CN115403829B - Organic phosphaphenanthrene derivative with fatty chain structure, preparation method and application thereof - Google Patents
Organic phosphaphenanthrene derivative with fatty chain structure, preparation method and application thereof Download PDFInfo
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- CN115403829B CN115403829B CN202110589936.2A CN202110589936A CN115403829B CN 115403829 B CN115403829 B CN 115403829B CN 202110589936 A CN202110589936 A CN 202110589936A CN 115403829 B CN115403829 B CN 115403829B
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- Prior art keywords
- derivative
- organic
- fatty
- phosphaphenanthrene
- chain structure
- Prior art date
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Links
- LJUXFZKADKLISH-UHFFFAOYSA-N benzo[f]phosphinoline Chemical class C1=CC=C2C3=CC=CC=C3C=CC2=P1 LJUXFZKADKLISH-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title abstract description 14
- -1 phosphaphenanthrene compound Chemical class 0.000 claims abstract description 64
- 150000002191 fatty alcohols Chemical class 0.000 claims abstract description 36
- 150000001263 acyl chlorides Chemical class 0.000 claims abstract description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims description 15
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 11
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 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 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 125000003277 amino group Chemical group 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 125000003700 epoxy group Chemical group 0.000 claims description 3
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims 1
- 125000001792 phenanthrenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 19
- 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 abstract description 14
- 239000003063 flame retardant Substances 0.000 abstract description 14
- 150000001735 carboxylic acids Chemical class 0.000 abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 54
- 238000012360 testing method Methods 0.000 description 53
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 48
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 45
- 239000000347 magnesium hydroxide Substances 0.000 description 44
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 44
- 239000000243 solution Substances 0.000 description 44
- 239000005038 ethylene vinyl acetate Substances 0.000 description 39
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 38
- 238000001514 detection method Methods 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 20
- 239000002131 composite material Substances 0.000 description 19
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 15
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 13
- 150000002987 phenanthrenes Chemical class 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- REZQBEBOWJAQKS-UHFFFAOYSA-N triacontan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCO REZQBEBOWJAQKS-UHFFFAOYSA-N 0.000 description 12
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 10
- 239000000155 melt Substances 0.000 description 9
- NQAYJDGCTANZCH-UHFFFAOYSA-N octadecan-2-yl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCC(C)OC(=O)C=C NQAYJDGCTANZCH-UHFFFAOYSA-N 0.000 description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical group CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000012752 auxiliary agent Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 230000002195 synergetic effect Effects 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 5
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 5
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 3
- YIIMEMSDCNDGTB-UHFFFAOYSA-N Dimethylcarbamoyl chloride Chemical compound CN(C)C(Cl)=O YIIMEMSDCNDGTB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 239000004262 Ethyl gallate Substances 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000012024 dehydrating agents Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 230000002087 whitening effect Effects 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- QWEXUGUTYLTMID-UHFFFAOYSA-N C1=CC=CC=2C3=CC=CC=C3C=CC12.[P] Chemical class C1=CC=CC=2C3=CC=CC=C3C=CC12.[P] QWEXUGUTYLTMID-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- PFKFTWBEEFSNDU-UHFFFAOYSA-N carbonyldiimidazole Chemical compound C1=CN=CN1C(=O)N1C=CN=C1 PFKFTWBEEFSNDU-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- DDJSWKLBKSLAAZ-UHFFFAOYSA-N cyclotetrasiloxane Chemical compound O1[SiH2]O[SiH2]O[SiH2]O[SiH2]1 DDJSWKLBKSLAAZ-UHFFFAOYSA-N 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- DWLVWMUCHSLGSU-UHFFFAOYSA-M n,n-dimethylcarbamate Chemical compound CN(C)C([O-])=O DWLVWMUCHSLGSU-UHFFFAOYSA-M 0.000 description 1
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- CUQOHAYJWVTKDE-UHFFFAOYSA-N potassium;butan-1-olate Chemical group [K+].CCCC[O-] CUQOHAYJWVTKDE-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical group [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
- BHTBHKFULNTCHQ-UHFFFAOYSA-H zinc;tin(4+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Sn+4] BHTBHKFULNTCHQ-UHFFFAOYSA-H 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
-
- 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 System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657172—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/222—Magnesia, i.e. magnesium oxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Abstract
The invention provides an organic phosphaphenanthrene derivative with a fatty chain structure, a preparation method and application thereof, wherein the organic phosphaphenanthrene compound with the fatty chain structure is obtained by reacting an organic phosphaphenanthrene compound with fatty alcohol ester compounds with fatty chains with 8-30 carbon atoms, the fatty alcohol ester compounds are obtained by reacting fatty alcohols with carboxylic acids, acyl chloride compounds and derivatives thereof, the fatty chains with 8-30 carbon atoms are positioned on the fatty alcohols, branched chains are arranged on the fatty chains, the number of carbon atoms on the branched chains is not more than 3, and the number of branched chains on the fatty chains is not more than 4; according to the scheme, the fatty chain with the carbon number of 8-30 is introduced into the organic phosphaphenanthrene derivative, so that the processability and flexibility of the organic phosphaphenanthrene derivative in a molten state are improved, and the organic phosphaphenanthrene derivative with the fatty chain structure is compounded into an EVA/MH system, so that the flame retardant property of the organic phosphaphenanthrene derivative is improved, and meanwhile, the processability of the material is improved.
