CN112480168B - 一种含磷阻燃剂和阻燃高分子材料 - Google Patents
一种含磷阻燃剂和阻燃高分子材料 Download PDFInfo
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- CN112480168B CN112480168B CN202011354352.9A CN202011354352A CN112480168B CN 112480168 B CN112480168 B CN 112480168B CN 202011354352 A CN202011354352 A CN 202011354352A CN 112480168 B CN112480168 B CN 112480168B
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- phosphorus
- temperature
- acrylate
- flame retardant
- retardant
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 72
- 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 65
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 49
- 239000011574 phosphorus Substances 0.000 title claims abstract description 49
- 239000002861 polymer material Substances 0.000 title claims abstract description 13
- -1 acrylic ester Chemical class 0.000 claims abstract description 23
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000178 monomer Substances 0.000 claims description 36
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 24
- 239000012043 crude product Substances 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 238000002360 preparation method Methods 0.000 claims description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000000047 product Substances 0.000 claims description 14
- 239000000839 emulsion Substances 0.000 claims description 13
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 10
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- KTLIMPGQZDZPSB-UHFFFAOYSA-N diethylphosphinic acid Chemical compound CCP(O)(=O)CC KTLIMPGQZDZPSB-UHFFFAOYSA-N 0.000 claims description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 6
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 6
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims description 6
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 6
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 239000003995 emulsifying agent Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- UTRYTADHKMZXAH-UHFFFAOYSA-N CCP(CC)(OCCCO)=O Chemical compound CCP(CC)(OCCCO)=O UTRYTADHKMZXAH-UHFFFAOYSA-N 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000003112 inhibitor Substances 0.000 claims description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000002390 rotary evaporation Methods 0.000 claims description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- 238000002474 experimental method Methods 0.000 claims 2
