A CN201910857837A CN112480323B CN 112480323 B CN112480323 B CN 112480323B CN 201910857837 A CN201910857837 A CN 201910857837A CN 112480323 B CN112480323 B CN 112480323B
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- CN
- China
- Prior art keywords
- flame retardant
- polystyrene
- retardant material
- polystyrene flame
- styrene
- Prior art date
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 175
- 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 173
- 239000004793 Polystyrene Substances 0.000 title claims abstract description 83
- 229920002223 polystyrene Polymers 0.000 title claims abstract description 82
- 239000000463 material Substances 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 58
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 46
- 239000011574 phosphorus Substances 0.000 claims abstract description 46
- 229920001971 elastomer Polymers 0.000 claims abstract description 33
- 239000005060 rubber Substances 0.000 claims abstract description 33
- 239000003999 initiator Substances 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims description 24
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical group CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 14
- 229920003193 cis-1,4-polybutadiene polymer Polymers 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 238000010559 graft polymerization reaction Methods 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 8
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 150000002978 peroxides Chemical group 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 claims description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 15
- 238000001556 precipitation Methods 0.000 abstract description 7
- 238000010526 radical polymerization reaction Methods 0.000 abstract description 5
- 150000003384 small molecules Chemical class 0.000 abstract description 5
- 239000012634 fragment Substances 0.000 abstract description 3
- 239000000178 monomer Substances 0.000 abstract description 3
- 238000004090 dissolution Methods 0.000 abstract description 2
- 230000007062 hydrolysis Effects 0.000 abstract description 2
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 2
- 125000002947 alkylene group Chemical group 0.000 description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000000203 mixture Substances 0.000 description 15
- 229920002554 vinyl polymer Polymers 0.000 description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 239000000654 additive Substances 0.000 description 11
- 230000000996 additive effect Effects 0.000 description 11
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 10
- 239000002904 solvent Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 7
- 229920005669 high impact polystyrene Polymers 0.000 description 6
- 239000004797 high-impact polystyrene Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229960000549 4-dimethylaminophenol Drugs 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical class [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229920005990 polystyrene resin Polymers 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000004114 Ammonium polyphosphate Substances 0.000 description 3
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 3
- 229920001276 ammonium polyphosphate Polymers 0.000 description 3
- 125000000732 arylene group Chemical group 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- BZQKBFHEWDPQHD-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-[2-(2,3,4,5,6-pentabromophenyl)ethyl]benzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1CCC1=C(Br)C(Br)=C(Br)C(Br)=C1Br BZQKBFHEWDPQHD-UHFFFAOYSA-N 0.000 description 2
- DEIGXXQKDWULML-UHFFFAOYSA-N 1,2,5,6,9,10-hexabromocyclododecane Chemical compound BrC1CCC(Br)C(Br)CCC(Br)C(Br)CCC1Br DEIGXXQKDWULML-UHFFFAOYSA-N 0.000 description 2
- LBSXSAXOLABXMF-UHFFFAOYSA-N 4-Vinylaniline Chemical compound NC1=CC=C(C=C)C=C1 LBSXSAXOLABXMF-UHFFFAOYSA-N 0.000 description 2
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 2
- 125000005237 alkyleneamino group Chemical group 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical group O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- DMIROTRQOLGJJY-UHFFFAOYSA-N diethyl hydroxymethyl phosphite Chemical compound CCOP(OCC)OCO DMIROTRQOLGJJY-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 125000001072 heteroaryl group Chemical group 0.000 description 2
- 125000005549 heteroarylene group Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- KEYLJVFXWVSVSP-UHFFFAOYSA-N hydroxymethyl dimethyl phosphite Chemical compound P(OCO)(OC)OC KEYLJVFXWVSVSP-UHFFFAOYSA-N 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 125000000468 ketone group Chemical group 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- -1 methylene, ethylene, propylene, butylene Chemical group 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000011257 shell material Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- VFPLSXYJYAKZCT-VOTSOKGWSA-N 4-[(e)-2-phenylethenyl]aniline Chemical compound C1=CC(N)=CC=C1\C=C\C1=CC=CC=C1 VFPLSXYJYAKZCT-VOTSOKGWSA-N 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- XVBROVFRHZPJNC-UHFFFAOYSA-N COP(CO)(O)OC Chemical compound COP(CO)(O)OC XVBROVFRHZPJNC-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000000354 decomposition reaction 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
- 238000004821 distillation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 125000004043 oxo group Chemical group O=* 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical group C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- 125000004417 unsaturated alkyl group Chemical group 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/22—Amides of acids of phosphorus
- C07F9/24—Esteramides
- C07F9/2404—Esteramides the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/2408—Esteramides the ester moiety containing a substituent or a structure which is considered as characteristic of hydroxyalkyl compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/22—Amides of acids of phosphorus
- C07F9/24—Esteramides
- C07F9/2454—Esteramides the amide moiety containing a substituent or a structure which is considered as characteristic
- C07F9/247—Esteramides the amide moiety containing a substituent or a structure which is considered as characteristic of aromatic amines (N-C aromatic linkage)
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/22—Amides of acids of phosphorus
- C07F9/24—Esteramides
- C07F9/2454—Esteramides the amide moiety containing a substituent or a structure which is considered as characteristic
- C07F9/2475—Esteramides the amide moiety containing a substituent or a structure which is considered as characteristic of aralkylamines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4075—Esters with hydroxyalkyl compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
- C07F9/572—Five-membered rings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a polystyrene flame retardant material and a preparation method and application thereof, wherein the raw materials for preparing the polystyrene flame retardant material comprise styrene, a reactive phosphorus-containing flame retardant, toughening rubber and an initiator, and the reactive phosphorus-containing flame retardant has a structure shown as a formula I or a formula II and contains vinyl groups; the reactive phosphorus-containing flame retardant and styrene are taken together as monomers to participate in free radical polymerization reaction, and finally exist in the polystyrene in the form of molecular chain fragments, so that the phenomena of precipitation, water dissolution or hydrolysis of small molecules are avoided, and the high-efficiency and stable environment-friendly flame retardance is truly realized. The polystyrene flame-retardant material provided by the invention has excellent flame-retardant property and mechanical property, and is simple in preparation process and has wide industrial application prospect.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a polystyrene flame-retardant material, and a preparation method and application thereof.