Description
Technical Field
The invention belongs to the field of organic phosphorus halogen-free flame-retardant synergistic auxiliary agents, and particularly relates to an organic phosphorus phenanthrene derivative with a fatty chain structure, a preparation method and application thereof.
Background
Ethylene Vinyl Acetate (EVA)/Magnesium Hydroxide (MH) systems are commonly used in wire and cable materials for their excellent properties. In order to meet the flame-retardant requirement, a large amount of filling (MH) is needed in the EVA matrix, but the addition of MH can deteriorate the processability and flexibility of the material, and the practical application of the material is affected. It is therefore often necessary to add flame retardant synergists to the system. At present, a few inorganic component EVA/MH system synergistic auxiliary agents are commonly used in researches, such as zinc borate, zinc hydroxystannate, clay ore and the like, but the inorganic rigid structure of the inorganic component EVA/MH system synergistic auxiliary agents is difficult to positively promote the processability and flexibility of materials.
Research shows that the organic phosphaphenanthrene derivative has a synergistic effect with other flame-retardant structures, such as phosphazene, triazine, triazinetrione and cyclotetrasiloxane of the flame-retardant structures; commercial flame retardants or char formers aluminum alkyl phosphinate, melamine cyanurate, polyphenylene oxide, and the like; inorganic flame retardant materials such as montmorillonite, aluminum hydroxide, magnesium hydroxide and the like. And the high cost of the organic phosphaphenanthrene derivative is considered, so that the organic phosphaphenanthrene derivative is more suitable for being applied as a flame-retardant synergistic auxiliary agent.
The application number is: the Chinese patent of CN202010387923.2 discloses a nano metal hydroxide halogen-free flame retardant and a preparation method of a composite material thereof, wherein an organic phosphaphenanthrene group and MH are linked by silane, and the silane is introduced into EVA after preparing surface modified MH, so that the dispersibility of MH in EVA can be improved, the flame retardant property of the material is improved, and meanwhile, the processability and flexibility of the material can be improved. However, the DOPO needs a complex process flow to be grafted on the MH surface, so that the production cost is greatly improved, and the application of the organic phosphaphenanthrene derivative as a flame-retardant synergistic auxiliary agent to an EVA/MH system is more feasible. There is therefore an urgent need for an organophosphorous phenanthrene derivative having a higher melt index that is capable of being blended by melting in an EVA/MH system.
In addition, the molecular fluorescence property of the organic phosphaphenanthrene is also characterized and applied. The EVA/MH material is often required to be white, and because impurities exist in the system, the material is yellow to influence the use of the EVA/MH material, so that the brightness and the whitening effects are achieved in the system by adding the fluorescent whitening agent in the prior art, but the whitening agent cannot contribute to the thermal stability and the working performance of the system.
The present invention has been made in view of this.
Disclosure of Invention
The present invention has been made in view of the above-mentioned problems occurring in the prior art, and an object of the present invention is to provide an organophosphorous phenanthrene derivative having a fatty chain structure, which improves processability and flexibility of the organophosphorous phenanthrene derivative in a molten state by introducing a fatty chain structure into the organophosphorous phenanthrene derivative.
The invention also provides a preparation method of the organic phosphaphenanthrene derivative with the fatty chain structure, which uses carboxylic acids, acyl chloride compounds and derivatives thereof with at least two active groups to connect fatty alcohol with the organic phosphaphenanthrene, thereby realizing the introduction of fatty chains in the organic phosphaphenanthrene derivative.
The invention further provides an application of the organic phosphaphenanthrene derivative with the fatty chain structure as a synergist, and the organic phosphaphenanthrene derivative with the fatty chain structure is added, so that the flame retardant property of the material is improved, and meanwhile, the processing property of the material is also improved.
In order to achieve the above object, a first aspect of the present invention provides an organophosphorous phenanthrene derivative having a fatty chain structure, which is obtained by reacting an organophosphorous phenanthrene compound with a fatty alcohol ester compound having a fatty chain with 8 to 30 carbon atoms.
In the scheme, the number of carbon atoms in the fatty chain is a range which can obviously improve the melt index and is obtained by experimenters on the basis of a large number of experiments, and the organic phosphaphenanthrene derivative with the fatty chain structure in the range has higher melt index.
Further, the fatty alcohol ester compound is obtained by reacting fatty alcohol with carboxylic acid, acyl chloride compound and derivative thereof, wherein the carboxylic acid, the acyl chloride compound and derivative thereof have at least one-COOH group or-COCl group capable of reacting with-OH group on the fatty alcohol.
In the scheme, the fatty chain is introduced into the organic phosphaphenanthrene derivative through the reaction of-OH on fatty alcohol and-COOH or-COCl on carboxylic acid, acyl chloride compounds and derivatives thereof.
Further, the fatty chain has a branched chain, and the number of carbon atoms of the branched chain is not more than 3.
Further, the fatty chain has branches, and the number of branches on the fatty chain is not more than 4.