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 claims 1
- 239000012969 di-tertiary-butyl peroxide Substances 0.000 claims 1
- 230000001804 emulsifying effect Effects 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- 238000005303 weighing Methods 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 11
- 239000001257 hydrogen Substances 0.000 abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 9
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 6
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 abstract description 3
- 150000001266 acyl halides Chemical class 0.000 abstract description 2
- 239000000470 constituent Substances 0.000 abstract description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 39
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 25
- 239000003054 catalyst Substances 0.000 description 16
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 14
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 12
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 12
- 239000002253 acid Substances 0.000 description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 8
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 8
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 8
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 8
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 description 7
- 235000011181 potassium carbonates Nutrition 0.000 description 7
- KGENPKAWPRUNIG-UHFFFAOYSA-N 1-[chloro(ethyl)phosphoryl]ethane Chemical compound CCP(Cl)(=O)CC KGENPKAWPRUNIG-UHFFFAOYSA-N 0.000 description 6
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 6
- 150000001299 aldehydes Chemical class 0.000 description 6
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 6
- 150000002576 ketones Chemical class 0.000 description 6
- 239000011736 potassium bicarbonate Substances 0.000 description 6
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 6
- 235000015497 potassium bicarbonate Nutrition 0.000 description 6
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 6
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 6
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 6
- MBAOYGOGBJKMLV-UHFFFAOYSA-N 2-diethylphosphoryloxyethanol Chemical compound CCP(=O)(CC)OCCO MBAOYGOGBJKMLV-UHFFFAOYSA-N 0.000 description 5
- 239000004925 Acrylic resin Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 230000009471 action Effects 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 5
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 4
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 4
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 4
- QUVMSYUGOKEMPX-UHFFFAOYSA-N 2-methylpropan-1-olate;titanium(4+) Chemical compound [Ti+4].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] QUVMSYUGOKEMPX-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 4
- GCTFWCDSFPMHHS-UHFFFAOYSA-M Tributyltin chloride Chemical compound CCCC[Sn](Cl)(CCCC)CCCC GCTFWCDSFPMHHS-UHFFFAOYSA-M 0.000 description 4
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 4
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 4
- PIMYDFDXAUVLON-UHFFFAOYSA-M chloro(triethyl)stannane Chemical compound CC[Sn](Cl)(CC)CC PIMYDFDXAUVLON-UHFFFAOYSA-M 0.000 description 4
- KWTSZCJMWHGPOS-UHFFFAOYSA-M chloro(trimethyl)stannane Chemical compound C[Sn](C)(C)Cl KWTSZCJMWHGPOS-UHFFFAOYSA-M 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- RJGHQTVXGKYATR-UHFFFAOYSA-L dibutyl(dichloro)stannane Chemical compound CCCC[Sn](Cl)(Cl)CCCC RJGHQTVXGKYATR-UHFFFAOYSA-L 0.000 description 4
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 4
- 239000000347 magnesium hydroxide Substances 0.000 description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 4
- 125000005395 methacrylic acid group Chemical group 0.000 description 4
- 229940098779 methanesulfonic acid Drugs 0.000 description 4
- 229960004063 propylene glycol Drugs 0.000 description 4
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000001119 stannous chloride Substances 0.000 description 4
