CN102190681A - Phosphoric butane derivative capable of generating tertiary carbon free radical and preparation method thereof - Google Patents
Phosphoric butane derivative capable of generating tertiary carbon free radical and preparation method thereof Download PDFInfo
- Publication number
- CN102190681A CN102190681A CN2011100556057A CN201110055605A CN102190681A CN 102190681 A CN102190681 A CN 102190681A CN 2011100556057 A CN2011100556057 A CN 2011100556057A CN 201110055605 A CN201110055605 A CN 201110055605A CN 102190681 A CN102190681 A CN 102190681A
- Authority
- CN
- China
- Prior art keywords
- aromatic base
- peroxide
- free radical
- alkyl
- tertiary carbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 150000001723 carbon free-radicals Chemical group 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical class CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 title abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 89
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 88
- -1 cumenyl phosphates Chemical class 0.000 claims abstract description 70
- 150000001875 compounds Chemical class 0.000 claims abstract description 64
- 238000003756 stirring Methods 0.000 claims abstract description 45
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 44
- 239000003999 initiator Substances 0.000 claims abstract description 12
- 150000003254 radicals Chemical class 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 239000001307 helium Substances 0.000 claims abstract description 5
- 229910052734 helium Inorganic materials 0.000 claims abstract description 5
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims abstract description 5
- 230000000977 initiatory effect Effects 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 96
- 238000010792 warming Methods 0.000 claims description 78
- 125000003118 aryl group Chemical group 0.000 claims description 56
- 238000001953 recrystallisation Methods 0.000 claims description 44
- 125000000217 alkyl group Chemical group 0.000 claims description 28
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 13
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 11
- 239000008096 xylene Substances 0.000 claims description 11
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 8
- XXQBEVHPUKOQEO-UHFFFAOYSA-N potassium superoxide Chemical compound [K+].[K+].[O-][O-] XXQBEVHPUKOQEO-UHFFFAOYSA-N 0.000 claims description 8
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 7
- YKTNISGZEGZHIS-UHFFFAOYSA-N 2-$l^{1}-oxidanyloxy-2-methylpropane Chemical group CC(C)(C)O[O] YKTNISGZEGZHIS-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 6
- 150000002978 peroxides Chemical class 0.000 claims description 6
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical group [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 claims description 5
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 claims description 4
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 150000002900 organolithium compounds Chemical class 0.000 claims description 4
- 150000002901 organomagnesium compounds Chemical class 0.000 claims description 4
- OKJADYKTJJGKDX-UHFFFAOYSA-N Butyl pentanoate Chemical class CCCCOC(=O)CCCC OKJADYKTJJGKDX-UHFFFAOYSA-N 0.000 claims description 3
- 239000004343 Calcium peroxide Substances 0.000 claims description 3
- ZJRXSAYFZMGQFP-UHFFFAOYSA-N barium peroxide Chemical compound [Ba+2].[O-][O-] ZJRXSAYFZMGQFP-UHFFFAOYSA-N 0.000 claims description 3
- LHJQIRIGXXHNLA-UHFFFAOYSA-N calcium peroxide Chemical compound [Ca+2].[O-][O-] LHJQIRIGXXHNLA-UHFFFAOYSA-N 0.000 claims description 3
- 235000019402 calcium peroxide Nutrition 0.000 claims description 3
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 3
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 3
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 claims description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- SPAGIJMPHSUYSE-UHFFFAOYSA-N Magnesium peroxide Chemical compound [Mg+2].[O-][O-] SPAGIJMPHSUYSE-UHFFFAOYSA-N 0.000 claims description 2
- 150000001351 alkyl iodides Chemical class 0.000 claims description 2
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 229940043232 butyl acetate Drugs 0.000 claims description 2
- 239000012933 diacyl peroxide Substances 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 claims description 2
- HPGPEWYJWRWDTP-UHFFFAOYSA-N lithium peroxide Chemical compound [Li+].[Li+].[O-][O-] HPGPEWYJWRWDTP-UHFFFAOYSA-N 0.000 claims description 2
- 229960004995 magnesium peroxide Drugs 0.000 claims description 2
- 125000000864 peroxy group Chemical group O(O*)* 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-M hydroperoxide group Chemical group [O-]O MHAJPDPJQMAIIY-UHFFFAOYSA-M 0.000 claims 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims 1
- 230000004048 modification Effects 0.000 abstract description 6
- 238000012986 modification Methods 0.000 abstract description 6
- 229920000642 polymer Polymers 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 5
- 238000012545 processing Methods 0.000 abstract description 4
- 229910019142 PO4 Inorganic materials 0.000 abstract 3
- 235000021317 phosphate Nutrition 0.000 abstract 3
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 125000002592 cumenyl group Chemical group C1(=C(C=CC=C1)*)C(C)C 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract 1
- 239000010452 phosphate Substances 0.000 abstract 1
- 238000005303 weighing Methods 0.000 description 55
- 238000004458 analytical method Methods 0.000 description 41
- 238000001816 cooling Methods 0.000 description 41
- 238000002329 infrared spectrum Methods 0.000 description 41
- 238000001819 mass spectrum Methods 0.000 description 41
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 41
- 229940023462 paste product Drugs 0.000 description 41
- 238000005406 washing Methods 0.000 description 41
- 239000004743 Polypropylene Substances 0.000 description 29
- 229920001155 polypropylene Polymers 0.000 description 29
- 239000003063 flame retardant Substances 0.000 description 22
- JMEROBIHUFJHHG-UHFFFAOYSA-N (4-propan-2-ylphenyl) dihydrogen phosphate Chemical compound CC(C)C1=CC=C(OP(O)(O)=O)C=C1 JMEROBIHUFJHHG-UHFFFAOYSA-N 0.000 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 description 18
- 239000000126 substance Substances 0.000 description 18
- 238000005453 pelletization Methods 0.000 description 14
- SGQUHMXHLSTYIH-UHFFFAOYSA-N 2-phenylbutan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(CC)C1=CC=CC=C1 SGQUHMXHLSTYIH-UHFFFAOYSA-N 0.000 description 11
- XSEJRZMALXVCGH-UHFFFAOYSA-N P(=O)(OC)(OC)OC1=CC=C(C=C1)C(C)C Chemical compound P(=O)(OC)(OC)OC1=CC=C(C=C1)C(C)C XSEJRZMALXVCGH-UHFFFAOYSA-N 0.000 description 11
- 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 11
- ZRSIMJAGZCCFIM-UHFFFAOYSA-N C(C)(C)C1=CC=C(C=C1)OP(O)(O)=O.C1(=CC=CC=C1)C1=CC=CC=C1 Chemical compound C(C)(C)C1=CC=C(C=C1)OP(O)(O)=O.C1(=CC=CC=C1)C1=CC=CC=C1 ZRSIMJAGZCCFIM-UHFFFAOYSA-N 0.000 description 9
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- OZHJEQVYCBTHJT-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-methylbenzene Chemical class CC1=C(Br)C(Br)=C(Br)C(Br)=C1Br OZHJEQVYCBTHJT-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000001273 butane Substances 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 5
- 230000002459 sustained effect Effects 0.000 description 5
- 125000004861 4-isopropyl phenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 4
- FRIJBUGBVQZNTB-UHFFFAOYSA-M magnesium;ethane;bromide Chemical compound [Mg+2].[Br-].[CH2-]C FRIJBUGBVQZNTB-UHFFFAOYSA-M 0.000 description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 3
- GLXRXOBBHHHDHL-UHFFFAOYSA-N tert-butyl propan-2-yl hydrogen phosphate Chemical compound CC(C)OP(O)(=O)OC(C)(C)C GLXRXOBBHHHDHL-UHFFFAOYSA-N 0.000 description 3
- ACEHKCPIWMEJPF-UHFFFAOYSA-N 4-bromobutylmercury Chemical compound BrCCCC[Hg] ACEHKCPIWMEJPF-UHFFFAOYSA-N 0.000 description 2
- 0 CC(C)(C(*)(*)c(cc1)ccc1OP(Oc1ccccc1)(Oc1ccccc1)=O)c(cc1)ccc1OP(Oc1ccccc1)(Oc1ccccc1)=O Chemical compound CC(C)(C(*)(*)c(cc1)ccc1OP(Oc1ccccc1)(Oc1ccccc1)=O)c(cc1)ccc1OP(Oc1ccccc1)(Oc1ccccc1)=O 0.000 description 2
- 230000031709 bromination Effects 0.000 description 2