The scheme is that the experimenters obtain a parameter range on the basis of a large number of experiments, and as the number of branched chains and the length of the branched chains are increased, entanglement is easy to occur among the branched chains, so that the melt index of the organic phosphaphenanthrene derivative with a fatty chain structure is influenced, and the fluidity in a molten state is reduced; and also reduces the dispersibility of the organophosphazene derivative having a fatty chain structure.
Preferably, the fatty alcohol has no branching.
Further, the fatty alcohol ester is provided with at least one active group besides a-COOH group or a-COCl group, and the active group on the fatty alcohol ester reacts with the organic phosphaphenanthrene compound to obtain the organic phosphaphenanthrene derivative with a fatty chain structure.
Further, the reactive group includes at least an isocyanate group, an acetylene group, a vinyl group, a carboxyl group, an epoxy group, an amino group, or a halogen atom.
Further, the structural general formula of the organic phosphaphenanthrene compound is shown as a formula-I:
-a in formula-i is selected from any one of the following structures:
and (3) reacting the-A in the organic phosphaphenanthrene compound with the active group in the fatty alcohol ester to obtain the organic phosphaphenanthrene derivative with the fatty chain structure.
In a second aspect, the present invention provides a method for producing an organophosphorous phenanthrene derivative having a fatty chain structure, comprising the steps of:
s1, preparing fatty alcohol ester compounds;
s2, slowly adding the fatty alcohol ester compound into the organic phosphaphenanthrene compound solution mixed with the catalyst to prepare the organic phosphaphenanthrene derivative with the fatty chain structure.
In step S1, the fatty alcohol is dissolved in an organic solvent to form a solution, and then carboxylic acid or acyl chloride compounds and derivatives thereof are added, and the fatty alcohol ester compounds are obtained through stirring, filtering, extracting and drying.
Further, in the step S1, the molar ratio of the fatty alcohol, the organic solvent and the carboxylic acid or the acid chloride derivative is 1: (10-25): (1-1.3).
The scheme is specifically as follows:
dispersing and dissolving 1 mole part of fatty alcohol into 10-25 mole parts of organic solvent to form fatty alcohol solution;
adding 1.1-1.3 mol parts of triethylamine into the fatty alcohol solution;
adding 1.0-1.3 mol parts of acid or acyl chloride compounds and derivatives thereof into the fatty alcohol solution under the ice water bath condition, heating and stirring for reaction, and filtering to obtain a filtrate to obtain a crude fatty alcohol ester derivative product;
evaporating the crude product of the fatty alcohol ester derivative to dryness, adding 15 mole parts of organic solvent, adding saturated sodium bicarbonate aqueous solution for multiple extraction, taking the organic phase, drying over anhydrous magnesium sulfate, and evaporating the solvent under reduced pressure to obtain the pure fatty alcohol ester derivative product.
In the process, when an alkaline catalyst is used, the fatty alcohol solution reacts with carboxylic acids, acyl chloride compounds and derivatives thereof at normal temperature, wherein the alkaline catalyst is 4-dimethylaminopyridine;
when an acid catalyst is used, the temperature range of the reaction of the fatty alcohol solution and carboxylic acids, acyl chloride compounds and derivatives thereof is 75-120 ℃, and the acid catalyst is one or more of concentrated sulfuric acid, p-toluenesulfonic acid, phosphoric acid, boric acid and the like.
Further, the fatty alcohol solution reacts with carboxylic acids, acyl chloride compounds and derivatives thereof under the condition of dehydrating agents, wherein the dehydrating agents are N, N-dicyclohexylcarbodiimide or N, N-carbonyl diimidazole.
Further, in the step S1, when the acid chloride compound and the derivative thereof are used to react with the fatty alcohol, an acid-binding agent is further added to the fatty alcohol solution before the acid chloride compound and the derivative thereof are added to the fatty alcohol solution, and the molar ratio of the fatty alcohol to the acid-binding agent is 1: (1.1-1.3).
Preferably, the acid binding agent is triethylamine.
In the scheme, HCl is released when-COCl in acyl chloride compounds and derivatives thereof react with-OH in fatty alcohol, and the generated HCl is consumed through triethylamine, so that the PH of the system is kept stable; because the reaction is rapid, in order to enable the triethylamine to timely eliminate HCl generated by the reaction, the triethylamine is firstly added into the fatty alcohol solution, and then the acyl chloride compound and the derivative thereof are added.
Further, in the step S2, the fatty alcohol ester compound is slowly added into the organic phosphaphenanthrene compound solution mixed with the catalyst to prepare the organic phosphaphenanthrene derivative with the fatty chain structure.
The scheme is specifically as follows:
1.2-1.5 mol parts of organic phosphaphenanthrene compound is dissolved in 10-25 mol parts of organic solution to prepare organic phosphaphenanthrene solution;
dissolving fatty alcohol ester derivative in 10-25 mol parts of organic solution to obtain fatty alcohol ester derivative solution;
adding 0.1-0.025 mol portion of catalyst into the organic phosphaphenanthrene solution, then dripping fatty alcohol ester derivative solution into the organic phosphaphenanthrene solution, heating, stirring, reacting, rotary steaming, recrystallizing, and drying to obtain the organic phosphaphenanthrene derivative with a fatty chain structure.
Further, the dropping speed of the fatty alcohol ester derivative solution is controlled to finish dropping in 3-8 hours.