Background
Polystyrene (abbreviated as PS) is one of five general synthetic resins, and is a polymer formed by radical polymerization of styrene monomer. The general polystyrene is a homopolymer of styrene, the molecular weight is about 5-30 ten thousand, the glass transition temperature is 95 ℃, the lateral group of the macromolecular chain is benzene ring, the random arrangement of the benzene ring determines that the general polystyrene is a typical hard plastic, the general polystyrene has light transparent color, good fluidity, easy processing and forming and good electrical property, but has the defects of brittleness, solvent intolerance, ultraviolet light intolerance, oxygen intolerance, elongation rate of only 1-3 percent and the like. In order to solve the brittleness problem of general polystyrene, styrene monomer and butadiene rubber are grafted and copolymerized to obtain high impact polystyrene (HIPS for short), and a two-phase system is formed by a rubber phase and a polystyrene phase, so that the toughness and the impact resistance of the polystyrene are greatly improved, and the polystyrene is widely applied to lining and shell materials of electric elements, household appliances, office equipment, automobile parts and the like.
Polystyrene materials are generally inflammable, have a limiting oxygen index of only about 18%, can be continuously combusted after leaving a fire source, and have large heat release and smoke generation and release toxic gases. In order to improve the use safety of polystyrene, the polystyrene must be flame-retardant modified.
CN102219929A discloses a modified magnesium hydroxide flame retardant, a high impact polystyrene composite flame retardant material composed of the same and a preparation method thereof, wherein the modified magnesium hydroxide flame retardant is prepared from the materials with the average particle diameter of 1-100 mu m and the BET specific surface of 0.5-20 m 2 The magnesium hydroxide powder per gram is obtained by surface treatment of sulfonated high-impact polystyrene, the high-impact polystyrene composite flame retardant material comprises high-impact polystyrene, the modified magnesium hydroxide flame retardant and other common auxiliary agents of polystyrene, and the composite flame retardant material has good tensile strength, bending strength and impact strength, excellent flame retardance and oxygen index of 29%.
CN100372886C discloses a flame retardant polystyrene composition and a preparation method thereof, wherein the composition comprises 100 weight parts of polystyrene, 8-25 weight parts of halogen flame retardant and 2-6 weight parts of synergistic flame retardant; wherein the halogen flame retardant is a mixture of decabromodiphenyl ethane and thermally stable hexabromocyclododecane, the mixing ratio of the decabromodiphenyl ethane and the thermally stable hexabromocyclododecane is 2:1-1:2, and the synergistic flame retardant is antimonous oxide. The flame-retardant polystyrene composition prepared by melt blending the components has good flame retardant property, the flame retardant grade can reach FV-0 grade, the oxygen index can reach 28%, and the flame-retardant polystyrene composition is suitable for various severe environments.
CN108178883a discloses a halogen-free flame-retardant polystyrene with selectively distributed flame retardant and a preparation method thereof, the halogen-free flame-retardant polystyrene is prepared from polystyrene, flame retardant, char forming agent and flame retardant synergist under a hot pressing process, wherein the flame retardant is one or a mixture of more of ammonium polyphosphate, ammonium phosphate or melamine phosphate, the char forming agent is one or a mixture of more of pentaerythritol, dipentaerythritol or phenolic resin, and the flame retardant synergist is carbon materials such as graphene, nano graphite microchip, nano graphite powder and the like; the halogen-free flame-retardant polystyrene has low consumption of flame retardant, good flame retardant effect and limit oxygen index of 28-37%.
However, in the prior art, the flame retardant efficiency of inorganic flame retardants such as magnesium hydroxide, graphite and the like is low, a large amount of inorganic filler is required to be added to realize a good flame retardant effect, but the mechanical property of the material is influenced by the large amount of inorganic filler; although the flame retardant material containing halogen such as bromine has excellent flame retardant performance, the flame retardant material can generate products such as dioxin which are difficult to degrade during combustion, so that serious environmental pollution is caused and the human health is endangered; although the combustion products of the additive type phosphorus-nitrogen halogen-free flame retardant material cannot cause environmental pollution, the additive type phosphorus-nitrogen halogen-free flame retardant material has mobility and precipitation in the production, storage, use and scrapping treatment processes, and most of additive type flame retardants are easy to hydrolyze, so that molecules, decomposition products or water-soluble substances of the additive type flame retardant material enter the environment to pollute the environment, and therefore, the actual environment-friendly flame retardant cannot be realized.
Therefore, developing a high-performance polystyrene material which can truly achieve safety, environmental protection and flame retardance to meet application requirements is an important research point in the field.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a polystyrene flame-retardant material, a preparation method and application thereof, wherein a flame retardant is taken as a reaction monomer to participate in the polymerization process of polystyrene and finally exists in the form of molecular chain fragments in polystyrene resin, so that the polystyrene flame-retardant material grease provided by the invention has excellent flame-retardant performance, and meanwhile, small molecules cannot migrate and separate out, thereby truly realizing safety and environmental protection.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a polystyrene flame retardant material, wherein the polystyrene flame retardant material is prepared from styrene, a reactive phosphorus-containing flame retardant, toughening rubber and an initiator.