- 235000011150 stannous chloride Nutrition 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- PWBHRVGYSMBMIO-UHFFFAOYSA-M tributylstannanylium;acetate Chemical compound CCCC[Sn](CCCC)(CCCC)OC(C)=O PWBHRVGYSMBMIO-UHFFFAOYSA-M 0.000 description 4
- 229920000178 Acrylic resin Polymers 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 3
- 229910000024 caesium carbonate Inorganic materials 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 3
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 3
- 229910001947 lithium oxide Inorganic materials 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 description 3
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 3
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- 229910001887 tin oxide Inorganic materials 0.000 description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 description 2
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- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
Classifications
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- 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
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/32—Esters thereof
- C07F9/3258—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/3264—Esters with hydroxyalkyl compounds
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- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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- Life Sciences & Earth Sciences (AREA)
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- Molecular Biology (AREA)
- Fireproofing Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
技术领域
本发明涉及阻燃剂技术领域,具体涉及一种含磷阻燃剂和阻燃高分子材料。
背景技术
聚丙烯酸类树脂由于具有强度高、透光性好、耐候性和尺寸稳定性优良等特点,在建筑材料、光学纤维和光学透镜等领域中应用广泛。但聚丙烯酸酯遇火易燃,通常需要添加阻燃剂来改善其使用性能。尤其是随着法律法规的日益严苛,传统的含卤阻燃剂,由于燃烧时容易产生具有毒性,金属腐蚀性的气体,正逐渐被含磷阻燃剂所替代。丙烯酸树酯的无卤阻燃改性通常有两类方法:一是加入无卤添加型阻燃剂,如多聚磷酸酯,聚磷酸铵等;但这类阻燃剂往往与聚丙烯酸酯相容性不佳,且这类阻燃剂大多为粉体,加入后存在析出,表面白化,吸潮,阻燃效率降低等问题;另一类为加入无卤反应型阻燃剂,即通过反应性的单体与丙烯酸酯单体进行共聚,将磷等阻燃元素嵌入到聚丙烯酸酯分子链中,从而起到阻燃的作用。这类添加方式可以最大限度保留原丙烯酸树脂的机械性能,电气性能,光学性能,具有广阔的应用前景。
专利CN 106574020A中公开了一种含磷阻燃剂单体,其具有如式(A)的分子结构:
其中,R1为甲基或者氢,R2为C1-C4的亚烷基,R3,R4为氢或者C1-C10的烷基。将该阻燃剂单体与甲基丙烯酸酯,丙烯酸等进行共聚,可制得阻燃丙烯酸树脂,控制该阻燃剂单体的添加量,可以制得具有较好的阻燃性能及较高的玻璃化转变温度的聚丙烯酸树脂。
