CN105503957B - A kind of biradical compound based on phosphonitrile and triazine group and preparation method thereof - Google Patents
A kind of biradical compound based on phosphonitrile and triazine group and preparation method thereof Download PDFInfo
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- CN105503957B CN105503957B CN201610073442.8A CN201610073442A CN105503957B CN 105503957 B CN105503957 B CN 105503957B CN 201610073442 A CN201610073442 A CN 201610073442A CN 105503957 B CN105503957 B CN 105503957B
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- Prior art keywords
- dihydroxy
- phosphonitrile
- diaminourea
- triazine group
- organic solvent
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 69
- ZSTLPJLUQNQBDQ-UHFFFAOYSA-N azanylidyne(dihydroxy)-$l^{5}-phosphane Chemical compound OP(O)#N ZSTLPJLUQNQBDQ-UHFFFAOYSA-N 0.000 title claims abstract description 40
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- XEVRDFDBXJMZFG-UHFFFAOYSA-N carbonyl dihydrazine Chemical compound NNC(=O)NN XEVRDFDBXJMZFG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000003960 organic solvent Substances 0.000 claims description 23
- -1 4,4- dioxydiphenyl methanes Chemical class 0.000 claims description 17
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 14
- 239000011230 binding agent Substances 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 10
- 238000000967 suction filtration Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 9
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 9
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 7
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 6
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- GUUVPOWQJOLRAS-UHFFFAOYSA-N diphenyl disulphide Natural products C=1C=CC=CC=1SSC1=CC=CC=C1 GUUVPOWQJOLRAS-UHFFFAOYSA-N 0.000 claims description 5
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 claims description 4
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 4
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 4
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical group NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 claims description 4
- WHJMGMTWMIGGQF-UHFFFAOYSA-N 1,1'-biphenyl;methanamine Chemical group NC.C1=CC=CC=C1C1=CC=CC=C1 WHJMGMTWMIGGQF-UHFFFAOYSA-N 0.000 claims description 3
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical group NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 3
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 claims description 3
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 claims description 3
- GSOIPAHAPAKFEV-UHFFFAOYSA-N C1=C(C(=CC(=C1Cl=O)Cl=O)N)N Chemical compound C1=C(C(=CC(=C1Cl=O)Cl=O)N)N GSOIPAHAPAKFEV-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 claims description 3
- SSJXIUAHEKJCMH-UHFFFAOYSA-N cyclohexane-1,2-diamine Chemical compound NC1CCCCC1N SSJXIUAHEKJCMH-UHFFFAOYSA-N 0.000 claims description 3
- RLMGYIOTPQVQJR-UHFFFAOYSA-N cyclohexane-1,3-diol Chemical class OC1CCCC(O)C1 RLMGYIOTPQVQJR-UHFFFAOYSA-N 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims description 3
- ZJTLZYDQJHKRMQ-UHFFFAOYSA-N menadiol Chemical compound C1=CC=CC2=C(O)C(C)=CC(O)=C21 ZJTLZYDQJHKRMQ-UHFFFAOYSA-N 0.000 claims description 3
- XOOMNEFVDUTJPP-UHFFFAOYSA-N naphthalene-1,3-diol Chemical class C1=CC=CC2=CC(O)=CC(O)=C21 XOOMNEFVDUTJPP-UHFFFAOYSA-N 0.000 claims description 3
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 claims description 3
- RUOPINZRYMFPBF-UHFFFAOYSA-N pentane-1,3-diol Chemical class CCC(O)CCO RUOPINZRYMFPBF-UHFFFAOYSA-N 0.000 claims description 3
- 239000001294 propane Substances 0.000 claims description 3
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical group CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 3
- AXPZIVKEZRHGAS-UHFFFAOYSA-N 3-benzyl-5-[(2-nitrophenoxy)methyl]oxolan-2-one Chemical compound [O-][N+](=O)C1=CC=CC=C1OCC1OC(=O)C(CC=2C=CC=CC=2)C1 AXPZIVKEZRHGAS-UHFFFAOYSA-N 0.000 claims description 2
- 229960000549 4-dimethylaminophenol Drugs 0.000 claims description 2
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 2
- 229940113088 dimethylacetamide Drugs 0.000 claims description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 2
- 230000009267 minimal disease activity Effects 0.000 claims description 2
- 150000003568 thioethers Chemical class 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 4
- SVTBMSDMJJWYQN-UHFFFAOYSA-N hexylene glycol Natural products CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 claims 4