The reactive phosphorus-containing flame retardant has a structure shown in a formula I or a formula II:
wherein L is 1 、L 2 Each independently selected from vinyl-terminated groups.
Z 1 、Z 2 Each independently selected from phosphorus-containing groups.
M 1 Selected from linear alkylene, branched alkylene or arylene groups.
M 2 Selected from any organic group that satisfies the chemical environment.
Y 1 、Y 2 Each independently selected from the group consisting of an inert group, -OH, a sulfur atom, an oxygen atom, or-H.
X 1 Selected from any sub-organic group that satisfies the chemical environment.
X 2 Aliphatic groups containing carbon-carbon double bonds selected from C2-C30.
a. b, c, d, f, g, h are each independently selected from integers from 0 to 5, for example 0, 1, 2, 3, 4 or 5; and a, b are not 0 at the same time, f, g are not 0 at the same time, g, h are not 0 at the same time, b+c+h.ltoreq.5 (e.g. b+c+h=0, 1, 2, 3, 4 or 5) and a+d+g.ltoreq.5 (e.g. a+d+g=0, 1, 2, 3, 4 or 5).
e is an integer from 0 to 100, such as 0, 1, 3, 5, 8, 10, 20, 30, 40, 50, 60, 70, 80, 90 or 95, and specific point values between the above point values, are limited in space and for brevity, the invention is not intended to be exhaustive of the specific point values encompassed by the described ranges.
The polystyrene flame-retardant material provided by the invention comprises styrene, toughened rubber, a flame retardant and an initiator, wherein the flame retardant is a reactive phosphorus-containing flame retardant containing carbon-carbon double bonds. In the preparation process of the polystyrene flame-retardant material, carbon-carbon double bonds in the reactive phosphorus-containing flame retardant and double bonds in the styrene generate free radicals under the initiation of an initiator to jointly generate free radical polymerization, so that flame-retardant groups are embedded into the macromolecular structure of the polystyrene through stable chemical bonds, and the flame-retardant modification of the polystyrene resin is realized; when styrene and a flame retardant containing carbon-carbon double bonds are copolymerized, part of free radicals are transferred to a rubber chain to generate grafting points, and the styrene is polymerized on the grafting points to form branched chains, so that the graft copolymer is obtained. Therefore, in the polystyrene flame-retardant material provided by the invention, the flame retardant is taken as a polymerization monomer to participate in free radical polymerization reaction during the synthesis of the polystyrene resin, and finally exists in the polystyrene resin in a molecular chain segment form, so that the phenomenon of precipitation of small molecules is avoided, and the phenomenon that the additive flame retardant is easily dissolved in water to precipitate or hydrolyze is avoided; more importantly, the flame retardant groups are introduced into the polymer in a chemical bond mode through copolymerization, so that microscopic phase separation caused by physical blending in the additive flame retardant modification process is avoided, the mechanical properties of the polystyrene are not affected, and the flame retardant has a certain reinforcing and toughening effect on the polystyrene through the molecular structure of the reactive phosphorus-containing flame retardant.
Preferably, the polystyrene flame retardant material comprises the following raw materials:
in the present invention, the styrene may be used in an amount of 61 parts by weight, 63 parts by weight, 65 parts by weight, 68 parts by weight, 70 parts by weight, 75 parts by weight, 78 parts by weight, 80 parts by weight, 82 parts by weight, 84 parts by weight, 85 parts by weight, 88 parts by weight, 90 parts by weight, 95 parts by weight or 98 parts by weight, and specific point values between the above point values are limited and for the sake of brevity, the present invention is not exhaustive of the specific point values included in the range.
In the present invention, the reactive phosphorus-containing flame retardant may be used in an amount of 4 parts by weight, 5 parts by weight, 7 parts by weight, 9 parts by weight, 10 parts by weight, 13 parts by weight, 15 parts by weight, 20 parts by weight, 23 parts by weight, 25 parts by weight, 28 parts by weight, 30 parts by weight, 35 parts by weight or 40 parts by weight, and specific point values between the above point values, which are not exhaustive for the sake of brevity and conciseness.
In the present invention, the amount of the toughening rubber may be 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight or 15 parts by weight, and specific point values among the above point values are limited in length and for brevity, and the present invention is not exhaustive of the specific point values included in the range.
In the present invention, the initiator may be used in an amount of 0.02 parts by weight, 0.04 parts by weight, 0.06 parts by weight, 0.08 parts by weight, 0.1 parts by weight, 0.2 parts by weight, 0.3 parts by weight, 0.4 parts by weight or 0.45 parts by weight, and specific point values between the above point values are limited in space and for brevity, the present invention is not exhaustive of the specific point values included in the range.
Preferably, the L 1 、L 2 Each independently selected fromWherein j is an integer of 0 to 20 (e.g., 0, 1, 2, 3, 5, 6, 8, 10, 12, 13, 15, 16, 18, or 20, etc.), R 10 Alkyl of C1-C10 (e.g. C2, C3, C4, C5, C6, C7, C8 or C9), and# denotes the position of attachment of the group.
Preferably, said Z 1 、Z 2 Each independently selected from One of R 1 Any one selected from saturated or unsaturated alkyl, aryl or heteroaryl is further preferred to be methyl, ethyl or phenyl.