- 238000005893 bromination reaction Methods 0.000 description 2
- 230000009970 fire resistant effect Effects 0.000 description 2
- LWLPYZUDBNFNAH-UHFFFAOYSA-M magnesium;butane;bromide Chemical compound [Mg+2].[Br-].CCC[CH2-] LWLPYZUDBNFNAH-UHFFFAOYSA-M 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- HGTUJZTUQFXBIH-UHFFFAOYSA-N (2,3-dimethyl-3-phenylbutan-2-yl)benzene Chemical compound C=1C=CC=CC=1C(C)(C)C(C)(C)C1=CC=CC=C1 HGTUJZTUQFXBIH-UHFFFAOYSA-N 0.000 description 1
- MVDFAZTVTBODFM-UHFFFAOYSA-N C(C)C1=C(C=CC=C1)OP(OC1=CC=C(C=C1)C(C)C)(O)=O Chemical compound C(C)C1=C(C=CC=C1)OP(OC1=CC=C(C=C1)C(C)C)(O)=O MVDFAZTVTBODFM-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- KVQUSJYYSPQXNR-UHFFFAOYSA-N O1CCCC1.C1(=CC=CC=C1)[Li] Chemical compound O1CCCC1.C1(=CC=CC=C1)[Li] KVQUSJYYSPQXNR-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- WSXMFMCRLSKYBP-UHFFFAOYSA-N [C].CCCC Chemical group [C].CCCC WSXMFMCRLSKYBP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- AWGTVRDHKJQFAX-UHFFFAOYSA-M chloro(phenyl)mercury Chemical compound Cl[Hg]C1=CC=CC=C1 AWGTVRDHKJQFAX-UHFFFAOYSA-M 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- UASCKEPOXNHTNJ-UHFFFAOYSA-N iodobenzene oxolane Chemical compound O1CCCC1.IC1=CC=CC=C1 UASCKEPOXNHTNJ-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229940091250 magnesium supplement Drugs 0.000 description 1
- IWCVDCOJSPWGRW-UHFFFAOYSA-M magnesium;benzene;chloride Chemical compound [Mg+2].[Cl-].C1=CC=[C-]C=C1 IWCVDCOJSPWGRW-UHFFFAOYSA-M 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- MRQRDRTVPDZRKE-UHFFFAOYSA-N mercury;toluene Chemical compound [Hg].CC1=CC=CC=C1 MRQRDRTVPDZRKE-UHFFFAOYSA-N 0.000 description 1
- ZDHHIJSLJCLMPX-UHFFFAOYSA-M methylmercury(1+);bromide Chemical compound C[Hg]Br ZDHHIJSLJCLMPX-UHFFFAOYSA-M 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- ITJSVDCZHCYXQE-UHFFFAOYSA-N toluene;hydroiodide Chemical compound I.CC1=CC=CC=C1 ITJSVDCZHCYXQE-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention relates to a high-thermal-stability phosphatic butane derivative capable of generating tertiary carbon free radical and a preparation method thereof. The phosphatic butane derivative can be used for flame retardancy and property modification of polymers. The preparation method is realized in a way that: cumenyl-containing phosphate, which is used as the raw material, is reacted under the initiation of a free radical initiator to synthesize the target compound. The method comprises the following steps: putting one or two different cumenyl phosphates into a reaction vessel, and adding a solvent which accounts for 150% by mass of the cumenyl phosphates; in a nitrogen or helium atmosphere, adding the free-radical initiator while stirring, heating to 5-120 DEG C, keeping the reaction for 6-24 hours, and removing the solvent and excessive reaction products; and rectifying or recrystallizing to obtain the target compound. The phosphoric butane derivative capable of generating tertiary carbon free radical only starts to generate free radical when the temperature reaches 260 DEG C, thereby satisfying the requirement for the processing temperature of most polymers and having a wide application range.
Description
Technical field
The invention belongs to the preparation field of the butane derivative that can produce the tertiary carbon free radical, particularly relate to the phosphorous butane derivative and preparation method thereof of produced tertiary carbon free radical that a class can be used for the high thermal stability of the fire-retardant and property modification of polymkeric substance.
Background technology
Along with the development of society, the application of polymkeric substance is increasingly extensive, and people also improve day by day to the requirement of polymer properties such as flame retardant properties, mechanical property and moulding processability etc.Therefore selecting suitable properties-correcting agent is the effective way of guaranteeing that polymkeric substance is rationally used to improve polymer properties.In recent years, having the butane compounds that can produce the tertiary carbon free radical is being used widely as fields such as polymkeric substance retardant synergist, vinyl polymer linking agent and graft copolymerization evocating agents, as document 1 (new type of polymer properties-correcting agent, south of the River institute journal, in September, 1999, the 14th volume, the 3rd phase, the 85-88 page or leaf) introduced 2,3-dimethyl-2,3-diphenyl butane and derivative thereof are in the application of aspect such as polymkeric substance is fire-retardant, crosslinked.Document 2 (Chinese patent application number 200510099017.8) has been reported and has been adopted 2,3-dimethyl-2, and 3-diphenyl butane synergy bromide fire retardant is used for polymkeric substance such as polypropylene flame redardant.Document 3 (United States Patent (USP): 3850882) reported a series of synthetic methods with butane derivative of tertiary carbon structure.But above-mentioned document all focuses on the butane of research basic structure and the fire retardation of derivative thereof, does not all disclose synthetic method and application that relevant phosphorated has the butane derivative that can produce the tertiary carbon free radical.
Above-mentioned document 1 and document 2 disclosed 2,3-dimethyl-2, properties-correcting agent such as the 3-diphenyl butane is crosslinked as retardant synergist and vinyl polymer, grafting have obtained to use, but because this compound begins to produce free radical in the time of 210 ℃, therefore it is bad to add the man-hour thermostability in the higher polymer modification of melt temperature, often lost efficacy, and caused the polymkeric substance flame retardant rating to descend, property modification such as crosslinked misses one's aim.The technical scheme of document 3 records also exists same problem.Up to now, the butane and the derivative thereof of also having no talent and working out the phosphorous of high thermal stability and can produce the tertiary carbon free radical.
Summary of the invention
Technical problem to be solved by this invention provides a kind of phosphorous butane derivative of produced tertiary carbon free radical of high thermal stability and the method for preparation thereof.
Of the present invention have the phosphorous butane derivative that can produce the tertiary carbon free radical and have following structure (1):
Phosphorous butane derivant structure (1)
Wherein, R1=H, C1-18 alkyl, aromatic base or condensed ring aromatic base etc.; R2=H, C1-18 alkyl, aromatic base or condensed ring aromatic base etc.; R3=H, C1-18 alkyl, aromatic base or condensed ring aromatic base etc.; R4=H, C1-18 alkyl, aromatic base or condensed ring aromatic base etc.
Of the present invention have the phosphorous butane derivative that can produce the tertiary carbon free radical and adopt the phosphoric acid ester that contains cumyl to do raw material, by radical initiator initiation reaction, synthesising target compound.Concrete synthesis step is as follows:
The cumyl phosphoric acid ester that one or both are different drops in the reaction vessel, adding mass percent is the solvent of the 0-150% of cumyl phosphoric acid ester total mass, under nitrogen or helium protection, stir, and adding radical initiator, add-on is the radical initiator that every mole of cumyl phosphoric acid ester adds the 0.5-50.0 gram, keep reaction 6-24 hour after being warming up to 5-120 ℃, slough solvent and excessive reactant, behind rectifying or recrystallization, obtain target compound;
Wherein, described solvent is benzene,toluene,xylene, butylbenzene, chlorobenzene, acetone, pimelinketone, ether, tetrahydrofuran (THF), ethyl acetate or ethylene dichloride.
The chemical equation of synthetic route is as follows:
Wherein, compound (2) can be that same compound also can be different with compound (3).R1=H, C1-18 alkyl, aromatic base or condensed ring aromatic base etc.; R2=H, C1-18 alkyl, aromatic base or condensed ring aromatic base etc.; R3=H, C1-18 alkyl, aromatic base or condensed ring aromatic base etc.; R4=H, C1-18 alkyl, aromatic base or condensed ring aromatic base etc.