- 229940051250 hexylene glycol Drugs 0.000 claims 3
- 150000004999 2,4-diaminotoluenes Chemical class 0.000 claims 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims 2
- 150000001412 amines Chemical class 0.000 claims 2
- 230000001681 protective effect Effects 0.000 claims 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- 229910052786 argon Inorganic materials 0.000 claims 1
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 claims 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- DFQICHCWIIJABH-UHFFFAOYSA-N naphthalene-2,7-diol Chemical compound C1=CC(O)=CC2=CC(O)=CC=C21 DFQICHCWIIJABH-UHFFFAOYSA-N 0.000 claims 1
- 239000003063 flame retardant Substances 0.000 abstract description 18
- 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 9
- 239000003610 charcoal Substances 0.000 abstract description 6
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 238000002485 combustion reaction Methods 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 239000011159 matrix material Substances 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 3
- 125000001309 chloro group Chemical group Cl* 0.000 abstract description 2
- 230000001629 suppression Effects 0.000 abstract description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 150000001805 chlorine compounds Chemical class 0.000 description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- 150000002169 ethanolamines Chemical class 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- PCHPORCSPXIHLZ-UHFFFAOYSA-N diphenhydramine hydrochloride Chemical compound [Cl-].C=1C=CC=CC=1C(OCC[NH+](C)C)C1=CC=CC=C1 PCHPORCSPXIHLZ-UHFFFAOYSA-N 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 230000000979 retarding effect Effects 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 229920006305 unsaturated polyester Polymers 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- MYOXMAQGEINAEF-UHFFFAOYSA-N [C].N1=NN=CC=C1 Chemical compound [C].N1=NN=CC=C1 MYOXMAQGEINAEF-UHFFFAOYSA-N 0.000 description 1
- YVNRUPSDZZZUQJ-UHFFFAOYSA-N [O].NC1=CC=CC=C1 Chemical compound [O].NC1=CC=CC=C1 YVNRUPSDZZZUQJ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- GLUUGHFHXGJENI-UHFFFAOYSA-N diethylenediamine Natural products C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002171 ethylene diamines Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000004987 o-phenylenediamines Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- DYFXGORUJGZJCA-UHFFFAOYSA-N phenylmethanediamine Chemical compound NC(N)C1=CC=CC=C1 DYFXGORUJGZJCA-UHFFFAOYSA-N 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000003921 pyrrolotriazines Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—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
- C07F9/6581—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 nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
- C07F9/65812—Cyclic phosphazenes [P=N-]n, n>=3
- C07F9/65815—Cyclic phosphazenes [P=N-]n, n>=3 n = 3
-
- 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
- C08K5/5399—Phosphorus bound to nitrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses a kind of biradical compound based on phosphonitrile and triazine group, its preparation method is that triazine group is introduced into six chlorine atoms for having in intrinsically flame retarded hexachlorocyclotriph,sphazene and replacing its side chain, and the side chain of triazine group will be further introduced containing diaminourea or dihydroxy compounds, prepare the biradical compound based on phosphonitrile and triazine group.The compound is rich in N, P element, because containing phosphonitrile and triazine group simultaneously, in combustion, can be by the way that gas phase is fire-retardant and condensed phase mechanism plays fire retardation, also have good into charcoal effect, the layer of charcoal of generation is heat-insulated, suppression oxygen, plays a part of expansion type flame retardant；In addition, phosphonitrile and triazine group have the effect of cooperative flame retardant in matrix combustion process.And the heat endurance of the compound is good, charring rate is high, good processability, can be widely applied to various high polymer materials it is flame-retardant modified in.
Description
Technical field
The invention belongs to technical field of polymer materials, it is related to a kind of fire retardant and preparation method thereof, and in particular to a kind of
Biradical compound based on phosphonitrile and triazine group and preparation method thereof.