专利CN 110121501A中公开了一种新型的反应型阻燃剂单体,该单体具有如式(B)的结构:
式(B)中,R1,R2为芳基,R3,R4为氢或者烷基。该专利中同时公开了该阻燃剂的合成路线。通过二芳基氧化磷与醛或者酮进行加成反应,制得二芳基羟甲基磷酸酯,然后继续与丙烯酸单体进行反应后,得到式(B)含磷丙烯酸单体。该单体与丙烯酸酯,苯乙烯或者丙烯腈进行共聚,制备含磷阻燃共聚物。制备式(B)阻燃剂要用到醛或者酮做原料,产品中会有醛或者酮的残留,进而影响其在涂料、纺织等品质要求比较高的领域的应用。
专利CN 107603510A中公开了一种含磷的丙烯酸单体,其具有式(C)的化学结构:
将含有该单体的含磷阻燃剂与EVA树脂,交联助剂,硅烷偶联剂等一起共混挤出,可制得阻燃EVA薄膜。
目前已报道的反应型含磷阻燃剂单体,大多采用含有P-H键的磷酸酯(亚磷酸酯)先与醛,酮进行反应,然后再与丙烯酸类单体进行酯化反应后制得。制备过程复杂,产品中大多残留醛,酮等小分子结构,影响了该类产品在涂料,纺织等领域中的推广使用;其次,这类阻燃剂,起始原料多为磷酸酯(亚磷酸酯),分子中多含有P-O-C基团,热稳定性较差;在水性条件下使用,由于P-O-C结构的水解,该类丙烯酸酯制品会产生吸潮,表面白化,阻燃效率下降等问题,给后期的应用带来困扰。
发明内容
针对上述技术问题,本发明提供了一种含磷阻燃剂,可作为反应型阻燃剂,结构中仅含一个P-O-C键,与传统的磷酸酯类阻燃剂(结构中有三个P-O-C键)相比,不易吸潮、稳定性好,制备过程也无需醛、酮等原料,应用更广泛。
一种含磷阻燃剂,分子结构如下式(I)所示:
式(I)中,R1、R2分别独立选自C1-C4的烷基,R3选自氢或者甲基,R4选自氢或者甲基,n为1-20的整数。
本发明还提供了一种所述的含磷阻燃剂的制备方法,包括:
(A-1)二烷基次膦酸与环氧乙烷或环氧丙烷反应制得二烷基次膦酸羟基酯;所述反应在0.1-0.5MPa压力下进行,反应温度为50-90℃,反应时间为1-4h;
(A-2)所得二烷基次膦酸羟基酯与丙烯酸单体或甲基丙烯酸单体在催化剂1作用下于70-120℃、常压进行反应,制得式(I)所示的含磷阻燃剂;
所述催化剂1选自碳酸钾,碳酸钠,碳酸氢钠,碳酸氢钾,三甲胺,三乙胺,三丁胺,苄基二甲基胺,吡啶,硫酸(包括稀硫酸、浓硫酸、发烟硫酸等),甲基苯磺酸,甲基磺酸,甲醇钠,乙醇钠,氧化锂,乙酰丙酮化锂,碳酸铯,氧化钙,氧化镁,氢氧化镁,碳酸钙,氧化铝,偏铝酸钠,氧化锡,氧化亚锡,氯化亚锡,二丁基氧化锡,二月桂酸二丁基锡,二氯二丁基锡,三丁基乙酸锡,三丁基氯化锡,三乙基氯化锡,三甲基氯化锡,二氧化钛,钛酸四丁酯,钛酸四异丁酯,钛酸四异丙酯,氧化锆,锆酸四甲酯中的一种。
上述二烷基次膦酸羟基酯具有式(II)所示的分子结构:
式(II)中,R1、R2分别独立的选自C1-C4的烷基,R3选自氢或者甲基,n为1-20的整数。
步骤(A-1)反应结束,脱去过量的环氧乙烷或环氧丙烷,得到二烷基次膦酸羟基酯。
步骤(A-1)中,所用的二烷基次膦酸可由次磷酸钠与C2-C4的烯烃为原料,通过加成反应,先制备得到二烷基次磷酸钠,然后二烷基次磷酸钠与相应的酸,如硫酸,盐酸等反应后得到。
步骤(A-2)中,所述丙烯酸单体优选自丙烯酸,丙烯酰卤,丙烯酸甲酯,丙烯酸乙酯,丙烯酸丙酯,丙烯酸丁酯中的至少一种,进一步优选为丙烯酸,丙烯酰氯,丙烯酸甲酯中的至少一种;
所述甲基丙烯酸单体优选自甲基丙烯酸,甲基丙烯酰卤,甲基丙烯酸甲酯,甲基丙烯酸乙酯,甲基丙烯酸丙酯,甲基丙烯酸丁酯中的至少一种,进一步优选为甲基丙烯酸,甲基丙烯酰氯,甲基丙烯酸甲酯中的至少一种。
在一优选例中,催化剂1为碳酸钾,碳酸钠,碳酸氢钠,三甲胺,三乙胺,三丁胺,苄基二甲基胺,吡啶,浓硫酸,甲基苯磺酸,甲基磺酸,甲醇钠,乙醇钠,乙酰丙酮化锂,氧化镁,氢氧化镁,氧化亚锡,氯化亚锡,二丁基氧化锡,二月桂酸二丁基锡,二氯二丁基锡,三丁基乙酸锡,三丁基氯化锡,三乙基氯化锡,三甲基氯化锡,二氧化钛,钛酸四丁酯,钛酸四异丁酯,钛酸四异丙酯中的一种。
当所用丙烯酸单体为丙烯酸、丙烯酰卤,甲基丙烯酸单体为甲基丙烯酸,甲基丙烯酰卤时,催化剂1优选自碳酸钾,碳酸钠,碳酸氢钠,碳酸氢钾,三甲胺,三乙胺,三丁胺,苄基二甲基胺,吡啶中的一种。
当所用丙烯酸单体为丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸丁酯,甲基丙烯酸单体为甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丙酯、甲基丙烯酸丁酯时,所用催化剂1优选自硫酸(包括稀硫酸、浓硫酸、发烟硫酸等),甲基苯磺酸,甲基磺酸,甲醇钠,乙醇钠,氧化锂,乙酰丙酮化锂,碳酸钾,碳酸钠,碳酸氢钠,碳酸氢钾,碳酸铯,氧化钙,氧化镁,氢氧化镁,碳酸钙,氧化铝,偏铝酸钠,氧化锡,氧化亚锡,氯化亚锡,二丁基氧化锡,二月桂酸二丁基锡,二氯二丁基锡,三丁基乙酸锡,三丁基氯化锡,三乙基氯化锡,三甲基氯化锡,二氧化钛,钛酸四丁酯,钛酸四异丁酯,钛酸四异丙酯,氧化锆,锆酸四甲酯中的一种。