The initiator of above-mentioned reaction indication is an organomercury compound, organo-magnesium compound, organoiodine compound, organolithium compound, and a kind of or mixture more than 2 kinds and 2 kinds of superoxide etc.
Above-mentioned organomercury compound is the compound with following structure:
R5=H wherein, C1-18 alkyl, aromatic base or condensed ring aromatic base etc.; R6=H, C1-18 alkyl, aromatic base or condensed ring aromatic base etc.; R7=H, C1-18 alkyl, aromatic base or condensed ring aromatic base etc.; X=Cl, Br or I.
Above-mentioned organo-magnesium compound is the compound with following structure:
R
8-MgX, R8=H, C1-18 alkyl, aromatic base or condensed ring aromatic base etc.; X=Cl, Br or I.
Above-mentioned organoiodine compound is meant alkyl iodide, aromatic hydrocarbons iodine substituent, as methyl iodide, iodobenzene etc.;
Above-mentioned organolithium compound is meant lithium alkylide, aryl lithium, as butyllithium, phenyl lithium etc.;
The superoxide of above-mentioned initiator indication comprises inorganic peroxide and organo-peroxide.
The inorganic peroxide of above-mentioned indication is selected from sodium peroxide, Potassium peroxide, lithium peroxide, calcium peroxide, Magnesium peroxide, barium peroxide etc.;
The organo-peroxide of above-mentioned indication is selected from hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxy esters, ketone peroxide etc.; as tertbutyl peroxide, ditertiary butyl peroxide, dicumyl peroxide, benzoyl peroxide, the peroxyacetic acid tert-butyl ester, t-butylperoxyl benzoate, 2; 5-dimethyl-2; 5-two (t-butylperoxy)-3-acetylene, 4; two (tert-butyl peroxy base) n-butyl pentanoates, 2 of 4-; 5-dimethyl-2,5-two (tert-butyl peroxy base) hexane etc.
The institute of the present invention phosphorous butane derivative of synthetic not only has and 2,3-dimethyl-2, the effect that tertiary carbon butane compounds such as 3-diphenyl butane similarly can produce the tertiary carbon free radical, the fire-resistant synergistic system that can be used for polymkeric substance, and polymkeric substance is crosslinked, graft copolymerization etc., simultaneously because the introducing of phosphorus has improved the temperature and the thermostability of tertiary carbon free-radical generating, can satisfy the higher machine-shaping temperature range requirement of polymkeric substance, as 2,3-dimethyl-2, its processing temperature generally can not surpass 230 ℃ when 3-diphenyl butane and bromide compositional flame-retardant polymkeric substance, and can be 260 ℃ of normal process uses when adopting phosphorous butane of the present invention and bromide compositional flame-retardant polymkeric substance.
Phosphorous butane preparation method of the present invention: the phosphoric acid ester of a certain amount of cumyl is dropped in the reaction vessel; adding the certain amount of solvent dissolving can also be without solubilizing agent; under protection of inert gas such as nitrogen or helium, stir; add initiator; keep the reaction certain hour after rising to certain temperature; slough solvent and excessive reactant, behind rectifying or recrystallization, obtain target compound.
Product of the present invention can be used for the retardant synergist of polymkeric substance, and crosslinked, copolymerization or graft modification agent.
Beneficial effect
The phosphorous butane derivative that produces the tertiary carbon free radical of the present invention has high thermal stability, just begins to produce free radical in the time of 260 ℃, therefore can satisfy the processing temperature requirement of most polymkeric substance, has more wide applications.
The preparation method who produces the phosphorous butane derivative of tertiary carbon free radical of the present invention, this method is simple and direct, efficient, and is environmentally friendly, and cost is low, has good application value; And the phosphorous butane derivative that makes has excellent fire retardant and causes dual-use function, has the thermostability height simultaneously, with characteristics such as the superpolymer consistency are good, not only can be used for the fire-resistant synergistic system of polymkeric substance, can also be used for crosslinked, graft copolymerization of polymkeric substance etc.The phosphorous butane derivative that produces the tertiary carbon free radical of the present invention just begins to produce free radical in the time of 260 ℃, the processing temperature that therefore can satisfy most polymkeric substance requires (can under 260 ℃ temperature normal process), has more wide applications.
Embodiment
Below in conjunction with embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
The phosphorous butane derivative that produces the tertiary carbon free radical of the present invention has following structure:
Wherein, R
1=H, C1-18 alkyl, aromatic base or condensed ring aromatic base;
R
2=H, C1-18 alkyl, aromatic base or condensed ring aromatic base;
R
3=H, C1-18 alkyl, aromatic base or condensed ring aromatic base;
R
4=H, C1-18 alkyl, aromatic base or condensed ring aromatic base.
Embodiment 1:
Take by weighing in the reaction vessel of 1 cubic metre of 4-isopropyl phenyl phosphoric acid ester 216KG input; under nitrogen protection, stir and be warming up to 45 ℃; in 4 hours, add the 0.5KG ditertiary butyl peroxide; holding temperature continues reaction 24 hours for 45 ℃; be cooled to 30 ℃ of after washings and get paste product 185KG 3 times, add xylene soluble then, the cooling recrystallization obtains the 160KG target product; analyze proof through ultimate analysis, IR, NMR and mass spectrum etc., product is following structural compounds:
Embodiment 2:
Take by weighing in the reaction vessel of 1 cubic metre of ethylphenyl (4-isopropyl phenyl) phosphoric acid ester 320KG and 180KG benzene input; under nitrogen protection, add 300KG benzene; stirring is warming up to 60 ℃; 1KG sodium peroxide in 4 hours; slowly be warming up to 80 ℃ after adding and continue reaction 18 hours; be cooled to 40 ℃ of after washings and get paste product 256KG 3 times; add xylene soluble then; the cooling recrystallization obtains the 214KG product; analyze proof through ultimate analysis, IR, NMR and mass spectrum etc., product is following structural compounds:
Embodiment 3:
Take by weighing in the reaction vessel of 1 cubic metre of two (octadecyl base) (4-isopropyl phenyl) phosphoric acid ester 360KG input; under nitrogen protection, add 350KG dimethylbenzene; stir holding temperature at 25 ℃; in 4 hours, add 10KG methyl mercuric bromide tetrahydrofuran solution; slowly be warming up to 120 ℃ after adding and continue reaction 6 hours; be cooled to 30 ℃ of after washings and get paste product 313KG 3 times; add the ethylene dichloride dissolving then; the cooling recrystallization obtains the 242KG product; analyze proof through ultimate analysis, IR, NMR and mass spectrum etc., product is following structural compounds:
Embodiment 4:
Take by weighing in the reaction vessel of 0.5 cubic metre of dimethyl (4-isopropyl phenyl) phosphoric acid ester 244KG input; add 350KG toluene; under nitrogen protection, stir and be warming up to 75 ℃; in 4 hours, add the 0.5KG benzoyl peroxide; slowly be warming up to 110 ℃ after adding and continue reaction 16 hours; be cooled to 30 ℃ of after washings and get paste product 205KG 3 times; add xylene soluble then; the cooling recrystallization obtains the 176KG product; analyze proof through ultimate analysis, IR, NMR and mass spectrum etc., product is following structural compounds:
Embodiment 5:
Take by weighing in 244 gram dimethyl (4-isopropyl phenyl) phosphoric acid ester and 368 gram phenylbenzene (4-isopropyl phenyl) the phosphoric acid ester input 1000ml there-necked flasks; under nitrogen protection, add 300 gram pimelinketone; stirring is warming up to 45 ℃; in 4 hours, add 100 gram phenyl lithium diethyl ether solutions; slowly be warming up to 105 ℃ after adding and continue reaction 24 hours; be cooled to 30 ℃ of after washings and get paste product 520 grams for 3 times; add the hexanaphthene dissolving then; the cooling recrystallization obtains 459 products; analyze proof through ultimate analysis, IR, NMR and mass spectrum etc., product is following structural compounds:
Embodiment 6:
Take by weighing in the reaction vessel of 1 cubic metre of phenylbenzene (4-isopropyl phenyl) phosphoric acid ester 368KG and 40KG ether input; stirring the maintenance temperature under nitrogen protection is 5 ℃; in 5 hours, add the 20KG ethylmagnesium bromide; slowly be warming up to 35 ℃ after adding and continue reaction 18 hours; be cooled to 20 ℃ of after washings and get paste product 320KG 3 times, add the toluene dissolving then, the cooling recrystallization obtains the 252KG product; analyze proof through ultimate analysis, IR, NMR and mass spectrum etc., product is following structural compounds:
Embodiment 7:
Taking by weighing three (4-isopropyl phenyl) phosphoric acid ester 452KG and 100KG ethylene dichloride puts in 1 cubic metre the reaction vessel; under nitrogen protection, stir and be warming up to 70 ℃; in 4 hours, add methyl iodide 2.5KG; slowly be warming up to 100 ℃ after adding and continue reaction 16 hours; be cooled to 30 ℃ of after washings and get paste product 361KG for 3 times, add the toluene dissolving then, the cooling recrystallization obtains the 289KG product; analyze proof through ultimate analysis, IR, NMR and mass spectrum etc., product is following structural compounds:
Embodiment 8:
Take by weighing in the reaction vessel of 1 cubic metre of two (octadecyl base) (4-isopropyl phenyl) phosphoric acid ester 360KG input; under nitrogen protection, stir holding temperature at 60 ℃; in 4 hours, add 10KG iodobenzene tetrahydrofuran solution; slowly be warming up to 120 ℃ after adding and continue reaction 10 hours; be cooled to 30 ℃ of after washings and get paste product 287KG 3 times; add the ethylene dichloride dissolving then; the cooling recrystallization obtains the 232KG product; analyze proof through ultimate analysis, IR, NMR and mass spectrum etc., product is following structural compounds:
Embodiment 9:
Take by weighing in 244 gram dimethyl (4-isopropyl phenyl) phosphoric acid ester and 368 gram phenylbenzene (4-isopropyl phenyl) the phosphoric acid ester input 1000ml there-necked flasks; add 200 gram toluene; under nitrogen protection, stir and be warming up to 50 ℃; in 4 hours, add 100 gram sodium peroxides; slowly be warming up to 90 ℃ after adding and continue reaction 24 hours; be cooled to 30 ℃ of after washings and get paste product 512 grams for 3 times; add the hexanaphthene dissolving then; the cooling recrystallization obtains 464 gram products; analyze proof through ultimate analysis, IR, NMR and mass spectrum etc., product is following structural compounds:
Embodiment 10:
Take by weighing in the reaction vessel of 1 cubic metre of phenylbenzene (4-isopropyl phenyl) phosphoric acid ester 368KG input; under nitrogen protection, stir and be warming up to 45 ℃; in 4 hours, add the 15KG ethyl magnesium bromide etherate; slowly be warming up to 110 ℃ after adding and continue reaction 6 hours; be cooled to 40 ℃ of after washings and get paste product 315KG 3 times, add the toluene dissolving then, the cooling recrystallization obtains the 264KG product; analyze proof through ultimate analysis, IR, NMR and mass spectrum etc., product is following structural compounds:
Embodiment 11:
Taking by weighing three (4-isopropyl phenyl) phosphoric acid ester 452KG and 60KG butylbenzene puts in 1 cubic metre the reaction vessel; under nitrogen protection, stir and be warming up to 70 ℃; in 4 hours, add the 40KG t-butylperoxyl benzoate; slowly be warming up to 110 ℃ after adding and continue reaction 10 hours; be cooled to 30 ℃ of after washings and get paste product 375KG for 3 times, add the toluene dissolving then, the cooling recrystallization obtains the 321KG product; analyze proof through ultimate analysis, IR, NMR and mass spectrum etc., product is following structural compounds:
Embodiment 12:
Take by weighing in the reaction vessel of 1 cubic metre of two (octadecyl base) (4-isopropyl phenyl) phosphoric acid ester 360KG input; under nitrogen protection, stir and be warming up to 50 ℃; in 4 hours, add 0.25KG phenylmercuric chloride tetrahydrofuran solution; slowly be warming up to 120 ℃ after adding and continue reaction 10 hours; be cooled to 30 ℃ of after washings and get paste product 294KG 3 times; add the ethylene dichloride dissolving then; the cooling recrystallization obtains the 252KG product; analyze proof through ultimate analysis, IR, NMR and mass spectrum etc., product is following structural compounds:
Embodiment 13:
Take by weighing in the reaction vessel of 1 cubic metre of dimethyl (4-isopropyl phenyl) phosphoric acid ester 244KG input; add 366KG toluene; under nitrogen protection, stir and be warming up to 75 ℃; in 4 hours, add the 50KG benzoyl peroxide; slowly be warming up to 100 ℃ after adding and continue reaction 22 hours; be cooled to 30 ℃ of after washings and get paste product 204KG 3 times; add xylene soluble then; the cooling recrystallization obtains the 172KG product; analyze proof through ultimate analysis, IR, NMR and mass spectrum etc., product is following structural compounds:
Embodiment 14:
Take by weighing in the reaction vessel of 1 cubic metre of phenylbenzene (4-isopropyl phenyl) phosphoric acid ester 368KG input; under nitrogen protection, stir and be warming up to 45 ℃; in 4 hours, add the 0.5KG ethylmagnesium bromide; slowly be warming up to 110 ℃ after adding and continue reaction 6 hours; be cooled to 40 ℃ of after washings and get paste product 324KG 3 times, add the toluene dissolving then, the cooling recrystallization obtains the 276KG product; analyze proof through ultimate analysis, IR, NMR and mass spectrum etc., product is following structural compounds:
Embodiment 15:
Taking by weighing three (4-isopropyl phenyl) phosphoric acid ester 452KG and 60KG butylbenzene puts in 1 cubic metre the reaction vessel; under nitrogen protection, stir and be warming up to 70 ℃; in 4 hours, add the 5KG phenyl-magnesium-chloride; slowly be warming up to 110 ℃ after adding and continue reaction 10 hours; be cooled to 30 ℃ of after washings and get paste product 368KG for 3 times, add the toluene dissolving then, the cooling recrystallization obtains the 316KG product; analyze proof through ultimate analysis, IR, NMR and mass spectrum etc., product is following structural compounds:
Embodiment 16:
Take by weighing in the reaction vessel of 1 cubic metre of two (octadecyl base) (4-isopropyl phenyl) phosphoric acid ester 360KG input; under nitrogen protection, stir and be warming up to 50 ℃; in 4 hours, add 20KG phenyl lithium tetrahydrofuran solution; slowly be warming up to 120 ℃ after adding and continue reaction 10 hours; be cooled to 30 ℃ of after washings and get paste product 287KG 3 times; add the ethylene dichloride dissolving then; the cooling recrystallization obtains the 246KG product; analyze proof through ultimate analysis, IR, NMR and mass spectrum etc., product is following structural compounds:
Embodiment 17:
Take by weighing in the reaction vessel of 1 cubic metre of dimethyl (4-isopropyl phenyl) phosphoric acid ester 244KG input; add 300KG toluene; under nitrogen protection, stir and be warming up to 75 ℃; in 4 hours, add the 50KG calcium peroxide, slowly be warming up to 100 ℃ after adding and continue reaction 22 hours, be cooled to 30 ℃ of after washings and get paste product 221KG 3 times; add xylene soluble then; the cooling recrystallization obtains the 184KG product, analyzes proof through ultimate analysis, IR, NMR and mass spectrum etc., and product is following structural compounds:
Embodiment 18:
Take by weighing in the reaction vessel of 1 cubic metre of phenylbenzene (4-isopropyl phenyl) phosphoric acid ester 368KG input; under nitrogen protection, stir and be warming up to 45 ℃; in 4 hours, add the 2.5KG mercury methyl; slowly be warming up to 90 ℃ after adding and continue reaction 20 hours; be cooled to 40 ℃ of after washings and get paste product 316KG 3 times, add the toluene dissolving then, the cooling recrystallization obtains the 265KG product; analyze proof through ultimate analysis, IR, NMR and mass spectrum etc., product is following structural compounds:
Embodiment 19:
Taking by weighing three (4-isopropyl phenyl) phosphoric acid ester 452KG and 50KG chlorobenzene puts in 1 cubic metre the reaction vessel; under nitrogen protection, stir and be warming up to 70 ℃; in 4 hours, add the 1.5KG Potassium peroxide; slowly be warming up to 110 ℃ after adding and continue reaction 10 hours; be cooled to 30 ℃ of after washings and get paste product 374KG for 3 times, add the toluene dissolving then, the cooling recrystallization obtains the 325KG product; analyze proof through ultimate analysis, IR, NMR and mass spectrum etc., product is following structural compounds:
Embodiment 20:
Take by weighing in the reaction vessel of 1 cubic metre of two (octadecyl base) (4-isopropyl phenyl) phosphoric acid ester 360KG and 40KG tetrahydrofuran (THF) input; under nitrogen protection, stir and be warming up to 50 ℃; in 4 hours, add the 20KG tertbutyl peroxide; slowly be warming up to 70 ℃ after adding and continue reaction 24 hours; be cooled to 30 ℃ of after washings and get paste product 277KG 3 times; add the ethylene dichloride dissolving then; the cooling recrystallization obtains the 243KG product; analyze proof through ultimate analysis, IR, NMR and mass spectrum etc., product is following structural compounds:
Embodiment 21:
Take by weighing in the reaction vessel of 1 cubic metre of dimethyl (4-isopropyl phenyl) phosphoric acid ester 244KG input; add 300KG toluene; under nitrogen protection, stir and be warming up to 75 ℃; in 4 hours, add the 40KG peroxyacetic acid tert-butyl ester; slowly be warming up to 100 ℃ after adding and continue reaction 14 hours; be cooled to 30 ℃ of after washings and get paste product 194KG 3 times; add the toluene dissolving then; the cooling recrystallization obtains the 172KG product; analyze proof through ultimate analysis, IR, NMR and mass spectrum etc., product is following structural compounds:
Embodiment 22:
Take by weighing in the reaction vessel of 0.5 cubic metre of phenylbenzene (4-isopropyl phenyl) phosphoric acid ester 184KG input; under nitrogen protection, stir and be warming up to 45 ℃; in 4 hours, add 7.5KG methylbenzene mercury; slowly be warming up to 60 ℃ after adding and continue reaction 24 hours; be cooled to 40 ℃ of after washings and get paste product 152KG 3 times, add the toluene dissolving then, the cooling recrystallization obtains the 124KG product; analyze proof through ultimate analysis, IR, NMR and mass spectrum etc., product is following structural compounds:
Embodiment 23:
Taking by weighing three (4-isopropyl phenyl) phosphoric acid ester 225KG and 25KG toluene puts in 0.5 cubic metre the reaction vessel; under nitrogen protection, stir and be warming up to 50 ℃; in 4 hours, add the 1.5KG Potassium peroxide; slowly be warming up to 100 ℃ after adding and continue reaction 24 hours; be cooled to 30 ℃ of after washings and get paste product 176KG 3 times, add the toluene dissolving then, the cooling recrystallization obtains the 157KG product; analyze proof through ultimate analysis, IR, NMR and mass spectrum etc., product is following structural compounds:
Embodiment 24:
Take by weighing in the reaction vessel of 1 cubic metre of two (octadecyl base) (4-isopropyl phenyl) phosphoric acid ester 360KG and 140KG chlorobenzene input; under nitrogen protection, stir and be warming up to 50 ℃; in 4 hours, add the 25KG tertbutyl peroxide; slowly be warming up to 120 ℃ after adding and continue reaction 6 hours; be cooled to 30 ℃ of after washings and get paste product 283KG 3 times; add the ethylene dichloride dissolving then; the cooling recrystallization obtains the 249KG product; analyze proof through ultimate analysis, IR, NMR and mass spectrum etc., product is following structural compounds:
Embodiment 25:
Take by weighing in the reaction vessel of 1 cubic metre of dimethyl (4-isopropyl phenyl) phosphoric acid ester 244KG input; add 300KG toluene; under nitrogen protection, stir and be warming up to 45 ℃; in 4 hours, add 40KG octadecyl bromination magnesium; slowly be warming up to 100 ℃ after adding and continue reaction 12 hours; be cooled to 30 ℃ of after washings and get paste product 187KG 3 times; add the toluene dissolving then; the cooling recrystallization obtains the 162KG product; analyze proof through ultimate analysis, IR, NMR and mass spectrum etc., product is following structural compounds:
Embodiment 26:
Take by weighing in the reaction vessel of 0.5 cubic metre of phenylbenzene (4-isopropyl phenyl) phosphoric acid ester 184KG input; under nitrogen protection, stir and be warming up to 45 ℃; in 4 hours, add 7.5KG octadecyl bromination mercury; keep 45 ℃ to continue reaction 24 hours; be cooled to 40 ℃ of after washings and get paste product 141KG 3 times, add the toluene dissolving then, the cooling recrystallization obtains the 103KG product; analyze proof through ultimate analysis, IR, NMR and mass spectrum etc., product is following structural compounds:
Embodiment 27:
Taking by weighing three (4-isopropyl phenyl) phosphoric acid ester 225KG and 100KG toluene puts in 0.5 cubic metre the reaction vessel; under nitrogen protection, stir and be warming up to 50 ℃; in 4 hours, add 25KG butyl magnesium bromide; slowly be warming up to 100 ℃ after adding and continue reaction 18 hours; be cooled to 30 ℃ of after washings and get paste product 187KG 3 times, add the toluene dissolving then, the cooling recrystallization obtains the 163KG product; analyze proof through ultimate analysis, IR, NMR and mass spectrum etc., product is following structural compounds:
Embodiment 28:
Take by weighing in the reaction vessel of 1 cubic metre of two (octadecyl base) (4-isopropyl phenyl) phosphoric acid ester 360KG and 40KG ethylene dichloride input; under nitrogen protection, stir and be warming up to 50 ℃; in 4 hours, add 25KG 2; 5-dimethyl-2; 5-two (tert-butyl peroxy base) hexane; slowly be warming up to 80 ℃ after adding and continue reaction 8 hours; be cooled to 30 ℃ of after washings and get paste product 294KG 3 times; add the ethylene dichloride dissolving then; the cooling recrystallization obtains the 256KG product; analyze proof through ultimate analysis, IR, NMR and mass spectrum etc., product is following structural compounds:
Embodiment 29:
Take by weighing in the reaction vessel of 0.5 cubic metre of dimethyl (4-isopropyl phenyl) phosphoric acid ester 244KG input; add the 300KG butylacetate; under nitrogen protection, stir and be warming up to 45 ℃; in 4 hours, add 40KG butyl magnesium bromide; slowly be warming up to 100 ℃ after adding and continue reaction 12 hours; be cooled to 30 ℃ of after washings and get paste product 190KG 3 times; add the toluene dissolving then; the cooling recrystallization obtains the 165KG product; analyze proof through ultimate analysis, IR, NMR and mass spectrum etc., product is following structural compounds:
Embodiment 30:
Take by weighing in the reaction vessel of 0.5 cubic metre of phenylbenzene (4-isopropyl phenyl) phosphoric acid ester 184KG input; under nitrogen protection, stir and be warming up to 45 ℃; in 4 hours, add 7.5KG 2; 5-dimethyl-2; 5-two (t-butylperoxy)-3-acetylene; slowly be warming up to 100 ℃ and continue reaction 6 hours; be cooled to 40 ℃ of after washings and get paste product 151KG 3 times; add the toluene dissolving then; the cooling recrystallization obtains the 114KG product; analyze proof through ultimate analysis, IR, NMR and mass spectrum etc., product is following structural compounds:
Embodiment 31:
Taking by weighing three (4-isopropyl phenyl) phosphoric acid ester 225KG and 225KG toluene puts in 1 cubic metre the reaction vessel; under nitrogen protection, stir and be warming up to 50 ℃; in 4 hours, add the 0.5KG sodium peroxide; slowly be warming up to 100 ℃ after adding and continue reaction 12 hours; be cooled to 30 ℃ of after washings and get paste product 167KG 3 times, add the toluene dissolving then, the cooling recrystallization obtains the 142KG product; analyze proof through ultimate analysis, IR, NMR and mass spectrum etc., product is following structural compounds:
Embodiment 32:
Take by weighing in the reaction vessel of 1 cubic metre of two (octadecyl base) (4-isopropyl phenyl) phosphoric acid ester 360KG and 20KG ethyl acetate input; under nitrogen protection, stir and be warming up to 50 ℃; in 4 hours, add the 25KG toluene iodide; slowly be warming up to 90 ℃ after adding and continue reaction 18 hours; be cooled to 30 ℃ of after washings and get paste product 306KG 3 times; add the ethylene dichloride dissolving then; the cooling recrystallization obtains the 266KG product; analyze proof through ultimate analysis, IR, NMR and mass spectrum etc., product is following structural compounds:
Embodiment 33:
Take by weighing in the reaction vessel of 0.5 cubic metre of dimethyl (4-isopropyl phenyl) phosphoric acid ester 244KG input; under nitrogen protection, stir and be warming up to 45 ℃; in 4 hours, add 0.5KG 4; two (tert-butyl peroxy base) n-butyl pentanoates of 4-; slowly be warming up to 120 ℃ after adding and continue reaction 6 hours; be cooled to 30 ℃ of after washings and get paste product 185KG 3 times; add the toluene dissolving then; the cooling recrystallization obtains the 159KG product; analyze proof through ultimate analysis, IR, NMR and mass spectrum etc., product is following structural compounds:
Embodiment 34:
Take by weighing in the reaction vessel of 1 cubic metre of phenylbenzene (4-isopropyl phenyl) phosphoric acid ester 368KG and 180KG acetone input; under nitrogen protection, stir and be warming up to 35 ℃; in 4 hours, add the 1KG sodium peroxide; slowly be warming up to 55 ℃ after adding and continue reaction 10 hours; be cooled to 20 ℃ of after washings and get paste product 304KG 3 times, add xylene soluble then, the cooling recrystallization obtains the 244KG product; analyze proof through ultimate analysis, IR, NMR and mass spectrum etc., product is following structural compounds:
Embodiment 35:
Take by weighing in the reaction vessel of 1 cubic metre of three (4-isopropyl phenyl) phosphoric acid ester 452KG and 250KG toluene input; under nitrogen protection, stir and be warming up to 50 ℃; in 4 hours, add the 3KG ditertiary butyl peroxide; slowly be warming up to 80 ℃ after adding and continue reaction 18 hours; be cooled to 50 ℃ of after washings and get paste product 405KG 3 times; add xylene soluble then; the cooling recrystallization obtains the 335KG product; analyze proof through ultimate analysis, IR, NMR and mass spectrum etc., product is following structural compounds (4):
Embodiment 36:
Take by weighing in the reaction vessel of 1 cubic metre of xylyl (4-isopropyl phenyl) phosphoric acid ester 400KG input; add 50KG toluene; under nitrogen protection, stir and be warming up to 75 ℃; in 4 hours, add the 50KG t-butylperoxyl benzoate; slowly be warming up to 80 ℃ after adding and continue reaction 22 hours; be cooled to 30 ℃ of after washings and get paste product 332KG 3 times; add xylene soluble then; the cooling recrystallization obtains the 284KG product; analyze proof through ultimate analysis, IR, NMR and mass spectrum etc., product is following structural compounds:
Embodiment 37:
Take by weighing in the reaction vessel of 0.5 cubic metre of phenylbenzene (4-isopropyl phenyl) phosphoric acid ester 366KG input; under nitrogen protection, stir and be warming up to 60 ℃; in 4 hours, add 5.5KG butyl mercuric bromide tetrahydrofuran solution; slowly be warming up to 100 ℃ after adding and continue reaction 12 hours; be cooled to 50 ℃ of after washings and get paste product 320KG 3 times; add the toluene dissolving then; the cooling recrystallization obtains the 276KG product; analyze proof through ultimate analysis, IR, NMR and mass spectrum etc., product is following structural compounds (5):
Embodiment 38:
Take by weighing in the reaction vessel of 0.5 cubic metre of dimethyl (4-isopropyl phenyl) phosphoric acid ester 213KG input; under nitrogen protection, stir holding temperature at 10 ℃; in 4 hours, add the 2.6KG ethyl magnesium bromide etherate; slowly be warming up to 55 ℃ after adding and continue reaction 24 hours; be cooled to 30 ℃ of after washings and get paste product 175KG 3 times; add the ethylene dichloride dissolving then; the cooling recrystallization obtains the 146KG product; analyze proof through ultimate analysis, IR, NMR and mass spectrum etc., product is following structural compounds (6):
Embodiment 39:
Take by weighing in the reaction vessel of 1 cubic metre of two (octadecyl base) (4-isopropyl phenyl) phosphoric acid ester 349.5KG input; add the 300KG butylbenzene; under nitrogen protection, stir and be warming up to 75 ℃; in 4 hours, add the 2.6KG barium peroxide; slowly be warming up to 110 ℃ after adding and continue reaction 16 hours; be cooled to 30 ℃ of after washings and get paste product 305KG 3 times; add xylene soluble then; the cooling recrystallization obtains the 228KG product; analyze proof through ultimate analysis, IR, NMR and mass spectrum etc., product is following structural compounds (7):
Embodiment 40:
Take by weighing in 213 gram dimethyl (4-isopropyl phenyl) phosphoric acid ester and 366 gram phenylbenzene (4-isopropyl phenyl) the phosphoric acid ester input 1000ml there-necked flasks; under nitrogen protection, stir and be warming up to 45 ℃; in 6 hours, add 35 gram butyllithium diethyl ether solutions; slowly be warming up to 85 ℃ after adding and continue reaction 24 hours; be cooled to 30 ℃ of after washings and get paste product 497 grams for 3 times; add the hexanaphthene dissolving then; the cooling recrystallization obtains 432 products; analyze proof through ultimate analysis, IR, NMR and mass spectrum etc., product is following structural compounds (8):
Embodiment 41:
Take by weighing in 216 gram 4-isopropyl phenyl phosphoric acid ester and 368 gram phenylbenzene (4-isopropyl phenyl) the phosphoric acid ester input 1000ml there-necked flasks; under the helium protection, stir and be warming up to 50 ℃; in 6 hours, add 80 gram butyl mercuric bromide tetrahydrofuran solutions; slowly be warming up to 100 ℃ after adding and continue reaction 24 hours; be cooled to 30 ℃ of after washings and get paste product 496 grams for 3 times; add the hexanaphthene dissolving then; the cooling recrystallization obtains 416 gram target products; analyze proof through ultimate analysis, IR, NMR and mass spectrum etc., product is following structural compounds (9):
Embodiment 42:
After taking by weighing 500 gram pentabromotoluenes, 150 gram antimonous oxides, 9250 gram polypropylene and the phosphorous butane compounds of 100 grams (4) mixing, in twin screw extruder in 220 ℃ of extruding pelletizations, the polypropylene flame redardant that obtains is lighted the average self-extinguishing time in back in air be 9 seconds, and flame retardant rating is UL94V-2 (1.6mm) level.
Comparative example 1: take by weighing 500 gram pentabromotoluenes, 150 gram antimonous oxides, 9250 gram polypropylene and 100 grams 2,3-dimethyl-2, after the 3-diphenyl butane mixes, in twin screw extruder in 220 ℃ of extruding pelletizations, the polypropylene flame redardant that obtains is lighted the 35 seconds sustained combustion time of back in air, flame retardant rating can not reach UL94V-2 (1.6mm) level.
Embodiment 43:
Take by weighing 500 grams three (2,2-two brooethyls-3-bromopropyl) after phosphoric acid ester, 150 gram antimonous oxides, 9250 gram polypropylene and the 100 phosphorous butane compounds of gram (6) mix, in twin screw extruder in 190 ℃ of extruding pelletizations, the polypropylene flame redardant that obtains is lighted the average self-extinguishing time in back in air be 5 seconds, and flame retardant rating is UL94V-1 (1.6mm) level.