Background technology
Triaizine compounds with its excellent carbon-forming performance, be easy to reaction molecular characterization and relative low price advantage and
As research emphasis.Early in nineteen ninety, triaizine compounds and phosphide just are used to build self-gravitation type thermoplastic by Cipolli R etc.
Property polymer or elastomer.2006, Li Bin etc. optimized the synthesis technique of triazine and has invented a kind of hydroxyl and two amidos
Triazine system oligomer and be applied to polyolefin.Hereafter, structure of the people constantly to triaizine compounds is optimized and changed
Enter, designed and synthesized out a series of pyrrolotriazine derivatives.Such as, the triazine macromolecular compound of the chain structure containing aromatic series, main chain contains
The triazine carbon forming agent of piperazine structure, the siliceous triazine oligomer of side chain and hyperbranched triazine macromolecular carbon forming agent etc..Above-mentioned three
Piperazine compound is required for compounding phosphonium flame retardant during fire-retardant, by promoting into charcoal, element collaboration, group cooperative effect
Flame retarding efficiency is set to be further enhanced etc. mode.As can be seen here, it is structure triazine group and phosphor-containing flame-proof group to be carried out compound
Build the effective way of fire retardant new, efficient, that molten drop can be suppressed.
In the combination of the triazine studied with phosphor-containing flame-proof group, using it is most be APP.But polyphosphoric acid
There are many problems when ammonium is used.First, the easy moisture absorption of APP, resistance to migration is poor；Second, APP and polymeric matrix
Compatibility it is bad, influence flame retarding efficiency raising；3rd, the heat endurance of APP is not high, just has portion in process
Decompose.Accordingly, it would be desirable to which developing a kind of new phosphorus-containing flame retardant substitutes APP.
The unique heterocycle structure of cyclic phosphazene compound and higher phosphorus, nitrogen content, make it have excellent heat endurance
And fire resistance, and such compound has good biocompatibility and biological degradability, meets current increasingly harsh
Environmental requirement.The research of ring phosphonitrile fire retardant starts later, and at present, phosphonitrile fire retardant mainly includes：Alkoxycyclotriphosphderivative, benzene
The phosphonitrile of epoxide ring three, the phosphonitrile of phenylamino basic ring three etc..These ring phosphonitrile fire retardants are applied to many macromolecules by researchers
In material, such as polyethylene, acrylonitrile-butadiene-styrene copolymer (ABS), epoxy resin, unsaturated polyester (UP), PLA etc.,
All obtain good flame retardant effect.This explanation phosphazene compound can turn into a kind of efficient fire retardant.But, at present on
The research of phosphonitrile and the biradical compound of triazine has not been reported.
The content of the invention
It is an object of the present invention to provide a kind of heat endurance is good, charring rate is high, with good flame-retardance can based on
The biradical compound of phosphonitrile and triazine group.
The invention provides a kind of biradical compound based on phosphonitrile and triazine group, the chemical structural formula of such compound
For：
Wherein, R is diaminourea or dihydroxy.
It is a further object of the present invention to provide a kind of method for preparing the biradical compound based on phosphonitrile and triazine group.
The preparation method is comprised the following steps that：
The non-proton organic solvent of Cyanuric Chloride is added in the non-proton organic solvent of monoethanolamine by step (1),
Acid binding agent is added in system, in nitrogen or argon atmosphere, is stirred 2~5 hours at -15~20 DEG C, obtains 2,4- bis- chloro-
6- hydroxyethylamino -1,3,5- triaizine compounds.