Preferably, said M 1 Selected from C, N,O、-O-R T -, a part of C1-C30 straight chainOr one of branched alkylene, C6-C30 arylene or C5-C7 heteroarylene; further preferably +.>-O-R T -, a C1-C5 linear alkylene group C3-C5 branched alkylene, phenyl or naphthyl; still more preferably C1-C3 linear alkylene, C3 branched alkylene, phenyl or naphthyl; wherein R is T Is selected from one of C1-C10 straight chain or branched chain alkyl and C6-C30 aryl.
The C1-C30 includes C2, C3, C5, C7, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28, C29, etc.
The C6-C30 includes C7, C9, C10, C12, C14, C15, C17, C20, C22, C24, C26, C28, C29, etc.
The C5-C7 includes C5, C6 or C7.
The C1-C5 straight-chain alkylene group comprises methylene, ethylene, propylene, butylene or pentylene.
The C3-C5 branched alkylene includes a C3, C4 or C5 branched alkylene.
The C1-C10 includes C2, C3, C5, C7, C9, and the like.
Preferably, said M 2 Selected from C, N,O、-O-R T -, C1-C30 linear or branched alkyl, C6-C30 aryl, C5-C7 heteroaryl, -, or->One of the following; wherein R is T Is selected from one of C1-C10 straight chain or branched chain alkyl and C6-C30 aryl, R 2 -R 9 Each independently selected from one of C1-C10 straight or branched chain alkylene groups, L 2 、Y 2 、Z 2 Attached at R 2 -R 9 N, m, i, k are each independently selected from integers from 0 to 100, such as 0, 1, 3, 5, 8, 10, 20, 30, 40, 50, 60, 70, 80, 90 or 95, and aboveSpecific point values between the point values are, for brevity and for simplicity, not an exhaustive list of specific point values within the range is included.
The C1-C30 includes C2, C3, C5, C7, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28, C29, etc.
The C6-C30 includes C7, C9, C10, C12, C14, C15, C17, C20, C22, C24, C26, C28, C29, etc.
The C5-C7 includes C5, C6 or C7.
The C1-C10 includes C2, C3, C4, C5, C6, C7, C8 or C9.
Preferably, said R 2 -R 9 Each independently selected from one of C1-C6 linear or branched alkylene, e.g., C1, C2, C3, C4, C5, or C6 linear or branched alkylene.
Preferably, each of said n, m, i, k is independently selected from integers from 0 to 30, such as 0, 1, 3, 5, 8, 10, 15, 20, 25 or 29, and specific point values between the above point values, are for brevity and for brevity, the invention is not intended to be exhaustive of the specific point values comprised in said range.
Preferably, said Y 1 、Y 2 Each independently selected from-H, -OH, or = O.
Preferably, the X 1 Selected from N, S, substituted or unsubstituted C1-C30 linear or branched alkylene, substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C5-C7 heteroarylene, substituted or unsubstituted C1-C30 alkyleneamino, substituted or unsubstituted C1-C30 alkyleneacyl, substituted or unsubstituted C1-C30 alkyleneester, substituted or unsubstituted C6-C30 aryleneamino, substituted or unsubstituted C6-C30 aryleneacyl, or C6-C30 aryleneester, further preferably a substituted or unsubstituted C1-C5 linear or branched alkylene group, a substituted or unsubstituted C1-C5 alkyleneamino group, a substituted or unsubstituted C1-C5 alkyleneacyl group, a substituted or unsubstituted C1-C5 alkyleneester group, more preferably-NH-R-; -R '-NH-, -R' -O-, -R V -C (O) -, substituted or unsubstituted C1-C5 linear or branched sub-groupAlkyl, wherein R, R', R ", R V Each independently selected from substituted or unsubstituted C1 to C10 linear or branched alkylene groups.
The term "substituted" as used herein means that any one or more hydrogen atoms on a given atom is substituted with a substituent selected from the specified group, provided that the given atom does not exceed a normal valence, and that the result of substitution is to produce a stable compound. When the substituent is an oxo group or a keto group (i.e., =o), then 2 hydrogen atoms on the atom are substituted. The ketone substituents are absent from the aromatic ring. By "stable compound" is meant a compound that is capable of being isolated from the reaction mixture sufficiently robustly to an effective purity and formulated to be effective.
The C1-C30 includes C2, C3, C5, C7, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28, C29, etc.
The C6-C30 includes C7, C9, C10, C12, C14, C15, C17, C20, C22, C24, C26, C28, C29, etc.
The C5-C7 includes C5, C6 or C7.
The C1-C5 includes C1, C2, C3, C4 or C5.
The C1-C10 includes C2, C3, C4, C5, C6, C7, C8 or C9.
Preferably, the X 2 Is thatWherein R is q 、R s Each independently selected from a single bond or a C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, or C9) alkylene group.
Preferably, the reactive phosphorus-containing flame retardant has a structure as shown in formula III, formula IV, formula V, formula VI, formula VII or formula VIII:
wherein L is 1 、L 2 Each independently selected fromWherein j is an integer of 0 to 3 (e.g., 1 or 2), R 10 Alkyl of C1-C3 (e.g., C1, C2 or C3), and # denotes the access position of the group.
M 1 Selected from the group consisting of-O-R T One of C1-C3 (e.g., C1, C2 or C3) straight chain alkylene, C3 branched alkylene, naphthyl or phenyl.