Comparative example 2: take by weighing 500 grams three (2,2-two brooethyls-3-bromopropyl) phosphoric acid ester, 150 gram antimonous oxides, 9250 gram polypropylene and 100 grams 2,3-dimethyl-2, after the 3-diphenyl butane mixes, in twin screw extruder in 190 ℃ of extruding pelletizations, the polypropylene flame redardant that obtains is lighted the average 11 seconds sustained combustion time of back in air, flame retardant rating is UL94V-2 level (1.6mm).
Embodiment 44:
After taking by weighing 500 gram three (tribromophenoxy) chlorinated isocyanurates, 150 gram antimonous oxides, 9250 gram polypropylene and the phosphorous butane compounds of 100 grams (4) mixing, in twin screw extruder in 230 ℃ of extruding pelletizations, the polypropylene flame redardant that obtains is lighted the average self-extinguishing time in back in air be 9 seconds, and flame retardant rating is UL94V-2 (1.6mm) level.
Comparative example 3: take by weighing 500 gram three (tribromophenoxy) chlorinated isocyanurates, 150 gram antimonous oxides, 9250 gram polypropylene, 38 gram methyl di-isopropyl phosphoric acid ester and 62 grams 2,3-dimethyl-2, after the 3-diphenyl butane mixes, in twin screw extruder in 230 ℃ of extruding pelletizations, the polypropylene flame redardant that obtains is lighted the average self-extinguishing time in back in air be 21 seconds, and flame retardant rating can not reach UL94V-2 (1.6mm) level.
Embodiment 45:
After taking by weighing 500 gram pentabromotoluenes, 150 gram antimonous oxides, 9250 gram polypropylene and the phosphorous butane compounds of 100 grams (5) mixing, in twin screw extruder in 190 ℃ of extruding pelletizations, the polypropylene flame redardant that obtains is lighted the average self-extinguishing time in back in air be 12 seconds, and flame retardant rating is UL94V-2 (1.6mm) level.
Comparative example 4: take by weighing 500 gram pentabromotoluenes, 150 gram antimonous oxides, 9250 gram polypropylene and 38 gram methyl di-isopropyl phosphoric acid ester and 62 grams 2,3-dimethyl-2, after the 3-diphenyl butane mixes, in twin screw extruder in 190 ℃ of extruding pelletizations, the polypropylene flame redardant that obtains is lighted the 24 seconds sustained combustion time of back in air, flame retardant rating can not reach UL94V-2 (1.6mm) level.
Embodiment 46:
Take by weighing 500 grams three (2,2-two brooethyls-3-bromopropyl) after phosphoric acid ester, 150 gram antimonous oxides, 9250 gram polypropylene and the 100 phosphorous butane compounds of gram (8) mix, in twin screw extruder in 220 ℃ of extruding pelletizations, the polypropylene flame redardant that obtains is lighted the average self-extinguishing time in back in air be 5 seconds, and flame retardant rating is UL94V-1 (1.6mm) level.
Comparative example 5: take by weighing 500 grams three (2,2-two brooethyls-3-bromopropyl) phosphoric acid ester, 150 gram antimonous oxides, 9250 gram polypropylene and 100 grams 2,3-dimethyl-2, after the 3-diphenyl butane mixes, in twin screw extruder in 220 ℃ of extruding pelletizations, the polypropylene flame redardant that obtains is lighted the average 11 seconds sustained combustion time of back in air, flame retardant rating is UL94V-2 level (1.6mm).
Embodiment 47:
After taking by weighing 500 gram pentabromotoluenes, 150 gram antimonous oxides, 9250 gram polypropylene and the phosphorous butane compounds of 100 grams (7) mixing, in twin screw extruder in 220 ℃ of extruding pelletizations, the polypropylene flame redardant that obtains is lighted the average self-extinguishing time in back in air be 10 seconds, and flame retardant rating is UL94V-2 (1.6mm) level.
Comparative example 6: take by weighing 500 gram pentabromotoluenes, 150 gram antimonous oxides, 9250 gram polypropylene, 38 gram methyl di-isopropyl phosphoric acid ester and 62 grams 2,3-dimethyl-2, after the 3-diphenyl butane mixes, in twin screw extruder in 220 ℃ of extruding pelletizations, the polypropylene flame redardant that obtains is lighted the average self-extinguishing time in back in air be 19 seconds, and flame retardant rating can not reach UL94V-2 (1.6mm) level.
Embodiment 48:
After taking by weighing 500 gram three (tribromophenoxy) chlorinated isocyanurates, 150 gram antimonous oxides, 9250 gram polypropylene and the phosphorous butane compounds of 100 grams (9) mixing, in twin screw extruder in 190 ℃ of extruding pelletizations, the polypropylene flame redardant that obtains is lighted the average self-extinguishing time in back in air be 9 seconds, and flame retardant rating is UL94V-2 (1.6mm) level.
Comparative example 7: take by weighing 500 gram three (tribromophenoxy) chlorinated isocyanurates, 150 gram antimonous oxides, 9250 gram polypropylene and 100 grams 2,3-dimethyl-2, after the 3-diphenyl butane mixes, in twin screw extruder in 190 ℃ of extruding pelletizations, the polypropylene flame redardant that obtains is lighted the 29 seconds sustained combustion time of back in air, flame retardant rating can not reach UL94V-2 (1.6mm) level.
Claims (10)
1. phosphorous butane derivative that can produce the tertiary carbon free radical, it is characterized in that: the described phosphorous butane derivative that produces the tertiary carbon free radical has following structure:
Wherein, R
1=H, C1-18 alkyl, aromatic base or condensed ring aromatic base;
R
2=H, C1-18 alkyl, aromatic base or condensed ring aromatic base;
R
3=H, C1-18 alkyl, aromatic base or condensed ring aromatic base;
R
4=H, C1-18 alkyl, aromatic base or condensed ring aromatic base.
2. preparation method that can produce the phosphorous butane derivative of tertiary carbon free radical is characterized in that: adopt the phosphoric acid ester that contains cumyl to do raw material, by the radical initiator initiation reaction, synthesize target compound, its structural formula is
Wherein, R
1=H, C1-18 alkyl, aromatic base or condensed ring aromatic base;
R
2=H, C1-18 alkyl, aromatic base or condensed ring aromatic base;
R
3=H, C1-18 alkyl, aromatic base or condensed ring aromatic base;
R
4=H, C1-18 alkyl, aromatic base or condensed ring aromatic base;
Concrete synthesis step is as follows:
The cumyl phosphoric acid ester that one or both are different drops in the reaction vessel, adding mass percent is the solvent of the 0-150% of cumyl phosphoric acid ester total mass, under nitrogen or helium protection, stir, and adding radical initiator, add-on is the radical initiator that every mole of cumyl phosphoric acid ester adds the 0.5-50.0 gram, keep reaction 6-24 hour after being warming up to 5-120 ℃, slough solvent and excessive reactant, behind rectifying or recrystallization, obtain target compound;
Wherein, described solvent is benzene,toluene,xylene, butylbenzene, chlorobenzene, acetone, pimelinketone, ether, tetrahydrofuran (THF), ethyl acetate, butylacetate or ethylene dichloride.
3. a kind of preparation method who produces the phosphorous butane derivative of tertiary carbon free radical according to claim 2, it is characterized in that described radical initiator is a kind of or its mixture in organomercury compound, organo-magnesium compound, organoiodine compound, organolithium compound or the superoxide.
4. a kind of preparation method who produces the phosphorous butane derivative of tertiary carbon free radical according to claim 3 is characterized in that described organomercury compound is the compound with following structure:
R wherein
5=H, C1-18 alkyl, aromatic base or condensed ring aromatic base;
R
6=H, C1-18 alkyl, aromatic base or condensed ring aromatic base;
R
7=H, C1-18 alkyl, aromatic base or condensed ring aromatic base;
X=Cl, Br or I.
5. a kind of preparation method who produces the phosphorous butane derivative of tertiary carbon free radical according to claim 3 is characterized in that described organo-magnesium compound is the compound with following structure:
R
8-MgX
R wherein
8=H, C1-18 alkyl, aromatic base or condensed ring aromatic base;
X=Cl, Br or I.
6. a kind of preparation method who produces the phosphorous butane derivative of tertiary carbon free radical according to claim 3 is characterized in that described organoiodine compound is meant alkyl iodide or aromatic hydrocarbons iodine substituent, preferred methyl iodide or iodobenzene.