The molecular structural formula of the chloro- 6- hydroxyethylaminos -1,3,5- triaizine compounds of described 2,4- bis- is
In the non-proton organic solvent of Cyanuric Chloride the concentration of Cyanuric Chloride be 0.16~1.6mol/L, monoethanolamine it is non-
The concentration of monoethanolamine is 0.18~1.8mol/L in protic organic solvent, and the two uses non-proton organic solvent of the same race, plus
Cyanuric Chloride, monoethanolamine, the molar ratio of acid binding agent entered is 1: 1: 1；
Described acid binding agent is triethylamine, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium acid carbonate, bicarbonate
One kind in potassium, pyridine, DMAP, N, N- diisopropylethylamine；
Described non-proton organic solvent is 1-METHYLPYRROLIDONE, N,N-dimethylformamide, N, N- dimethyl second
One kind in acid amides, tetrahydrofuran, dioxane, acetone, butanone, ethyl acetate；
Hexachlorocyclotriph,sphazene is added in the chloro- 6- hydroxyethylaminos -1,3,5- triaizine compounds of step (2) .2,4- bis-
Non-proton organic solvent, and add condensing reflux 5~8 hours under acid binding agent, 50~80 DEG C of stirring conditions；Described is non-proton
Property organic solvent and step (1) use non-proton organic solvent of the same race；
In the non-proton organic solvent of hexachlorocyclotriph,sphazene the concentration of hexachlorocyclotriph,sphazene be 0.06~0.6mol/L, 2,
The molar ratio of the chloro- 6- hydroxyethylaminos -1,3,5- triaizine compounds of 4- bis- and hexachlorocyclotriph,sphazene is 6: 1~12: 1；
Described acid binding agent use with step (1) acid binding agent of the same race, the molar ratio of acid binding agent and hexachlorocyclotriph,sphazene is 6
: 1~12: 1；
Step (3) adds the non-proton organic solvent of diaminourea or dihydroxy compounds into reaction solution；Rise temperature
Degree reacts 3~6 hours to 40~70 DEG C under stirring, condensing condition, continues to raise temperature to 80~120 DEG C, stirring, condensation bar
Reacted 3~6 hours under part；
Described non-proton organic solvent uses non-proton organic solvent of the same race with step (2)；
Diamino compounds or dihydroxy in described diaminourea or the non-proton organic solvent of dihydroxy compounds
The concentration of compound is 2~20mol/L, and the molar ratio of diamino compounds or dihydroxy compounds and hexachlorocyclotriph,sphazene is 12
: 1~24: 1；
The preferred p-phenylenediamine of described diamino compounds, hexamethylene diamine, butanediamine, 4,4- diaminodiphenyl ethers, 4,4- bis-
Aminodiphenyl sulfone, 4,4- MDAs, adjacent biphenyl methylamine, o-phenylenediamine, 1,2- propane diamine, 1,3- propane diamine, 2,4-
Double [4- (the 4- aminobenzene oxygen of diaminotoluene, 3- diethyl amino propylamines, 1,2- cyclohexanediamine, 4,5- dichloros o-phenylenediamine, 2,2-
Base phenyl)] propane, 4,4- diaminodiphenyl sulfides or 4,4- diaminourea diphenyl disulfide；
The preferred hydroquinones of described dihydroxy compounds, pentanediol, 4,4- dihydroxy diphenyl ethers, 4,4- dihydroxy hexichol
Methane, butanediol, ethylene glycol, 1,3-BDO, 1,3- pentanediols, 1,3- cyclohexanediols, Isosorbide-5-Nitrae-cyclohexanediol, 2- ethyls -1,
3- hexylene glycols, catechol, resorcinol, 1,5- dihydroxy naphthlenes, 1,3- naphthalenediols, 2,7- dihydroxy naphthlenes, methylnaphthohydroquinone, 4,4-
Dihydroxy diphenyl sulfide or 4,4- dihydroxy diphenyl disulfide；
After step (4) reactions terminate, by suction filtration, washing, dry, obtain biradicalization based on phosphonitrile and triazine group
Compound.
Cyanuric Chloride, monoethanolamine, acid binding agent, hexachlorocyclotriph,sphazene, diaminourea and dihydroxy compounds in the present invention are
Matured product, can be obtained by market purchase.
The present invention will have in intrinsically flame retarded hexachlorocyclotriph,sphazene and replace with being introduced into the triazine group that charcoal is acted on
Six chlorine atoms of its side chain, and the side chain of triazine group will be further introduced containing diaminourea or dihydroxy compounds, prepare
Biradical compound based on phosphonitrile and triazine group.The compound is rich in N, P element, because containing phosphonitrile and triazine group simultaneously,
In combustion, can be raw also with good into charcoal effect by the way that gas phase is fire-retardant and condensed phase mechanism plays fire retardation
Into layer of charcoal it is heat-insulated, suppression oxygen, play a part of expansion type flame retardant；In addition, phosphonitrile and triazine group are in matrix combustion process
Effect with cooperative flame retardant.And the heat endurance of the compound is good, charring rate is high, good processability, can be widely applied to
Various high polymer materials it is flame-retardant modified in.