本发明还提供了一种所述的含磷阻燃剂的制备方法,包括:
(B-1)二烷基次膦酰卤与乙二醇或二乙二醇或聚合度为1-20的聚乙二醇或1,2-丙二醇或二(1,2-丙二醇)或聚合度为1-20的聚(1,2-丙二醇)在催化剂2作用下进行反应,制得二烷基次膦酸羟基酯;
所述催化剂2选自碳酸钾,碳酸钠,碳酸氢钠,碳酸氢钾,三甲胺,三乙胺,三丁胺,苄基二甲基胺,吡啶中的一种;
(B-2)所得二烷基次膦酸羟基酯与丙烯酸单体或甲基丙烯酸单体在催化剂1作用下于70-120℃、常压进行反应,制得式(I)所示的含磷阻燃剂;
所述催化剂1选自碳酸钾,碳酸钠,碳酸氢钠,碳酸氢钾,三甲胺,三乙胺,三丁胺,苄基二甲基胺,吡啶,硫酸(包括稀硫酸、浓硫酸、发烟硫酸等),甲基苯磺酸,甲基磺酸,甲醇钠,乙醇钠,氧化锂,乙酰丙酮化锂,碳酸铯,氧化钙,氧化镁,氢氧化镁,碳酸钙,氧化铝,偏铝酸钠,氧化锡,氧化亚锡,氯化亚锡,二丁基氧化锡,二月桂酸二丁基锡,二氯二丁基锡,三丁基乙酸锡,三丁基氯化锡,三乙基氯化锡,三甲基氯化锡,二氧化钛,钛酸四丁酯,钛酸四异丁酯,钛酸四异丙酯,氧化锆,锆酸四甲酯中的一种。
步骤(B-1)中,所述二烷基次膦酰卤优选为二烷基次膦酰氯或二烷基次膦酰溴,进一步优选为二烷基次膦酰氯。
所述二烷基次膦酰卤可由次磷酸钠与C2-C4的烯烃为原料,先制备得到二烷基次磷酸钠,然后二烷基次磷酸钠与相应的酸,如硫酸,盐酸等酸性物质反应后二烷基次膦酸;二烷基次膦酸再与卤化试剂于常压、80-120℃反应后制备得到。
此处所用的卤化试剂包括氯化亚砜,三氯化磷,五氯化磷,三溴化磷,五溴化磷,三碘化磷,五碘化磷等;优选为氯化亚砜。
步骤(B-1)得到的二烷基次膦酸羟基酯分子结构如上式(II)所示。
步骤(B-2)的方法、丙烯酸单体、甲基丙烯酸单体和催化剂等的选择可与上述步骤(A-2)相同。
本发明还提供了一种所述的含磷阻燃剂的制备方法,包括:二烷基次膦酰卤与丙烯酸羟基酯在催化剂3作用下于80-110℃、常压进行反应,制得式(I)所示的含磷阻燃剂;
所述催化剂3选自碳酸钾,碳酸钠,碳酸氢钠,碳酸氢钾,三甲胺,三乙胺,三丁胺,苄基二甲基胺,吡啶中的一种;
所述丙烯酸羟基酯具有式(III)所示的结构:
式(III)中,R3选自氢或者甲基,R4选自氢或者甲基,n为1-20的整数。
上述制备方法中,所述二烷基次膦酰卤为二烷基次膦酰氯或二烷基次膦酰溴,优选为二烷基次膦酰氯。二烷基次膦酰卤可采用上文所述制备方法制备得到。
所述丙烯酸羟基酯可采用市售产品。
本发明还提供了一种阻燃高分子材料,其结构单元中含有式(IV)所示结构作为其构成成分:
式(IV)中,R1、R2分别独立选自C1-C4的烷基,R3选自氢或者甲基,R4选自氢或者甲基,n为1-20的整数,m为正整数。
本发明的阻燃高分子材料,可以通过使用本发明式(I)所示的化合物,与其它聚合性单体通过自由基共聚方式得到。聚合可以通过在引发剂作用下,在溶剂中进行。
作为优选,所述的阻燃高分子材料为上述式(I)所示化合物与聚合性单体的共聚物。
所述聚合性单体包括:苯乙烯、2-甲氧基苯乙烯、3-甲氧基苯乙烯、4-甲氧基苯乙烯、2-叔丁氧基苯乙烯;丙烯酸、丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸丙酯、甲基丙烯酸丙酯、丙烯酸正丁酯、甲基丙烯酸正丁酯、丙烯酸叔丁酯、甲基丙烯酸叔丁酯、丙烯酸己酯、甲基丙烯酸己酯、丙烯酸环己酯、甲基丙烯酸环己酯、丙烯酸2-乙基己酯、甲基丙烯酸2-乙基己酯、丙烯酸壬酯、甲基丙烯酸壬酯、丙烯酸苄酯、甲基丙烯酸苄酯、丙烯酸月桂酯、甲基丙烯酸月桂酯、丙烯酸正辛酯、甲基丙烯酸正辛酯、丙烯酸2-甲氧基乙酯、甲基丙烯酸2-甲氧基乙酯、丙烯酸2-羟乙酯、甲基丙烯酸2-羟乙酯、丙烯酸2-羟丙酯、甲基丙烯酸2-羟丙酯、丙烯酸缩水甘油酯、甲基丙烯酸缩水甘油酯,丙烯酰胺,N-羟甲基丙烯酰胺,丙烯腈。
所述聚合性单体优选为丙烯酸、甲基丙烯酸、丙烯酸酯、甲基丙烯酸酯、苯乙烯、丙烯酰胺、N-羟甲基丙烯酰胺、丙烯腈中的至少一种
上述的引发剂,可以使用偶氮类聚合物引发剂或者有机过氧化物类引发剂。如:偶氮二异丁基腈(AIBN)、偶氮二异庚腈(ADVN)、偶氮二异戊腈(AMBN);过氧化二苯甲酰(BPO)、二叔丁基过氧化氢(TBHP)、过氧化氢异丙苯。
进一步优选,式(I)所示化合物在所述共聚物中的质量百分比为1%-60%。式(I)所示化合物的含量增加时,聚合物的阻燃性能有提升的倾向,式(I)所示化合物的含量减少时,该聚合物的玻璃化转变温度有上升的倾向。为保证所得聚合物适宜的阻燃性能及最佳的使用效果,更进一步优选,式(I)所示化合物在所述共聚物中的质量百分比为3%-40%。
本发明与现有技术相比,主要优点包括:
1、本发明提供一种反应型含磷阻燃剂,其分子结构中含有活性的双键,可以用于制备具有永久阻燃效果的高分子材料。
2、本发明提供所述反应型含磷阻燃剂单体的制备方法,可以通过三种不同的方法制备得到,制备过程方便。