M 2 Selected from C, N,O、-O-R T -, C1-C6 (e.g.C2, C3, C4, C5 or C6) straight-chain or branched alkyl, -, -> Wherein R is T Is one of C1-C6 (e.g. C1, C2, C3, C4, C5 or C6) straight-chain or branched alkyl, phenyl or biphenyl, R 2 -R 9 Each independently selected from C1 to C6 (e.g., C1, C2, C3, C4, C5, or C6) straight or branched chain alkylene, n, m, i, k each independently selected from integers from 0 to 30, e.g., 0, 1, 3, 5, 8, 10, 15, 20, 25, or 29, and specific point values between the above point values, are limited in length and for brevity, the invention is not intended to be exhaustive of the specific point values included in the range.
L 2 、Y 2 、Z 2 Attached at R 2 -R 9 Is provided, is provided with a connecting means, and is provided with a connecting means.
R 1 Is methyl or ethyl.
R、R'、R”、R V 、R P Each independently selected from substituted or unsubstituted C1-C10 (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9, or C10) straight or branched chain alkylene.
R q 、R s Each independently selected from a single bond or a C1-C3 (e.g., C1, C2 or C3) alkylene group.
Y 1 、Y 2 Each independently selected from-H, -OH, or = O.
a. b, g and h are each independently selected from 0, 1 or 2, and a+b is not less than 2, f and g are not simultaneously 0, g and h are not simultaneously 0.
e is an integer from 0 to 20, such as 0, 1, 3, 5, 8, 10, 13, 15, 18 or 19, and specific point values between the above point values, are for brevity and for simplicity, the invention is not intended to be exhaustive of the specific point values encompassed by the described ranges.
f is 0 or 1.
Preferably, the reactive phosphorus-containing flame retardant is further preferably any one or a combination of at least two of the following structural compounds:
wherein R is P One selected from substituted or unsubstituted C1-C8 (e.g., C2, C3, C4, C5, C6, C7, or C8) straight or branched alkylene; r is R 1 Methyl or ethyl; e is an integer of 0 to 5 (e.g., 0, 1, 2, 3, 4, or 5).
Preferably, the toughening rubber is cis-1, 4-polybutadiene rubber and/or styrene-butadiene rubber, and more preferably cis-1, 4-polybutadiene rubber.
Preferably, the cis-1, 4-polybutadiene rubber includes a low cis-1, 4-polybutadiene rubber and a high cis-1, 4-polybutadiene rubber.
Preferably, the initiator is a peroxide initiator.
Preferably, the peroxide initiator is selected from one of dibenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, lauroyl peroxide or t-butyl peroxybenzoate.
Preferably, the polystyrene flame retardant material further comprises an organic solvent.
Preferably, the organic solvent is ethylbenzene.
Preferably, the ethylbenzene is added in an amount of 18-23% by mass of styrene, for example 18.5%, 19%, 20%, 20.5%, 21%, 22% or 23%, and specific point values between the above point values, are limited in space and for the sake of brevity, the invention is not exhaustive of the specific point values included in the range, more preferably 20%.
In another aspect, the present invention provides a method for preparing the polystyrene flame retardant material as described above, the method comprising the steps of: and mixing styrene, a reactive phosphorus-containing flame retardant, toughening rubber and an initiator, and performing bulk graft polymerization to obtain the polystyrene flame retardant material.
Preferably, the reaction temperature of the bulk graft polymerization is 80 to 230 ℃, such as 82 ℃, 84 ℃, 85 ℃, 88 ℃, 90 ℃, 92 ℃, 94 ℃, 95 ℃, 98 ℃, 100 ℃, 103 ℃, 105 ℃, 108 ℃, 110 ℃, 120 ℃, 125 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃ or 225 ℃, and specific point values between the above point values, limited in space and for brevity, the present invention is not exhaustive of the specific point values included in the range.
Preferably, the reaction time of the bulk graft polymerization is from 7 to 20 hours, for example 8 hours, 9 hours, 10 hours, 12 hours, 14 hours, 15 hours, 16 hours, 17 hours or 19 hours, and the specific point values between the above point values, are limited in length and for the sake of brevity, the invention is not intended to be exhaustive of the specific point values included in the range.
Preferably, the bulk graft polymerization is carried out under stirring.
Preferably, the bulk graft polymerization is carried out in a protective atmosphere.
Preferably, the protective atmosphere is nitrogen or argon.
Preferably, the preparation method further comprises post-treatment of the product.
Preferably, the post-treatment is performed by a devolatilizer.
Preferably, the preparation method specifically comprises the following steps: under the protection of nitrogen, mixing styrene, reactive phosphorus-containing flame retardant, toughening rubber, initiator and organic solvent, stirring at 80-230 ℃ for 7-20 h, and stopping the reaction; and removing residual styrene and organic solvent by using a devolatilization device to obtain the polystyrene flame-retardant material.
On the other hand, the invention provides application of the polystyrene flame-retardant material in the outer shell, inner lining and automobile parts of the electronic and electric appliance.