Further, nitrogen is always introduced into the system during the preparation of the organic phosphaphenanthrene solution and the preparation of the organic phosphaphenanthrene derivative with the fatty chain structure.
In the scheme, nitrogen is introduced into the reaction system, so that double-bond polymerization is effectively avoided, and the consistency of the chain structure of the organic phosphaphenanthrene derivative with the fat chain structure is improved.
The organic solvent in the above scheme is selected from one or more of benzene, toluene, xylene, chloroform, dichloromethane, dimethylformamide, dimethylacetamide, dioxane, acetone, tetrahydrofuran and acetonitrile;
the solvent in the recrystallization process is dimethyl sulfoxide;
the catalyst for the reaction of the organic phosphaphenanthrene solution and the fatty alcohol ester derivative solution is one or more of pyridine, sodium hydroxide, potassium hydroxide, tertiary potassium butoxide, sodium amide, quaternary ammonium base, triethylamine, trimethylamine, quinoline, picoline, dimethylaniline, sodium methoxide and sodium ethoxide.
In a third aspect, the present invention provides the use of an organophosphorous phenanthrene derivative having a fatty chain structure as a synergist.
The beneficial effects of the invention are as follows: by introducing a fatty chain into the organic phosphaphenanthrene derivative, the organic phosphaphenanthrene derivative with a fatty chain structure can directly add DOPO into an EVA/MH system in a melt blending mode, so that the flame retardant property and the dispersibility are improved, and meanwhile, the processability and the whiteness are improved; the number of carbon atoms in the linear structure of the fatty alcohol is 8-30, the range is a range which can be obtained by technicians on the basis of a large number of experiments and can obviously improve the melt index, and the melt index of the organic phosphaphenanthrene derivative with the fatty chain structure in the range is higher, and the melt fluidity is better; the number of branched chains in the fatty alcohol is not more than 4, the number of carbon atoms in each branched chain is not more than 3, and by limiting the number and the length of the branched chains in the fatty alcohol, the melt index is improved, the influence on the compatibility between the organic phosphaphenanthrene derivative with a fatty chain structure and an EVA// MH system is avoided, and the working performance of the organic phosphaphenanthrene derivative with the fatty chain structure is improved; when the fatty alcohol ester compound and the organic phosphaphenanthrene compound react, nitrogen is always introduced into the reaction system, double bond polymerization is avoided, and the structural consistency of the product is improved.
Drawings
FIG. 1 is an SEM photograph of a mixture of first organophosphorous phenanthrene derivatives having a fatty chain structure and an EVA/MH system according to the present invention.
FIG. 2 is an SEM photograph of a mixture of the second organophosphorous phenanthrene derivative having a fatty chain structure according to the present invention and an EVA/MH system.
FIG. 3 is an SEM photograph of the EVA/MH system described in comparative example one.
FIG. 4 is an SEM photograph of a mixture of an organophosphorous phenanthrene compound and an EVA/MH system as described in comparative example II.
FIG. 5 is an NMR spectrum of a first organic phosphaphenanthrene derivative having a fatty chain structure according to the present invention.
FIG. 6 is a graph showing the results of the fluorescence performance of DOPO derivatives using a fluorescence spectrometer in experimental example four.
Detailed Description
Exemplary embodiments of the present invention will be described in more detail below with reference to the accompanying drawings, and it will be understood by those skilled in the art that the following embodiments are only for explaining the technical principles of the present invention and are not intended to limit the scope of the present invention.
The invention provides an organic phosphaphenanthrene derivative with a fatty chain structure, which is obtained by reacting an organic phosphaphenanthrene compound with a fatty alcohol ester compound, wherein the fatty alcohol ester compound has a fatty chain with 8-30 carbon atoms.
Wherein the active group comprises at least an isocyanate group, an acetylene group, a vinyl group, a carboxyl group, an epoxy group, an amino group or a halogen atom;
the structural general formula of the organic phosphaphenanthrene compound is shown as the formula-I:
-A in the general structural formula is selected from any one of the following structures:
and (3) reacting the-A in the organic phosphaphenanthrene compound with the active group in the fatty alcohol ester to obtain the organic phosphaphenanthrene derivative with the fatty chain structure.
Example 1
As an embodiment of the present invention, this embodiment provides an organic phosphaphenanthrene derivative organic phosphaphenanthrene compound having a fatty chain structure, which has the structural formula:
in this example, the fatty alcohol ester is obtained by reacting acrylic acid with stearyl alcohol, and the-COOH group on acrylic acid and the-OH group on stearyl alcohol are esterified to obtain 2-stearyl acrylate.
Further, the preparation method of the 2-octadecyl acrylate specifically comprises the following steps:
1 mole part of stearyl alcohol is dispersed and dissolved in 10 to 25 mole parts of toluene to form a stearyl alcohol solution.
1.1 to 1.3 mole parts of triethylamine is added into the fatty alcohol solution.
Adding 1.0-1.3 mole parts of acrylic acid into an octadecyl alcohol solution under the ice water bath condition, adding catalyst concentrated sulfuric acid and a dehydrating agent N, N-dicyclohexylcarbodiimide, heating to 75-120 ℃, reacting under the stirring condition, filtering, and obtaining a filtrate to obtain a crude product of the 2-octadecyl acrylate.