3、本发明提供一种阻燃高分子材料。其结构中含有式(I)的阻燃剂单体。含有该单体的阻燃高分子材料,具有优异的阻燃性能,较低的吸收率,不吸潮,其耐酸、碱性能好,存储稳定性好,制品无色透明,具有较好的光学性能。
具体实施方式
下面结合具体实施例,进一步阐述本发明。应理解,这些实施例仅用于说明本发明而不用于限制本发明的范围。下列实施例中未注明具体条件的操作方法,通常按照常规条件,或按照制造厂商所建议的条件。
下面实施例中所使用的二乙基次膦酸通过自制得到。具体实施过程为:
将10mol一水合次磷酸钠,2300g水加入到压力釜中,抽真空至釜内压力400Pa以下,并用氮气置换三次。再次抽真空至釜内压力400Pa以下,通入乙烯并控制压力为0.5MPa,升温至100℃,补加乙烯,并控制反应压力为1.5MPa,通过柱塞泵打入二叔丁基过氧化物,至反应压力不再下降,继续保温1h,冷却放空,得到二乙基次磷酸钠水溶液3350g,加入50%硫酸溶液,调节pH至1-2,得到二乙基次膦酸的溶液。
将上述二乙基次磷酸水溶液在120℃继续蒸馏,脱去水分。继续升温至180-190℃,收集180-190℃/1.0KPa时的馏分,即得二乙基次膦酸纯品。
二乙基次膦酸酰氯的制备:
将上述490.2g二乙基次膦酸,升温至75℃,缓慢滴加氯化亚砜500.8g,约两小时滴加结束,升温至80℃保温反应1小时,回流,收集生成的氯化氢气体。减压蒸馏,收集110-113℃/1.0KPa的馏分,即得高纯度的二乙基次膦酸酰氯。
如无特别说明,原料均通过商业途径购买,不经特殊处理直接使用。
材料阻燃性能的测试方法:采用UL 94测试方法。将含磷丙烯酸乳液倒入模具中缓慢烘干,并将得到树脂片裁切成130mm*13mm*1.6mm的试验片,每组样品制备5根样条,评价阻燃性能。
材料吸水性能的测试方法:取上述样条,置于80℃,80%的恒温恒湿箱中,储存168h后,测试增重率。
增重率计算公式:
其中W2为恒温恒湿测试后样条重量,W1为恒温恒湿测试前样条重量。
实施例1
含磷丙烯酸酯的制备
a.氮气保护下,向装有电动搅拌器、温度计和回流冷凝管的500mL四口烧瓶中加入300.1g二乙基次膦酸,升温至45℃,缓慢通入110.2g环氧乙烷,保温50℃反应4h。得二乙基次膦酸羟乙酯的粗品。
b.将上述得到的二乙基次膦酸羟乙酯于旋转蒸发仪中旋蒸,脱去多余的环氧乙烷。得到浅黄色液体,404.2g。气相色谱显示,环氧乙烷残留量小于0.3%。
c.氮气保护下,向装有电动搅拌机,温度计,回流冷凝器的2000L烧瓶中,加入步骤b中得到的二乙基次膦酸羟乙酯403.1g,三乙胺248.7g,升温至70℃。缓慢滴加225.4g丙烯酰氯,约两小时滴完。降温,过滤除去生成的三乙胺盐酸盐固体。得到含磷丙烯酸酯粗品。将该粗品中加入10.2g对苯二酚阻聚剂,进一步精馏,收集170-173℃/2-5mmHg馏分,得到含磷丙烯酸酯成品。
实施例2
含磷丙烯酸酯的制备
a.氮气保护下,向装有电动搅拌器、冷却装置的1000mL高压釜中加入300.3g二乙基次膦酸,升温至80℃,缓慢通入145.2g环氧丙烷,保温90℃反应1h,反应压力0.17MPa。得二乙基次膦酸羟丙酯的粗品。
b.将上述得到的二乙基次膦酸羟丙酯于旋转蒸发仪中旋蒸,脱去多余的环氧丙烷。得到浅黄色液体,442.8g。
c.氮气保护下,向装有电动搅拌机,温度计,油水分离器的2000L烧瓶中,加入步骤b中得到的二乙基次膦酸羟丙酯439.5g,二月桂酸二丁基锡14.4g,升温至90℃。滴加250.7g甲基丙烯酸甲酯,约半小时滴完。持续保温反应3小时,收集生成的甲醇。降温,过滤。得到含磷丙烯酸酯粗品。将该粗品中加入14.4g对苯二酚阻聚剂,进一步精馏,收集191-194℃/2-5mmHg馏分,得到含磷丙烯酸酯成品。
实施例3
含磷丙烯酸酯的制备
a.氮气保护下,向装有电动搅拌器、冷凝及气体吸收装置的2000ml四口瓶中,加入320g二乙基次膦酰氯,203.1g三乙胺做催化剂,升温至100℃,缓慢滴入507.2g三(乙二醇),保温100℃反应3h,降温,过滤生成的固体。得到二乙基次膦酸羟基酯的粗品。
b.氮气保护下,向装有电动搅拌机,温度计,回流冷凝器的2000L烧瓶中,加入步骤a中得到的二乙基次膦酸羟基酯600.2g,三乙胺203.6g,升温至120℃。缓慢滴加180.9g丙烯酰氯,约1.5小时滴完。降温,过滤除去生成的三乙胺盐酸盐固体。得到含磷丙烯酸酯粗品。加入800ml水洗涤,分出水层,蒸馏脱水,干燥,得到含磷丙烯酸酯成品。
实施例4
含磷丙烯酸酯的制备
a.氮气保护下,向装有电动搅拌器、冷凝及气体吸收装置的2000ml四口瓶中,加入320g二乙基次膦酰氯,204.1g三乙胺做催化剂,升温至70℃,缓慢滴入180.2g1,2-丙二醇,保温90℃反应3h,降温,过滤生成的三乙胺盐酸盐。得二乙基次膦酸羟丙酯的粗品。
b.氮气保护下,向装有电动搅拌机,温度计,回流冷凝器的2000L烧瓶中,加入步骤b中得到的二乙基次膦酸羟乙酯粗品292.3g,三乙胺204.1g,升温至100℃。缓慢滴加183.5g丙烯酰氯,约3小时滴完。降温,过滤除去生成的固体。得到含磷丙烯酸酯粗品。将该粗品中加入8.2g对苯二酚阻聚剂,粗品进一步精馏,收集189-192℃/2-5mmHg馏分,得到含磷丙烯酸酯成品。