Compared with the prior art, the invention has the following beneficial effects:
the preparation raw materials of the polystyrene flame retardant material provided by the invention comprise styrene, a reactive phosphorus-containing flame retardant, toughening rubber and an initiator, wherein the reactive phosphorus-containing flame retardant contains vinyl and can undergo a free radical copolymerization reaction with a styrene monomer, so that the flame retardant finally exists in the polystyrene resin in a molecular chain segment form, the phenomenon of precipitation of small molecules is avoided, the phenomenon that certain additive flame retardants are easily dissolved in water to be precipitated or hydrolyzed is also avoided, and high-efficiency environment-friendly flame retardance is truly realized; the reactive phosphorus-containing flame retardant has a certain reinforcing and toughening effect on the polystyrene flame retardant material. The flame retardant polystyrene material provided by the invention has the combustibility reaching V-0 level, the combustion performance after water boiling still reaching V-0 level, high hardness, toughness and impact strength, the tensile strength reaching more than 41MPa, the elongation at break reaching 47.9-53%, and the impact strength reaching 8.5KJ/m 2 The flame retardant has excellent flame retardance, flame retardant stability and mechanical property, and the preparation method is simple in preparation process, easy in raw material acquisition and wide in industrialized application prospect.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Preparation example 1
A reactive phosphorus-containing flame retardant with vinyl has the following structure:
the preparation method comprises the following steps:
1mol of 4-aminostyrene, 2.2mol of dimethyl hydroxymethyl phosphite, 0.1mol of sodium hydroxide, 0.1g of DMAP and 500mL of ethanol are added into a reaction kettle, and the mixture is stirred and heated until the ethanol flows back; then continuing to react for 24 hours under the stirring condition; and after the reaction is finished, washing with water to be neutral, and removing impurities to obtain a target product.
1 H NMR(CDCl 3 400mhz, tms): delta 6.57-6.69,7.13-7.26 (m, 4H, H on benzene ring), 6.61-6.70 (t, 1H, =CH-), 5.69-5.75 (d, 1H, CH) 2 =h above), 5.11-5.23 (d, 1H, ch 2 =h above), 3.57-3.71 (d, 12H, -CH 3 )。
Preparation example 2
A reactive phosphorus-containing flame retardant with vinyl has the following structure:
the preparation method comprises the following steps:
1mol of N-methyl-3-phenyl-2-propylene-1-amine, 1.2mol of hydroxyethyl hydroxymethylphosphite, 0.1mol of sodium hydroxide, 0.1g of DMAP and 400mL of ethanol are added into a reaction kettle, and the mixture is stirred and heated until the ethanol flows back; then continuing to react for 24 hours under the stirring condition; and after the reaction is finished, washing with water to be neutral, and removing impurities to obtain a target product.
1 H NMR(CDCl 3 400mhz, tms): delta 7.01-7.19 (m, 5H, H on benzene ring), 6.42-6.55 (d, 1H, =CH-), 6.08-6.14 (m, 1H, =CH-), 1.27 (t, 6H, -CH) 3 )。
Preparation example 3
A reactive phosphorus-containing flame retardant with vinyl has the following structure:
the preparation method comprises the following steps:
1mol of 4-aminostilbene, 2.2mol of dimethyl hydroxymethyl phosphite, 0.1mol of sodium hydroxide, 0.1g of DMAP and 500mL of ethanol are added into a reaction kettle, and the mixture is stirred and heated until the ethanol flows back; then continuing to react for 24 hours under the stirring condition; and after the reaction is finished, washing with water to be neutral, and removing impurities to obtain a target product.
1 H NMR(CDCl 3 400mhz, tms): delta 7.23-7.61,6.67-6.73 (m, 7H, H on benzene ring), 6.74-6.81 (d, 2H, =CH-), 3.55-3.71 (d, 12H, -CH) 3 )。
Preparation example 4
A reactive phosphorus-containing flame retardant with vinyl has the following structure:
the preparation method comprises the following steps:
1mol of maleic anhydride, 2.1mol of dimethyl hydroxymethylphosphite, 500mL of cyclohexane and 0.3mol of NaHSO 4 ·H 2 And (3) putting O into a reaction kettle, heating to 120 ℃, carrying out reflux reaction for 6 hours under stirring, adding saturated sodium carbonate solution for extraction after the reaction is finished, stirring for 20min, separating an organic phase by using a separating funnel, and carrying out reduced pressure distillation to remove a solvent to obtain a target product.
1 H NMR(CDCl 3 ,400MHz,TMS):δ6.89-7.01(s,4H,-CH 2 -),6.35-6.52(d,2H,-CH＝CH-),3.42-3.58(d,12H,-CH 3 )。
Preparation example 5
A reactive phosphorus-containing flame retardant with vinyl has the following structure:
the preparation method comprises the following steps:
1mol of maleimide, 1.2mol of diethyl hydroxymethylphosphite, 0.1g of DMAP, 0.1mol of sodium hydroxide and 500mL of ethanol are added into a reaction kettle, the mixture is stirred and heated until the ethanol flows back, then the mixture is stirred and continuously reacted for 24 hours, and after the reaction is finished, the mixture is washed with water until the mixture is neutral, and impurities are removed to obtain a target product.
1H NMR(CDCl 3 ,400MHz,TMS):δ6.98-7.05(s,2H,-CH＝CH-),3.73-3.86(m,4H,-CH 2 -),1.24(t,6H,-CH 3 )。
Preparation example 6
A reactive phosphorus-containing flame retardant with vinyl has the following structure:
the preparation method comprises the following steps:
1mol of 4-aminostyrene, 2.2mol of diethyl hydroxymethylphosphite, 0.1mol of sodium hydroxide, 0.1g of DMAP and 500mL of ethanol are added into a reaction kettle, and the mixture is stirred and heated until the ethanol flows back; then continuing to react for 24 hours under the stirring condition; and after the reaction is finished, washing with water to be neutral, and removing impurities to obtain a target product.
1 H NMR(CDCl 3 400mhz, tms): delta 6.44-6.51,7.08-7.15 (m, 4H, H on benzene ring), 6.57-6.68 (t, 1H, =CH-), 5.64-5.71 (d, 1H, CH) 2 =h above), 5.18-5.29 (d, 1H, ch 2 =h above), 3.42-3.59 (m, 12H, -CH 2 -),1.21(t,12H,-CH 3 )。
Examples 1 to 6
The polystyrene flame-retardant material comprises the following raw materials:
wherein the reactive phosphorus-containing flame retardant is the reactive phosphorus-containing flame retardant with vinyl provided in preparation examples 1-6, the toughening rubber is low cis-1, 4-polybutadiene rubber (SKD-L), and the initiator is dibenzoyl peroxide (BPO); in order to avoid excessive viscosity and facilitate stirring and heat transfer, 15 parts by weight of ethylbenzene is also added as a solvent in the preparation process.