Or alternatively, the basic catalyst 4-dimethylaminopyridine is used as the catalyst for the esterification reaction,
adding 1.0-1.3 mole parts of acrylic acid into an octadecyl alcohol solution under the ice water bath condition, adding a catalyst of 4-dimethylaminopyridine and a dehydrating agent of N, N-dicyclohexylcarbodiimide, heating to a normal temperature state, reacting under the stirring condition, filtering, and obtaining a filtrate to obtain a crude product of the 2-octadecyl acrylate.
Evaporating the crude product of the 2-octadecyl acrylate to dryness, adding 15 mol parts of toluene solvent, adding saturated sodium bicarbonate aqueous solution for multiple extraction, taking an organic phase, drying over anhydrous magnesium sulfate, and evaporating the solvent under reduced pressure to obtain pure 2-octadecyl acrylate.
Further, octadecyl 2-acrylate is added into the organic phosphaphenanthrene compound solution mixed with the catalyst in a dropwise manner to prepare the organic phosphaphenanthrene derivative with the fatty chain structure.
The preparation method of the organic phosphaphenanthrene derivative with the fatty chain structure in the scheme specifically comprises the following steps:
1.2 to 1.5 mole parts of organic phosphaphenanthrene compound is dissolved in 10 to 25 mole parts of toluene to prepare organic phosphaphenanthrene solution;
2-octadecyl acrylate is dissolved in 10 to 25 mole parts of toluene to obtain 2-octadecyl acrylate solution;
adding 0.1-0.025 mole part of catalyst triethylamine into the organic phosphaphenanthrene solution, then dripping 2-octadecyl acrylate solution into the organic phosphaphenanthrene solution, heating and stirring for reaction, steaming, recrystallizing and drying to obtain the organic phosphaphenanthrene derivative with the fatty chain structure.
In the above reaction, the double bond on the 2-octadecyl acrylate reacts with-H on the P-H bond on the organic phosphaphenanthrene to obtain the organic phosphaphenanthrene derivative with a fatty chain structure.
Further, the dropping speed of the octadecyl 2-acrylate solution was controlled so that the dropping was completed within 3 to 8 hours.
Further, nitrogen is always introduced into the system in the processes of preparing the organic phosphaphenanthrene solution and preparing the organic phosphaphenanthrene derivative with the fatty chain structure, and double-bond polymerization is effectively avoided by introducing nitrogen into the reaction system, so that the consistency of the chain structure is improved.
It can be seen from FIG. 5 that the organic phosphaphenanthrene derivatives having a fatty chain structure prepared using the above method have a desired structure, in which-COOH on acrylic acid and-OH on stearyl alcohol react, and a double bond on acrylic acid and P-H bond on the organic phosphaphenanthrene derivatives react. In the scheme, the fatty chain of the organic phosphaphenanthrene derivative with the fatty chain structure has 18 carbon atoms, so that the melt index of the organic phosphaphenanthrene derivative with the fatty chain structure can be better improved, and the organic phosphaphenanthrene derivative with the fatty chain structure has better fluidity and compatibility when being used as a flame retardant auxiliary agent to be mixed with an EVA/MH system because the fatty chain does not have a branched chain.
Example two
As another embodiment of the present invention, this embodiment provides an organophosphorous phenanthrene derivative having a fatty chain structure, wherein the organophosphorous phenanthrene compound has the structural formula:
in this example, the fatty alcohol ester was obtained by reacting acryloyl chloride with n-octanol, and the-COCl group on the acryloyl chloride was reacted with the-OH group on the n-octanol to obtain n-octyl acrylate.
The preparation method of the n-octyl acrylate is the same as that described in the first embodiment, except that the acid-binding agent triethylamine is added to the n-octanol solution before the acryloyl chloride is added to the n-octanol solution, and the molar part ratio of the n-octanol to the triethylamine is 1: (1.1-1.3).
In the scheme, HCl is released when-COCl in acyl chloride compounds and derivatives thereof react with-OH in fatty alcohol, and the generated HCl is consumed through triethylamine, so that the PH of the system is kept stable; because the reaction is rapid, in order to enable the triethylamine to timely eliminate HCl generated by the reaction, the triethylamine is firstly added into the fatty alcohol solution, and then the acyl chloride compound and the derivative thereof are added.
Further, n-octyl acrylate is slowly added into the organic phosphaphenanthrene compound solution mixed with the catalyst to prepare the organic phosphaphenanthrene derivative with the fatty chain structure, and the specific preparation mode is the same as that of the first embodiment.
Example III
As another embodiment of the present invention, this embodiment provides an organophosphorous phenanthrene derivative having a fatty chain structure, wherein the organophosphorous phenanthrene compound has the structural formula:
in this example, the fatty alcohol ester was prepared by reacting dimethylcarbamoyl chloride with triacontanol and reacting the-COCl group on the dimethylcarbamoyl chloride with the-OH group on the triacontanol to give the triacontanol dimethylcarbamate.