7. the preparation method who produces the phosphorous butane derivative of tertiary carbon free radical according to claim 3 is characterized in that described organolithium compound is meant lithium alkylide or aryl lithium, preferred butyllithium or phenyl lithium.
8. a kind of preparation method who produces the phosphorous butane derivative of tertiary carbon free radical according to claim 3 is characterized in that described superoxide is inorganic peroxide or organo-peroxide.
9. a kind of preparation method who produces the phosphorous butane derivative of tertiary carbon free radical according to claim 8, it is characterized in that described inorganic peroxide is selected from sodium peroxide, Potassium peroxide, lithium peroxide, calcium peroxide, Magnesium peroxide or barium peroxide.
10. a kind of preparation method who produces the phosphorous butane derivative of tertiary carbon free radical according to claim 8; it is characterized in that; described organo-peroxide is selected from hydroperoxide; dialkyl peroxide; diacyl peroxide; peroxy esters or ketone peroxide; the preferred tertiary butylhydroperoxide; ditertiary butyl peroxide; dicumyl peroxide; benzoyl peroxide; the peroxyacetic acid tert-butyl ester; t-butylperoxyl benzoate; 2; 5-dimethyl-2; 5-two (t-butylperoxy)-3-acetylene; 4; two (tert-butyl peroxy base) n-butyl pentanoates or 2 of 4-; 5-dimethyl-2,5-two (tert-butyl peroxy base) hexane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110055605.7A CN102190681B (en) | 2011-03-09 | 2011-03-09 | Phosphoric butane derivative capable of generating tertiary carbon free radical and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110055605.7A CN102190681B (en) | 2011-03-09 | 2011-03-09 | Phosphoric butane derivative capable of generating tertiary carbon free radical and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102190681A true CN102190681A (en) | 2011-09-21 |
| CN102190681B CN102190681B (en) | 2014-04-30 |
Family
ID=44599636
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110055605.7A Active CN102190681B (en) | 2011-03-09 | 2011-03-09 | Phosphoric butane derivative capable of generating tertiary carbon free radical and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102190681B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107418047A (en) * | 2017-06-02 | 2017-12-01 | 中山康诺德新材料有限公司 | A kind of High glow wire halogen-free flame retardant polyolefin composition and preparation method |
| CN109734959A (en) * | 2018-12-17 | 2019-05-10 | 清远市普塞呋磷化学有限公司 | A kind of heat-resistance type radical initiator and its preparation method and application |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3850882A (en) * | 1971-12-01 | 1974-11-26 | Phillips Petroleum Co | Flame retarded compositions and additive systems therefor |
| US20020015847A1 (en) * | 2000-04-06 | 2002-02-07 | Yoshishige Shimizu | Flame retarding polypropylene fiber and production method thereof and flame retarding polypropylene film |
| CN1743369A (en) * | 2004-09-01 | 2006-03-08 | 第一Fr株式会社 | Flame retardant compositions for flammable plastics and flame retarded plastic compositions containing the same |
| CN101880420A (en) * | 2010-04-23 | 2010-11-10 | 上海美莱珀化工材料科技有限公司 | Surface precipitation-free flame-retardant polypropylene compound and preparation method thereof |
-
2011
- 2011-03-09 CN CN201110055605.7A patent/CN102190681B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3850882A (en) * | 1971-12-01 | 1974-11-26 | Phillips Petroleum Co | Flame retarded compositions and additive systems therefor |
| US20020015847A1 (en) * | 2000-04-06 | 2002-02-07 | Yoshishige Shimizu | Flame retarding polypropylene fiber and production method thereof and flame retarding polypropylene film |
| CN1743369A (en) * | 2004-09-01 | 2006-03-08 | 第一Fr株式会社 | Flame retardant compositions for flammable plastics and flame retarded plastic compositions containing the same |
| CN101880420A (en) * | 2010-04-23 | 2010-11-10 | 上海美莱珀化工材料科技有限公司 | Surface precipitation-free flame-retardant polypropylene compound and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107418047A (en) * | 2017-06-02 | 2017-12-01 | 中山康诺德新材料有限公司 | A kind of High glow wire halogen-free flame retardant polyolefin composition and preparation method |
| CN109734959A (en) * | 2018-12-17 | 2019-05-10 | 清远市普塞呋磷化学有限公司 | A kind of heat-resistance type radical initiator and its preparation method and application |
| CN109734959B (en) * | 2018-12-17 | 2021-03-23 | 清远市普塞呋磷化学有限公司 | Temperature-resistant free radical initiator and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102190681B (en) | 2014-04-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Facile synthesis of phosphorus-containing benzotriazole flame retardant for enhancement of mechanical and fire properties of epoxy resins | |
| Wu et al. | Synthesis of reactive phenylphosphoryl glycol ether oligomer and improved flame retardancy and mechanical property of modified rigid polyurethane foams | |
| CN109280219A (en) | A kind of high-efficiency furan ring-containing bio-based flame retardant and its synthesis method and application | |
| JP2013035848A (en) | Novel phosphorus-based biphenol, and method for preparing derivative thereof | |
| CN109134544B (en) | A phosphazene compound, a composition comprising the phosphazene compound, a flame retardant comprising it and applications | |
| CN100463952C (en) | A kind of phosphorus-containing triazine ring flame retardant and preparation method thereof | |
| CN102675895A (en) | Flame-retardant composite material with DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) modified nano mesoporous molecular sieve | |
| CN106220684A (en) | A kind of preparation method of nitrogenous Phosphaphenanthrene derivative flame retardant | |
| CN102260292B (en) | A kind of flame retardant and its preparation method and flame retardant acrylate emulsion using the flame retardant | |
| WO2010098047A1 (en) | Alkenylphosphorus compounds, alkenylphosphorus compound polymers, and alkenylphosphorus compound copolymers | |
| CN102190681B (en) | Phosphoric butane derivative capable of generating tertiary carbon free radical and preparation method thereof | |
| CN114349789A (en) | Furyl phosphate flame retardant and preparation method thereof | |
| CN105229082A (en) | Flame-retardant composition | |
| CN103146023A (en) | Efficient flame retardant aliphatic oligomeric phosphate/phosphonate ester and preparation method thereof | |
| CN108976261A (en) | A kind of preparation method of the aza epoxy curing agent of phosphorus | |
| CN102775445A (en) | Resorcinol-di(9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide)phosphate (RDD) and preparation method thereof | |
| CN109897224A (en) | A kind of reactive flame retardant and its preparation method and application | |
| CN114957655B (en) | Phosphorus-nitrogen high-molecular flame retardant and preparation method thereof | |
| CN109776780B (en) | Phosphorus-containing flame-retardant PTT and preparation method and application thereof | |
| KR101143387B1 (en) | Organic Phosphorous-nitrogen compound having oxazolinone derivatives, preparation method thereof and flame retardant composition containing the same | |
| CN103387673B (en) | Fire retardant and preparation method thereof and purposes | |
| KR101478808B1 (en) | The phosphate ester for flame retadant and preparations thereof | |
| CN109897159A (en) | A kind of reactive flame retardant and its preparation method and application | |
| CN109897164A (en) | A kind of reactive flame retardant and its preparation method and application | |
| CN109897220A (en) | A kind of reactive flame retardant and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: HUNAN MEILAIPO TECHNOLOGY DEVELOPMENT CO., LTD. Effective date: 20140711 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20140711 Address after: 201620 No. 2999 North Renmin Road, Xincheng District, Shanghai, Songjiang Patentee after: Shanghai Meilaipo Chemicals Co., Ltd. Patentee after: Hunan Meilaipo Technology Development Co., Ltd. Address before: 201620 No. 2999 North Renmin Road, Xincheng District, Shanghai, Songjiang Patentee before: Shanghai Meilaipo Chemicals Co., Ltd. |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20180823 Address after: 201600, 5, 13 building, 68 Chuang Chuang Road, Songjiang District, Shanghai. Patentee after: Shanghai Li Dao new material Polytron Technologies Inc Address before: No. 2999, Renmin North Road, Xincheng, Songjiang, Shanghai Co-patentee before: Hunan Meilaipo Technology Development Co., Ltd. Patentee before: Shanghai Meilaipo Chemicals Co., Ltd. |
|
| TR01 | Transfer of patent right |