The preparation method comprises the following steps:
(1) Adding styrene, a reactive phosphorus-containing flame retardant, toughened rubber, an initiator and ethylbenzene into reaction equipment, stirring and heating under the protection of nitrogen, and stirring and reacting for 5h at 90 ℃; then heating to 120 ℃, continuing stirring and reacting for 5 hours, and stopping the reaction;
(2) And (3) transferring the product obtained in the step (1) into a devolatilization device, and removing residual styrene monomer and solvent to ensure that the content of residual styrene is lower than 2.5%, thereby obtaining the polystyrene flame-retardant material.
Example 7
The embodiment provides a polystyrene flame-retardant material, which is prepared from the following raw materials:
wherein the reactive phosphorus-containing flame retardant is the reactive phosphorus-containing flame retardant with vinyl provided in preparation example 1, the toughening rubber is low cis-1, 4-polybutadiene rubber (SKD-L), and the initiator is BPO; in order to avoid excessive viscosity and facilitate stirring and heat transfer, 12 parts by weight of ethylbenzene is also added as a solvent in the preparation process.
The preparation method comprises the following steps:
(1) Adding styrene, a reactive phosphorus-containing flame retardant, toughened rubber, an initiator and ethylbenzene into reaction equipment, stirring and heating under the protection of nitrogen, and stirring and reacting for 7h at 85 ℃; then heating to 125 ℃, continuing stirring and reacting for 5 hours, and stopping the reaction;
(2) And (3) transferring the product obtained in the step (1) into a devolatilization device, and removing residual styrene monomer and solvent to ensure that the content of residual styrene is lower than 2.5%, thereby obtaining the polystyrene flame-retardant material.
Example 8
The embodiment provides a polystyrene flame-retardant material, which is prepared from the following raw materials:
wherein the reactive phosphorus-containing flame retardant is the reactive phosphorus-containing flame retardant with vinyl provided in preparation example 1, the toughening rubber is low cis-1, 4-polybutadiene rubber (SKD-L), and the initiator is BPO; in order to avoid excessive viscosity and facilitate stirring and heat transfer, 20 parts by weight of ethylbenzene is also added as a solvent in the preparation process.
The preparation method comprises the following steps:
(1) Adding styrene, a reactive phosphorus-containing flame retardant, toughened rubber, an initiator and ethylbenzene into reaction equipment, stirring and heating under the protection of nitrogen, and stirring and reacting for 4 hours at 95 ℃; then heating to 130 ℃, continuing to stir and react for 5.5 hours, and stopping the reaction;
(2) And (3) transferring the product obtained in the step (1) into a devolatilization device, and removing residual styrene monomer and solvent to ensure that the content of residual styrene is lower than 2.5%, thereby obtaining the polystyrene flame-retardant material.
Comparative example 1
This comparative example differs from example 1 in that the reactive phosphorus-containing flame retardant was replaced with equal parts by weight of styrene.
Comparative example 2
This comparative example differs from example 1 in that the reactive phosphorus-containing flame retardant was replaced with ammonium polyphosphate in equal parts by weight.
Comparative example 3
This comparative example differs from example 1 in that the reactive phosphorus-containing flame retardant was replaced with triphenyl phosphate in equal parts by weight.
Comparative example 4
This comparative example differs from example 1 in that the reactive phosphorus-containing flame retardant was replaced with 45 parts by weight of ammonium polyphosphate.
Comparative example 5
The comparative example differs from example 1 in that the reactive phosphorus-containing flame retardant was 2 parts by weight.
Comparative example 6
The comparative example differs from example 1 in that the reactive phosphorus-containing flame retardant was 43 parts by weight.
Performance test:
(1) Tensile strength and elongation at break: using a GMT4503 microcomputer control electronic universal tester, testing according to the standard specification of GB/T1040.2-2006, wherein the stretching speed is 50mm/min, the sample width is 5.0mm, the thickness is 2.0mm, 5 samples are tested in parallel in each group, and the average value is obtained;
(2) Impact strength: using an SE-2 type simply supported beam impact strength tester, testing according to the standard specification of GB/T1043-1993, wherein the impact speed is 3.5m/s, the sample width is 10mm, the length is 80mm, the thickness is 4.0mm, and 5 samples are tested in parallel in each group and the average value is obtained;
(3) Combustibility: testing according to the UL-94 vertical burning test standard;
(4) Flame retardant stability: after the polystyrene flame-retardant material is boiled in boiling water for 2 hours, the polystyrene flame-retardant material is dried, and the combustibility is measured again according to the UL-94 vertical burning test standard;
(5) Mobility: the polystyrene flame retardant material was baked at 150℃for 2 hours, and the weight change rate (%) before and after baking was measured.