The preparation method of the triacontyl dimethylcarbamate is the same as that in the first embodiment, except that the acid-binding agent triethylamine is added to the triacontyl alcohol solution before the dimethylcarbamoyl chloride is added to the triacontyl alcohol solution, and the molar part ratio of the triacontyl alcohol to the triethylamine is 1: (1.1-1.3).
In the scheme, HCl is released when-COCl in acyl chloride compounds and derivatives thereof react with-OH in fatty alcohol, and the generated HCl is consumed through triethylamine, so that the PH of the system is kept stable; because the reaction is rapid, in order to enable the triethylamine to timely eliminate HCl generated by the reaction, the triethylamine is firstly added into the fatty alcohol solution, and then the acyl chloride compound and the derivative thereof are added.
Further, the triacontyl dimethylcarbamate is slowly added into the organic phosphaphenanthrene compound solution mixed with the catalyst to prepare the organic phosphaphenanthrene derivative with the fat chain structure, the specific preparation mode of the organic phosphaphenanthrene derivative with the fat chain structure is the same as that of the first embodiment, and the amino group on the triacontyl dimethylcarbamate reacts with the carboxyl group on the organic phosphaphenanthrene compound to obtain the organic phosphaphenanthrene derivative with the fat chain structure.
Example IV
As another embodiment of the present invention, this embodiment provides an organic phosphaphenanthrene derivative having a fatty chain structure, which has the same production method as the embodiment, except that 2-ethylhexanol is used as the fatty alcohol.
Detection example 1
The present test example provides a DOPO derivative composite material having a fatty chain structure of EVA/MH/DOPO derivative having a fatty chain structure using an organophosphazene derivative having a fatty chain structure as described in example one.
In this test example, 50 parts by mass of pure EVA, 48 parts by mass of MH and 2 parts by mass of an organic phosphaphenanthrene derivative having a fatty chain structure were uniformly mixed, and blended in an internal mixer at a temperature of 140 ℃ for 6 minutes to obtain an EVA/MH/DOPO derivative composite material having a fatty chain structure, the SEM photograph of which is shown in FIG. 1.
Detection example two
The present test example provides a DOPO derivative composite material having a fatty chain structure of EVA/MH/DOPO derivative having a fatty chain structure as a synergist, using an organophosphazene derivative having a fatty chain structure as described in example II.
In this test example, 50 parts of pure EVA, 48 parts of MH and 2 parts of an organic phosphaphenanthrene derivative with a fatty chain structure are uniformly mixed, and the mixture is blended for 6 minutes in an internal mixer with the temperature of 140 ℃ to obtain an EVA/MH/DOPO derivative composite material with a fatty chain structure, and an SEM (scanning electron microscope) picture of the composite material is shown in figure 2.
Detection example III
The present test example provides a DOPO derivative composite material having a fatty chain structure of EVA/MH/DOPO derivative having a fatty chain structure as a synergist, using an organophosphazene derivative having a fatty chain structure as described in example III.
In the test example, 50 parts of pure EVA, 48 parts of MH and 2 parts of organic phosphaphenanthrene derivative with a fatty chain structure are uniformly mixed, and the mixture is blended for 6 minutes in an internal mixer with the temperature of 140 ℃ to obtain the EVA/MH/DOPO derivative composite material with the fatty chain structure to be tested.
Detection example four
The present test example provides a DOPO derivative composite material having a fatty chain structure of EVA/MH/DOPO derivative having a fatty chain structure as a synergist, using an organophosphazene derivative having a fatty chain structure as described in example IV.
In the test example, 50 parts of pure EVA, 48 parts of MH and 2 parts of organic phosphaphenanthrene derivative with a fatty chain structure are uniformly mixed, and the mixture is blended for 6 minutes in an internal mixer with the temperature of 140 ℃ to obtain the EVA/MH/DOPO derivative composite material with the fatty chain structure to be tested.
Comparative example one
The comparative example provides an EVA/MH composite material, which is prepared by the following steps:
50 parts of virgin EVA and 50 parts of MH were blended in an internal mixer at 140℃for 6 minutes to give a processed EVA/MH composite to be tested, the SEM photograph of which is shown in FIG. 3.
Comparative example two
The comparative example provides an EVA/MH/DOPO composite material, which is prepared by the following steps:
50 parts of pure EVA, 48 parts of MH and 2 parts of DOPO with organic phosphaphenanthrene are uniformly mixed, and blended for 6 minutes in an internal mixer at the temperature of 140 ℃ to obtain an EVA/MH/OA-DOPO composite material to be tested, and an SEM (scanning electron microscope) picture of the composite material is shown in figure 4.
Experimental example 1
Melt index testing was performed on test examples one, two, three, four and comparative example two using a melt index apparatus HAAKE MeltflixeHT from germany Thermo Fisher Scientific, and was performed according to standard ISO 1133: the test temperature was 190℃and the nominal load was 2.16kg, with a sample cut-off interval of 60s. The balance torque values for test examples one, two, three, four and comparative examples one, two were obtained using an internal mixer equipped with a HAAKE Polylab OS RheoDrive rheometer from Thermo Fisher Scientific, germany.