Brief description of the drawings
Fig. 1 applies the infrared spectrogram for the biradical compound based on phosphonitrile and triazine group that example is provided for the present invention；
Fig. 2 is the thermogravimetric analysis figure of the biradical compound provided in an embodiment of the present invention based on phosphonitrile and triazine group.
Embodiment
Embodiment 1.
2.00g Cyanuric Chlorides are dissolved in 15ml tetrahydrofuran solutions by step (1), are added to four dissolved with 0.68g monoethanolamines
In hydrogen tetrahydrofuran solution 40ml, sodium carbonate 1.15g is added, in N2In atmosphere, stirred 2 hours at -15 DEG C, obtain 2,4- bis- chloro-
6- hydroxyethylamino -1,3,5- triaizine compounds；
0.68g chlordenes ring three is added in the chloro- 6- hydroxyethylaminos -1,3,5- triaizine compounds of step (2) .2,4- bis-
The 30ml tetrahydrofuran solutions of phosphonitrile, add condensing reflux 5 hours under sodium carbonate 1.15g, 50 DEG C of stirring conditions；
Step (3) adds the 10ml tetrahydrofuran solutions of 1.30g ethylenediamines into reaction solution；Temperature is raised to 40 DEG C,
Reacted 3 hours under stirring, condensing condition, continue to raise temperature to 80 DEG C, reacted 3 hours under stirring, condensing condition；
After step (4) reactions terminate, by suction filtration, washing, dry, obtain biradicalization based on phosphonitrile and triazine group
Compound.
The infrared spectrogram for the biradical compound based on phosphonitrile and triazine group that this example is obtained is as shown in figure 1, its thermogravimetric
Analysis chart is as shown in Figure 2.
Embodiment 2.
4.00g Cyanuric Chlorides are dissolved in 30ml acetone solns by step (1), are added to the molten 50ml of acetone of 1.36g monoethanolamines
In, potassium hydroxide 1.22g is added, in N2In atmosphere, at -10 DEG C stir 2 hours, obtain the chloro- 6- hydroxyethylaminos of 2,4- bis- -
1,3,5- triaizine compounds；
1.36g chlordenes ring three is added in the chloro- 6- hydroxyethylaminos -1,3,5- triaizine compounds of step (2) .2,4- bis-
The 40ml acetone solns of phosphonitrile, add condensing reflux 5 hours under potassium hydroxide 1.22.00g, 50 DEG C of stirring conditions；
Step (3) adds the 15ml acetone solns of 2.80g hexamethylene diamines into reaction solution；Temperature is raised to 45 DEG C, is stirred
Mix, react 3 hours under condensing condition, continue to raise temperature to 85 DEG C, reacted 3 hours under stirring, condensing condition；
After step (4) reactions terminate, by suction filtration, washing, dry, obtain biradicalization based on phosphonitrile and triazine group
Compound.Embodiment 3.
6.00g Cyanuric Chlorides are dissolved in 40ml ethyl acetate solutions by step (1), are added to the second dissolved with 2.05g monoethanolamines
In acetate solution 60ml, sodium hydroxide 1.30g is added, in N2In atmosphere, stirred 2.5 hours at -5 DEG C, obtain 2,4- bis-
Chloro- 6- hydroxyethylaminos -1,3,5- triaizine compounds；
2.05g chlordenes ring three is added in the chloro- 6- hydroxyethylaminos -1,3,5- triaizine compounds of step (2) .2,4- bis-
The 50m ethyl acetate solutions of phosphonitrile, add condensing reflux 5.5 hours under sodium hydroxide 1.30g, 55 DEG C of stirring conditions；
Step (3) adds the 25ml ethyl acetate solutions of 6.90g p-phenylenediamine into reaction solution；Temperature is raised to 55
DEG C, reacted 3 hours under stirring, condensing condition, continue to raise temperature to 85 DEG C, reacted 3 hours under stirring, condensing condition；
After step (4) reactions terminate, by suction filtration, washing, dry, obtain biradicalization based on phosphonitrile and triazine group
Compound.