The polystyrene flame retardant materials provided in examples 1 to 8 and comparative examples 1 to 6 were tested for tensile strength, elongation at break, impact strength, combustibility, flame retardant stability and migration according to the above-described methods, and the test results are shown in table 1:
TABLE 1
As can be seen from the data in Table 1, the polystyrene flame retardant materials of examples 1 to 8, to which the vinyl group-containing reactive phosphorus flame retardant is added, have significantly superior combustibility and flame retardant stability, and improved mechanical properties, and the tensile strength can reach 41 to 49.5MPa, the elongation at break can reach 47.9 to 53%, and the impact strength can reach 8.5KJ/m, as compared with the polystyrene of comparative example 1, to which the flame retardant is not a flame retardant 2 The balance of hardness and toughness is better, and the impact strength is high; the reactive phosphorus-containing flame retardant with vinyl in the example 1 is replaced by the equivalent additive flame retardant (comparative example 2 and comparative example 3), the combustibility and mechanical property of the obtained polystyrene flame retardant material are obviously reduced, the flame retardant stability is poor, and the flame retardant property of the material is obviously reduced after the material is boiled in water; the burning property of the material can be optimized by increasing the consumption of the additive flame retardant (comparative example 4), but the flame retardant stability of the material is still poor, the flame retardant property after water boiling is reduced, and the weight change rate after baking is large, so that compared with the reactive flame retardant with vinyl, the additive flame retardant has low flame retardant efficiency and obvious migration and precipitation phenomena. If the content of the reactive phosphorus-containing flame retardant with vinyl in the polystyrene flame retardant material exceeds the range defined by the invention, the flame retardant performance cannot be effectively realized if the content of the flame retardant is too low (comparative example 5), and if the content of the flame retardant is too high (comparative example 6), the material is over-plasticized, so that the mechanical performance is reduced, and the resource waste is caused.
In conclusion, the polystyrene flame retardant material prepared by copolymerization of the preparation raw materials and the reactive phosphorus flame retardant with vinyl introduced in the preparation process has excellent flame retardance, and the flame retardance of the material can reach V-0 level; the flame retardant in the polystyrene flame-retardant material provided by the invention participates in free radical polymerization reaction and stably exists in the material in the form of molecular chain fragments, the flame retardant property of the material is stable, the phenomena of precipitation, water dissolution or hydrolysis of small molecules are avoided, the flame retardant is not reduced due to migration and precipitation of the flame retardant caused by water boiling or baking and other operations, and the flame retardant property of the material after water boiling can still reach V-0 level; more importantly, the reactive flame retardant is completely embedded into the polymer chain segment, so that the mechanical property of the material is not reduced due to the compatibility problem of the additive flame retardant, and the introduction of the reactive phosphorus flame retardant with vinyl has a certain reinforcing and toughening effect on the polystyrene flame retardant material, so that the polystyrene flame retardant material provided by the invention has good mechanical property.
The applicant states that the polystyrene flame retardant material of the present invention, and the preparation method and application thereof are illustrated by the above examples, but the present invention is not limited to the above examples, i.e., it does not mean that the present invention must be practiced by relying on the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (20)
1. The polystyrene flame-retardant material is characterized by comprising the following raw materials:
the reactive phosphorus-containing flame retardant is any one or a combination of at least two of the following compounds:
wherein R is 1 Is methyl or ethyl.
2. The polystyrene flame retardant material according to claim 1, wherein the toughening rubber is cis-1, 4-polybutadiene rubber and/or styrene butadiene rubber.
3. The polystyrene flame retardant material of claim 1, wherein the toughening rubber is cis-1, 4-polybutadiene rubber.
4. A polystyrene flame retardant material according to claim 2 or 3, wherein said cis-1, 4-polybutadiene rubber comprises a low cis-1, 4-polybutadiene rubber and a high cis-1, 4-polybutadiene rubber.
5. The polystyrene flame retardant material of claim 1, wherein the initiator is a peroxide initiator.
6. The polystyrene flame retardant material according to claim 5, wherein the peroxide initiator is one selected from dibenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, lauroyl peroxide and t-butyl peroxybenzoate.
7. The polystyrene flame retardant material according to claim 1, wherein the raw materials for preparing the polystyrene flame retardant material further comprise an organic solvent.
8. The polystyrene flame retardant material of claim 7, wherein the organic solvent is ethylbenzene.
9. The polystyrene flame retardant material according to claim 8, wherein the ethylbenzene is added in an amount of 18 to 23% by mass of styrene.
10. The polystyrene flame retardant material according to claim 9, wherein the ethylbenzene is added in an amount of 20% by mass of styrene.
11. A method for preparing the polystyrene flame retardant material according to any one of claims 1 to 10, characterized in that the preparation method comprises the steps of:
and mixing styrene, a reactive phosphorus-containing flame retardant, toughening rubber and an initiator, and performing bulk graft polymerization to obtain the polystyrene flame retardant material.
12. The process according to claim 11, wherein the reaction temperature of the bulk graft polymerization is 80 to 230 ℃.
13. The method according to claim 11, wherein the reaction time of the bulk graft polymerization is 7 to 20 hours.
14. The method of claim 11, wherein the bulk graft polymerization is performed under stirring.
15. The method of claim 11, wherein the bulk graft polymerization is carried out in a protective atmosphere.
16. The method of claim 15, wherein the protective atmosphere is nitrogen or argon.
17. The method of claim 11, further comprising post-treatment of the product.
18. The method of claim 17, wherein the post-treatment is performed by a devolatilizer.
19. The preparation method according to claim 11, characterized in that it comprises in particular the following steps:
under the protection of nitrogen, mixing styrene, reactive phosphorus-containing flame retardant, toughening rubber, initiator and organic solvent, stirring at 80-230 ℃ for 7-20 h, and stopping the reaction; and removing residual styrene and organic solvent by using a devolatilization device to obtain the polystyrene flame-retardant material.
20. Use of a polystyrene flame retardant material as defined in any one of claims 1 to 10 in the outer shell, inner liner and automotive parts of an electrical and electronic appliance.
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