The specific test results are as follows:
from the above test results, it can be seen that:
firstly, the organic phosphaphenanthrene derivative containing the fat chain structure is used in the first detection example, the second detection example, the third detection example and the fourth detection example, and the organic phosphaphenanthrene DOPO without the fat chain structure is used in the second comparison example, the first comparison example does not use the organic phosphaphenanthrene and the organic phosphaphenanthrene derivative, and the MFR of the first detection example, the second detection example, the third detection example and the fourth detection example is higher than that of the first comparison example and the second comparison example, and the balance torque of the first detection example, the second detection example, the third detection example and the fourth detection example is lower than that of the first comparison example and the second comparison example, so that the organic phosphaphenanthrene derivative with the fat chain structure can have better effect on the processing performance of an EVA/MH system.
Next, the length of the fatty chain in test example one was 18 carbon atoms, the length of the fatty chain in test example two was 8 carbon atoms, the length of the fatty chain in test example three was 30 carbon atoms, and the MFR of test example two was larger than that of test example one, and the MFR of test example one was larger than that of test example three; and the balance torque of the second detection example is smaller than that of the first detection example, and the balance torque of the first detection example is smaller than that of the third detection example, so that the improvement effect on the processability of the EVA/MH/DOPO derivative composite material with the fatty chain structure is gradually reduced along with the increase of the fatty chain length.
It can be seen that from the second test example and the fourth test example each having a fatty chain having 8 carbon atoms, wherein the second test example uses an organophosphorous phenanthrene derivative having no branched chain in the fatty chain, the fourth test example uses an organophosphorous phenanthrene derivative having a branched chain in the fatty chain, and the MFR of the second test example is higher than that of the fourth test example; the test example balancing torque was lower than test example four, indicating that the presence of the branches reduced the flame retardant effect of the EVA/MH/DOPO composite with fatty chains.
Experimental example two
Determination of limiting oxygen index for test examples one, two, three, four and comparative example one using FTT limiting oxygen index determinator from British FTT companyNumber (LOI) according to standard ISO4589, test spline specification 80X 10X 4mm 3 . The specific test results are as follows:
from the test results, the LOI of the first, second, third and fourth test examples is higher than that of the first test example, which shows that the addition of the DOPO derivative with the fatty chain into the EVA/MH system can improve the flame retardant property of the system.
Experimental example III
The color indexes of the first comparative example and the first detection example are measured by adopting a full-automatic color difference meter SC-80C of Beijing Kang Guang limited company of China, a disc-shaped sample with phi 25mm and 1mm is placed on a sample table, and the color indexes of the measured samples are measured by aiming at light air compression.
The color of the material was characterized by 5 whiteness indexes (CIE 86 whiteness: wg; R457 whiteness: wr; hunter whiteness: wh; stensby whiteness: ws; stephansen whiteness: wp) and two yellowness indexes (ASTM (D1925) yellowness: YID; ASTM (E313) yellowness: YIE), and the results were repeated three times, and the average value and standard deviation were recorded.
The specific test results are as follows:
comparative example one | Detection example 1 | |
CIE86 whiteness (W) g ) | 72.98±0.77 | 90.76±0.11 |
R457 whiteness (W) r ) | 80.98±0.30 | 88.31±0.21 |
Hunter whiteness (W) h ) | 91.01±0.16 | 92.95±0.13 |
Stensby whiteness (W) s ) | 82.40±0.70 | 94.49±0.45 |
Stephansen whiteness (W) p ) | 77.34±0.46 | 89.70±0.12 |
ASTM (D1925) Yellowness (YID) | 3.73±0.31 | -2.14±0.13 |
ASTM (E313) Yellowness (YIE) | 3.55±0.29 | -1.46±0.04 |
As can be seen from the test results, the first test example was W g 、W r 、W h 、W s 、W p Higher than comparative example one; meanwhile, YID and YIE are lower than those of the first comparative example, which shows that the addition of DOPO derivative with fatty chain into EVA/MH system can raise whiteness of material and reduce yellowness of material.
Experimental example four
Performing steady state fluorescence spectrum test on the first comparative example and the first detection example by using an FLS-980 steady state transient fluorescence spectrometer of the UK EDINBURGH INSTRUMENTS company; the excitation wavelength of the emission spectrum is set to 310nm, and the detection wavelength is 350-500 nm.
The test results are shown in fig. 6, and it can be seen from the test results that the fluorescence emission spectra of the first comparative example and the first test example, the fluorescence emission intensity of the first test example is higher than that of the first comparative example, which indicates that adding the DOPO derivative with a fatty chain into the EVA/MH system can improve the brightness of the material.
Experimental example five
The compatibility of the fillers MH and EVA matrix in comparative examples one and two and examples one and two was characterized by Scanning Electron Microscope (SEM) SU8020 from Hitachi Limited, japan, in the following manner:
the acceleration voltage was set to 10V; samples before testing were subject to brittle failure in liquid nitrogen, platinum-sprayed by a GIKOIB-3 ion applicator, and photographed using SEM.
Specific test results are shown in fig. 1 to 4, wherein fig. 1 is an SEM photograph of the EVA/MH/DOPO derivative composite material with fatty chain structure according to test example one;
FIG. 2 is an SEM photograph of a DOPO derivative composite material having a fatty chain structure using EVA/MH as described in test example II.