Embodiment 4.
8.00g Cyanuric Chlorides are dissolved in 50ml dioxane solutions by step (1), are added to two dissolved with 2.72g monoethanolamines
In the ring solution 70ml of oxygen six, triethylamine 4.40g is added, in N2In atmosphere, stirred 2.5 hours at 5 DEG C, obtain 2,4- bis- chloro-
6- hydroxyethylamino -1,3,5- triaizine compounds；
2.72g chlordenes ring three is added in the chloro- 6- hydroxyethylaminos -1,3,5- triaizine compounds of step (2) .2,4- bis-
The 65ml dioxane solutions of phosphonitrile, add condensing reflux 5 hours under triethylamine 4.40g, 50 DEG C of stirring conditions；
Step (3) adds the 30ml dioxane solutions of 9.20g o-phenylenediamines into reaction solution；Temperature is raised to 60
DEG C, reacted 3.5 hours under stirring, condensing condition, continue to raise temperature to 90 DEG C, reacted 3.5 hours under stirring, condensing condition；
After step (4) reactions terminate, by suction filtration, washing, dry, obtain biradicalization based on phosphonitrile and triazine group
Compound.
Embodiment 5.
10.00g Cyanuric Chlorides are dissolved in 50mlN by step (1), and dinethylformamide solution is added to dissolved with 3.4g second
In the DMF solution 50ml of hydramine, pyridine 4.18g is added, in N2In atmosphere, stir 3 hours, obtain at 10 DEG C
To the chloro- 6- hydroxyethylaminos -1,3,5- triaizine compounds of 2,4- bis-；
The phosphorus of 3.5g chlordenes ring three is added in the chloro- 6- hydroxyethylaminos -1,3,5- triaizine compounds of step (2) .2,4- bis-
The 60mlN of nitrile, dinethylformamide solution adds condensing reflux 6 hours under pyridine 4.18g, 60 DEG C of stirring conditions；
Step (3) adds the 40mlN of 11.88g hydroquinones, dinethylformamide solution into reaction solution；Rise
Temperature is reacted 4 hours to 65 DEG C under stirring, condensing condition, continues to raise temperature to 90 DEG C, reaction 4 is small under stirring, condensing condition
When；
After step (4) reactions terminate, by suction filtration, washing, dry, obtain biradicalization based on phosphonitrile and triazine group
Compound.
Embodiment 6.
12.00g Cyanuric Chlorides are dissolved in 60mlN- methylpyrrolidone solutions by step (1), are added to dissolved with 4.10g second
In the 1-METHYLPYRROLIDONE solution 50ml of hydramine, sodium acid carbonate 5.48g is added, in N2In atmosphere, stir 2 hours, obtain at 5 DEG C
To the chloro- 6- hydroxyethylaminos -1,3,5- triaizine compounds of 2,4- bis-；
4.09g chlordenes ring three is added in the chloro- 6- hydroxyethylaminos -1,3,5- triaizine compounds of step (2) .2,4- bis-
The 60mlN- methylpyrrolidone solutions of phosphonitrile, add condensing reflux 6.5 hours under sodium acid carbonate 5.48g, 65 DEG C of stirring conditions；
Step (3) adds the 10mlN- methylpyrrolidone solutions of 9.7g ethylene glycol into reaction solution；Raise temperature extremely
40 DEG C, stirring, react 4 hours under condensing condition, continue to raise temperature to 95 DEG C, reacted 3 hours under stirring, condensing condition；
After step (4) reactions terminate, by suction filtration, washing, dry, obtain biradicalization based on phosphonitrile and triazine group
Compound.
Embodiment 7.