实施例5
含磷丙烯酸酯的制备
a.氮气保护下,向装有电动搅拌器、冷凝装置的2000ml四口瓶中,加入320g二乙基次膦酰氯,204.3g三乙胺做催化剂,升温至90℃,缓慢滴入231.8g丙烯酸羟乙酯,保温110℃反应3h,降温,过滤生成的三乙胺盐酸盐。得二乙基次膦酸羟乙酯的粗品。
b.将上述粗品进一步精馏,收集171-174℃/2-5mmHg馏分,得到含磷丙烯酸酯成品。
实施例6
含磷丙烯酸酯的制备
a.氮气保护下,向装有电动搅拌器、冷凝装置的2000ml四口瓶中,加入320g二乙基次膦酰氯,201.7g三乙胺做催化剂,升温至80℃,缓慢滴入262g丙烯酸羟丙酯,保温80℃反应4h,降温,过滤生成的三乙胺盐酸盐。得二乙基次膦酸羟丙酯的粗品。
b.将上述粗品中加入10.3g对苯二酚进一步精馏,收集191-194℃/2-5mmHg馏分,得到含磷丙烯酸酯成品。
实施例7
聚合物的制备
称量实验各种单体1250g(配方见表1),乳化剂(组成:壬基酚聚氧乙烯醚硫酸铵盐(C0436)9.0g,壬基酚聚氧乙烯醚(NP-10)15g),加入到650g水中,搅拌,分散得乳液A;称量引发剂过硫酸铵10.0g,溶于250g水中,得溶液B。将A和B两种溶液于室温下高速分散,制得丙烯酸酯的预乳液。备用。
在装有搅拌器、冷凝管、氮气导入装置和滴液漏斗的5000mL四口烧瓶中加入900.0水、12.0g乳化剂(组成:壬基酚聚氧乙烯醚(NP-10)4.0g,烯丙基羟丙基磺酸钠(C0PS-1)8.0g),高速搅拌乳化15分钟后,升温至80℃,加入上述预乳液360g,10%的过硫酸钠溶液40g,继续升温到85℃进行反应,保温两小时后,继续滴加剩余的预乳液,约2h滴完,然后继续升温至95℃并保温1h。继续加入10%二叔丁基过氧化氢(DTBP)水溶液20g,保温1小时后加入2%吊白块水溶液40g保温1h,用5%氨水调节pH至9.0,得到成品丙烯酸乳液。
将含磷丙烯酸乳液倒入模具中缓慢烘干,并将得到树脂片裁切成130mm*13mm*1.6mm的试验片,评价阻燃性能及吸水性。
改变含磷阻燃剂单体的种类及配方组成,通过与实施例7相同的合成方法,得到不同的样条,进行测试。作为对比,选取常见的添加型阻燃剂,磷酸三乙酯(TEP),双酚A-双(二苯基磷酸酯)(BDP)作为对比。具体配方组成及测试结果见表1。
表1
此外应理解,在阅读了本发明的上述描述内容之后,本领域技术人员可以对本发明作各种改动或修改,这些等价形式同样落于本申请所附权利要求书所限定的范围。
Claims (1)
1.一种阻燃高分子材料的制备方法,其特征在于,称量实验各种单体1250g和乳化剂加入到650g水中,搅拌,分散得乳液A;称量引发剂过硫酸铵10.0g,溶于250g水中,得溶液B;将A和B两种溶液于室温下高速分散,制得丙烯酸酯的预乳液;备用;实验各种单体具体为丙烯酸丁酯500g,甲基丙烯酸甲酯100g,丙烯酸甲酯150g,苯乙烯150g,甲基丙烯酸30g,N-羟甲基丙烯酰胺20g,含磷阻燃剂300g;乳化剂组成:壬基酚聚氧乙烯醚硫酸铵盐C0436 9.0g,壬基酚聚氧乙烯醚NP-10 15g;
在装有搅拌器、冷凝管、氮气导入装置和滴液漏斗的 5000 mL 四口烧瓶中加入900.0g水、12.0g乳化剂,乳化剂组成:壬基酚聚氧乙烯醚NP-10 4.0g、烯丙基羟丙基磺酸钠C0PS-18.0g,高速搅拌乳化15分钟后,升温至 80℃,加入上述预乳液360g,10%的过硫酸钠溶液40g,继续升温到85℃进行反应,保温两小时后,继续滴加剩余的预乳液,2 h滴完,然后继续升温至95℃并保温 1 h,继续加入10%二叔丁基过氧化氢DTBP水溶液20g,保温1小时后加入2%吊白块水溶液40g保温1h,用5%氨水调节pH至9.0,得到成品丙烯酸乳液;
将含磷丙烯酸乳液倒入模具中缓慢烘干得到所述阻燃高分子材料;
所述含磷阻燃剂的制备过程:
a.氮气保护下,向装有电动搅拌器、冷却装置的1000mL高压釜中加入300.3g二乙基次膦酸,升温至80℃,缓慢通入145.2g环氧丙烷,保温90℃反应1h,反应压力0.17MPa;得二乙基次膦酸羟丙酯的粗品;
b.将上述得到的二乙基次膦酸羟丙酯于旋转蒸发仪中旋蒸,脱去多余的环氧丙烷;得到浅黄色液体,442.8g;
c.氮气保护下,向装有电动搅拌机,温度计,油水分离器的2000L烧瓶中,加入步骤b中得到的二乙基次膦酸羟丙酯439.5g,二月桂酸二丁基锡14.4g,升温至90℃;滴加250.7g甲基丙烯酸甲酯,半小时滴完;持续保温反应3小时,收集生成的甲醇;降温,过滤;得到含磷丙烯酸酯粗品;将该粗品中加入14.4g对苯二酚阻聚剂,进一步精馏,收集191-194℃/2-5mmHg馏分,得到含磷丙烯酸酯成品,即所述含磷阻燃剂。
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