As can be seen from fig. 1 to 4, the MH in the first and second test examples had good dispersion in EVA, while the MH in the first and second comparative examples had agglomeration in the matrix; it is described that this organic phosphaphenanthrene derivative with a fatty chain structure, which is a polar DOPO group at one end and a nonpolar fatty chain at the other end, may "bridge" the EVA and MH by intermolecular forces by affinity with MH and EVA at both ends, thereby improving the dispersibility of the filler MH in EVA.
Experimental example six
The first comparative example and the first test example were subjected to tensile testing by means of an Instron3365 universal materials tester from Instron company in the united states of america, according to standard ISO 527. The test sample bar is dumbbell type sample bar with specification of 75X4X2mm3, and the temperature is 21 deg.C and humidity is 20%.
The test results were as follows:
comparative example one | Detection example 1 | |
Tensile Strength (Mpa) | 13.8±0.6 | 10.5±0.7 |
Elongation at break (%) | 161±17 | 278±21 |
From the above test results, it can be seen that the test example has higher elongation at break and better flexibility, which indicates that the addition of DOPO derivative with fatty chain to EVA/MH system can improve the flexibility of the material.
The foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited to the above-mentioned embodiment, but is not limited to the above-mentioned embodiment, and any simple modification, equivalent change and modification made by the technical matter of the present invention can be further combined or replaced by the equivalent embodiment without departing from the scope of the technical solution of the present invention.
Claims (9)
1. The organic phosphaphenanthrene derivative with the fatty chain structure is characterized in that the organic phosphaphenanthrene derivative with the fatty chain is obtained by reacting an organic phosphaphenanthrene compound with a fatty alcohol ester compound, wherein the fatty alcohol ester compound is provided with a fatty chain with 8-30 carbon atoms;
the fatty alcohol ester compound is obtained by reacting fatty alcohol with carboxylic acid, acyl chloride compound and derivative thereof, wherein the fatty alcohol reacts with the carboxylic acid, the acyl chloride compound and derivative thereof to obtain the fatty chain, the fatty chain is provided with branched chains, and the number of carbon atoms of the branched chains is not more than 3.
2. The organic phosphaphenanthrene derivative with fatty chain structure according to claim 1, wherein at least one-COOH group or-COCl group capable of reacting with-OH group on fatty alcohol is present on the carboxylic acid, the acid chloride compound and the derivative thereof.
3. The organophosphazene derivative with a fatty chain structure according to claim 2, wherein the number of branches on the fatty chain is not more than 4.
4. An organophosphazene derivative with a fatty chain structure according to any one of claims 1-3, wherein the fatty alcohol ester has at least one active group in addition to a-COOH group or a-COCl group, and the active group on the fatty alcohol ester reacts with the organophosphazene compound to obtain the organophosphazene derivative with a fatty chain structure.
5. The organic phosphaphenanthrene derivative with fatty chain structure according to claim 4, wherein the active group comprises at least isocyanate group, ethynyl group, vinyl group, carboxyl group, epoxy group, amino group or halogen atom.
6. The organic phosphaphenanthrene derivative with a fatty chain structure according to claim 4, wherein the structural general formula of the organic phosphaphenanthrene compound is shown as a formula-I:
-A in the general structural formula is selected from any one of the following structures:
and (3) reacting the-A in the organic phosphaphenanthrene compound with the active group in the fatty alcohol ester to obtain the organic phosphaphenanthrene derivative with the fatty chain structure.
7. A method for producing an organophosphazene derivative having a fatty chain structure according to any one of claims 1 to 6, comprising the steps of:
s1, preparing fatty alcohol ester compounds;
s2, slowly adding the fatty alcohol ester compound into the organic phosphaphenanthrene compound solution mixed with the catalyst to prepare the organic phosphaphenanthrene derivative with the fatty chain structure.
8. The method for preparing an organophosphorous phenanthrene derivative with a fatty chain structure according to claim 7, wherein in the step S1, fatty alcohol is dissolved in an organic solvent to form a solution, then carboxylic acid or acyl chloride derivative is added, and the fatty alcohol ester compound is obtained through stirring, filtering, extracting and drying, wherein the molar ratio of the fatty alcohol to the organic solvent to the carboxylic acid or acyl chloride derivative is 1: (10-25): (1-1.3).
9. Use of an organophosphazene derivative having a fatty chain structure according to any one of claims 1-6 as a synergist.
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JPH0429237A (en) * | 1990-05-25 | 1992-01-31 | Konica Corp | Method for preventing color fading of organic coloring material and color photographic material |
JP2003252883A (en) * | 2002-02-28 | 2003-09-10 | Nof Corp | Method for producing phosphorus-containing carboxylic acid derivative |
CN105669760A (en) * | 2016-03-07 | 2016-06-15 | 中国科学院化学研究所 | Organic phosphaphenanthrene derivatives, and preparation method and application thereof |
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JPH0429237A (en) * | 1990-05-25 | 1992-01-31 | Konica Corp | Method for preventing color fading of organic coloring material and color photographic material |
JP2003252883A (en) * | 2002-02-28 | 2003-09-10 | Nof Corp | Method for producing phosphorus-containing carboxylic acid derivative |
CN105669760A (en) * | 2016-03-07 | 2016-06-15 | 中国科学院化学研究所 | Organic phosphaphenanthrene derivatives, and preparation method and application thereof |
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