16.00g Cyanuric Chlorides are dissolved in 60ml DMA solution by step (1), are added to dissolved with 5.5g
In the DMA solution 40ml of monoethanolamine, saleratus 8.69g is added, in N2In atmosphere, 2 are stirred at -15 DEG C
Hour, obtain the chloro- 6- hydroxyethylaminos -1,3,5-triazines compounds of 2,4- bis-；
The phosphorus of 5.5g chlordenes ring three is added in the chloro- 6- hydroxyethylaminos -1,3,5- triaizine compounds of step (2) .2,4- bis-
The 60ml DMA solution of nitrile, adds condensing reflux 5 hours under saleratus 8.69g, 70 DEG C of stirring conditions；
Step (3) adds the 10ml DMAC N,N' dimethyl acetamide solution of 27.6g butanediols into reaction solution；Rise temperature
Degree reacts 4 hours to 70 DEG C under stirring, condensing condition, continues to raise temperature to 100 DEG C, reaction 4 is small under stirring, condensing condition
When；
After step (4) reactions terminate, by suction filtration, washing, dry, obtain biradicalization based on phosphonitrile and triazine group
Compound.
Embodiment 8.
20.00g Cyanuric Chlorides are dissolved in 60ml solution dioxane by step (1), are added to dissolved with 6.95g monoethanolamines
In dioxane solution 60ml, potassium carbonate 20g is added, in N2In atmosphere, stirred 2.5 hours at -5 DEG C, obtain 2,4- bis- chloro-
6- hydroxyethylamino -1,3,5- triaizine compounds；
6.35g chlordenes ring three is added in the chloro- 6- hydroxyethylaminos -1,3,5- triaizine compounds of step (2) .2,4- bis-
The 30ml dioxane solutions of phosphonitrile, add condensing reflux 8 hours under potassium carbonate 20g, 80 DEG C of stirring conditions；
Step (3) adds the 10ml dioxane solutions of 12.96g hexamethylene diamines into reaction solution；Temperature is raised to 70
DEG C, reacted 6 hours under stirring, condensing condition, continue to raise temperature to 120 DEG C, reacted 3 hours under stirring, condensing condition；
After step (4) reactions terminate, by suction filtration, washing, dry, obtain biradicalization based on phosphonitrile and triazine group
Compound.
Claims (5)
1. a kind of preparation method of the biradical compound based on phosphonitrile and triazine group, it is characterised in that comprise the following steps：
The non-proton organic solvent of Cyanuric Chloride is added in the non-proton organic solvent of monoethanolamine by step (1), system
Middle addition acid binding agent, in protective gas atmosphere, stirs 2~5 hours at -15~20 DEG C, obtains the chloro- 6- hydroxyls second of 2,4- bis-
Amino -1,3,5- triaizine compounds；
Wherein, the concentration of Cyanuric Chloride is 0.16~1.6mol/L, second in the non-proton organic solvent of described Cyanuric Chloride
The concentration of monoethanolamine is 0.18~1.8mol/L in the non-proton organic solvent of hydramine, the Cyanuric Chloride of addition, monoethanolamine, is tied up
The molar ratio of sour agent is 1: 1: 1；
The non-matter of hexachlorocyclotriph,sphazene is added in the chloro- 6- hydroxyethylaminos -1,3,5- triaizine compounds of step (2) 2,4- bis-
Sub- property organic solvent, and add condensing reflux 5~8 hours under acid binding agent, 50~80 DEG C of stirring conditions；
Wherein, in the non-proton organic solvent of described hexachlorocyclotriph,sphazene the concentration of hexachlorocyclotriph,sphazene for 0.06~
The molar ratio of 0.6mol/L, 2,4- bis- chloro- 6- hydroxyethylaminos -1,3,5-triazines compounds and hexachlorocyclotriph,sphazene is 6
: 1~12: 1；The molar ratio of acid binding agent and hexachlorocyclotriph,sphazene is 6: 1~12: 1；
Step (3) is to step 2) diaminourea is added in obtained reaction solution or the aprotic of dihydroxy compounds is organic molten
Agent；Temperature is raised to 40~70 DEG C, is reacted 3~6 hours under stirring, condensing condition, continues to raise temperature to 80~120 DEG C, stirs
Mix, react 3~6 hours under condensing condition；
Wherein, diaminourea or dihydroxy compounds in the non-proton organic solvent of described diaminourea or dihydroxy compounds
Concentration is 2~20mol/L, and the molar ratio that diaminourea or dihydroxy compounds add hexachlorocyclotriph,sphazene with step (2) is
12: 1~24: 1；
After step (4) reaction terminates, by suction filtration, washing, dry, obtain the biradical compound based on phosphonitrile and triazine group；
Above-mentioned all non-proton organic solvents use same non-proton organic solvent；Above-mentioned all acid binding agents are equal
Using same acid binding agent；Described diamino compounds be p-phenylenediamine, hexamethylene diamine, butanediamine, 4,4- diaminodiphenyl ethers,
4,4- diaminodiphenylsulfones, 4,4- MDAs, adjacent biphenyl methylamine, o-phenylenediamine, 1,2- propane diamine, 1,3- the third two
Double [4- (the 4- ammonia of amine, 2,4- diaminotoluenes, 3- diethyl amino propylamines, 1,2- cyclohexanediamine, 4,5- dichloros o-phenylenediamine, 2,2-
Phenoxyl phenyl)] propane, 4,4- diaminodiphenyl sulfides or 4,4- diaminourea diphenyl disulfide；Described dihydroxy chemical combination
Thing is hydroquinones, pentanediol, 4,4- dihydroxy diphenyl ethers, 4,4- dioxydiphenyl methanes, butanediol, ethylene glycol, 1,3- fourths
Glycol, 1,3- pentanediols, 1,3- cyclohexanediols, Isosorbide-5-Nitrae-cyclohexanediol, 2- ethyls -1,3- hexylene glycol, catechol, isophthalic two
Phenol, 1,5- dihydroxy naphthlenes, 1,3- naphthalenediols, 2,7- dihydroxy naphthlenes, methylnaphthohydroquinone, 4,4- dihydroxy diphenyl sulfide or 4,4- bis-
Hydroxyl diphenyl disulfide.
2. the preparation method of biradical compound according to claim 1, it is characterised in that described protective gas is nitrogen
Or argon gas.
3. the preparation method of biradical compound according to claim 1, it is characterised in that described acid binding agent is three second
Amine, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium acid carbonate, saleratus, pyridine, DMAP, N, N-
One kind in diisopropylethylamine.
4. the preparation method of biradical compound according to claim 1, it is characterised in that described aprotic is organic molten
Agent be 1-METHYLPYRROLIDONE, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, tetrahydrofuran, dioxane, acetone,
One kind in butanone, ethyl acetate.
5. the biradical compound based on phosphonitrile and triazine group made from the method as described in claim any one of 1-4, it is special
Levy and be, the chemical structural formula of such compound is：
Wherein, R is containing diaminourea or dihydric group, from diaminourea or dihydroxy compounds, described diaminourea chemical combination
Thing is p-phenylenediamine, hexamethylene diamine, butanediamine, 4,4- diaminodiphenyl ethers, 4,4- diaminodiphenylsulfones, 4,4- diaminourea hexichol first
Alkane, adjacent biphenyl methylamine, o-phenylenediamine, 1,2- propane diamine, 1,3- propane diamine, 2,4- diaminotoluenes, 3- diethyl amino propylamines, 1,
2- cyclohexanediamine, 4,5- dichloros o-phenylenediamine, 2,2- double [4- (4- aminophenoxy phenyls)] propane, 4,4- diaminourea diphenyl sulfides
Ether or 4,4- diaminourea diphenyl disulfide；Described dihydroxy compounds is hydroquinones, pentanediol, 4,4- dihydroxy hexichol
Ether, 4,4- dioxydiphenyl methanes, butanediol, ethylene glycol, 1,3-BDO, 1,3- pentanediols, 1,3- cyclohexanediols, Isosorbide-5-Nitrae-ring
Hexylene glycol, 2- ethyls -1,3- hexylene glycol, catechol, resorcinol, 1,5- dihydroxy naphthlenes, 1,3- naphthalenediols, 2,7- dihydroxy
Naphthalene, methylnaphthohydroquinone, 4,4- dihydroxy diphenyl sulfide or 4,4- dihydroxy diphenyl disulfide.
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| CN112358507B (en) * | 2020-10-16 | 2021-12-21 | 华南理工大学 | Star-structure fluorine-containing phosphazene flow modifier and preparation method and application thereof |
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