CN109053935A - A kind of novel high polymer self-supported salicylic alidehyde imine metal titanium complex, synthetic method and application method - Google Patents
A kind of novel high polymer self-supported salicylic alidehyde imine metal titanium complex, synthetic method and application method Download PDFInfo
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- CN109053935A CN109053935A CN201810748868.8A CN201810748868A CN109053935A CN 109053935 A CN109053935 A CN 109053935A CN 201810748868 A CN201810748868 A CN 201810748868A CN 109053935 A CN109053935 A CN 109053935A
- Authority
- CN
- China
- Prior art keywords
- titanium complex
- allyl
- metal titanium
- alidehyde imine
- supported
- Prior art date
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Links
- 239000010936 titanium Substances 0.000 title claims abstract description 203
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 187
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 187
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 137
- 239000002184 metal Substances 0.000 title claims abstract description 137
- 150000002466 imines Chemical class 0.000 title claims abstract description 131
- 229920000642 polymer Polymers 0.000 title claims abstract description 88
- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000010189 synthetic method Methods 0.000 title claims abstract description 27
- 239000005977 Ethylene Substances 0.000 claims abstract description 49
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 48
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000000178 monomer Substances 0.000 claims abstract description 48
- 239000003054 catalyst Substances 0.000 claims abstract description 44
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 34
- 229920002521 macromolecule Polymers 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 11
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 78
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 68
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 60
- 239000003446 ligand Substances 0.000 claims description 59
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 56
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 48
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 claims description 48
- 206010001497 Agitation Diseases 0.000 claims description 44
- 238000013019 agitation Methods 0.000 claims description 44
- 238000003786 synthesis reaction Methods 0.000 claims description 39
- 239000000047 product Substances 0.000 claims description 37
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 235000019441 ethanol Nutrition 0.000 claims description 33
- 239000001257 hydrogen Substances 0.000 claims description 33
- 229910052739 hydrogen Inorganic materials 0.000 claims description 33
- 239000007787 solid Substances 0.000 claims description 32
- 229910052757 nitrogen Inorganic materials 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 27
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 26
- 238000001914 filtration Methods 0.000 claims description 26
- 230000015572 biosynthetic process Effects 0.000 claims description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- 239000000126 substance Substances 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 24
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 19
- 238000012662 bulk polymerization Methods 0.000 claims description 17
- 239000003426 co-catalyst Substances 0.000 claims description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- 239000012190 activator Substances 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 238000006392 deoxygenation reaction Methods 0.000 claims description 16
- 229920001038 ethylene copolymer Polymers 0.000 claims description 16
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 16
- 229910001220 stainless steel Inorganic materials 0.000 claims description 16
- 239000010935 stainless steel Substances 0.000 claims description 16
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 14
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 14
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 14
- 229910052794 bromium Inorganic materials 0.000 claims description 14
- 239000000460 chlorine Substances 0.000 claims description 14
- 229910052801 chlorine Inorganic materials 0.000 claims description 14
- 239000003513 alkali Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 9
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 8
- 150000001299 aldehydes Chemical class 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000012043 crude product Substances 0.000 claims description 8
- 238000006073 displacement reaction Methods 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 8
- 235000019253 formic acid Nutrition 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 239000003208 petroleum Substances 0.000 claims description 8
- 230000001376 precipitating effect Effects 0.000 claims description 8
- 238000001953 recrystallisation Methods 0.000 claims description 8
- 239000012453 solvate Substances 0.000 claims description 8
- 238000006467 substitution reaction Methods 0.000 claims description 8
- UDJZTGMLYITLIQ-UHFFFAOYSA-N 1-ethenylpyrrolidine Chemical class C=CN1CCCC1 UDJZTGMLYITLIQ-UHFFFAOYSA-N 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 150000002576 ketones Chemical class 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 5
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 229940090668 parachlorophenol Drugs 0.000 claims description 3
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 229920002866 paraformaldehyde Polymers 0.000 claims description 2
- 241000219000 Populus Species 0.000 claims 1
- 150000004705 aldimines Chemical class 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 239000012535 impurity Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 12
- 239000003999 initiator Substances 0.000 description 10
- CTXUTPWZJZHRJC-UHFFFAOYSA-N 1-ethenylpyrrole Chemical class C=CN1C=CC=C1 CTXUTPWZJZHRJC-UHFFFAOYSA-N 0.000 description 8
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 8
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000005507 spraying Methods 0.000 description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 5
- 125000003963 dichloro group Chemical group Cl* 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 3
- WKBALTUBRZPIPZ-UHFFFAOYSA-N 2,6-di(propan-2-yl)aniline Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N WKBALTUBRZPIPZ-UHFFFAOYSA-N 0.000 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 description 3
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004342 Benzoyl peroxide Substances 0.000 description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- RCEJCSULJQNRQQ-UHFFFAOYSA-N 2-methylbutanenitrile Chemical compound CCC(C)C#N RCEJCSULJQNRQQ-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 2
- 235000019628 coolness Nutrition 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- FYLJKQFMQFOLSZ-UHFFFAOYSA-N cyclohexylperoxycyclohexane Chemical group C1CCCCC1OOC1CCCCC1 FYLJKQFMQFOLSZ-UHFFFAOYSA-N 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- 125000000950 dibromo group Chemical group Br* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- YNJSNEKCXVFDKW-UHFFFAOYSA-N 3-(5-amino-1h-indol-3-yl)-2-azaniumylpropanoate Chemical compound C1=C(N)C=C2C(CC(N)C(O)=O)=CNC2=C1 YNJSNEKCXVFDKW-UHFFFAOYSA-N 0.000 description 1
- MKKSTJKBKNCMRV-UHFFFAOYSA-N 5-bromo-2-hydroxybenzaldehyde Chemical compound OC1=CC=C(Br)C=C1C=O MKKSTJKBKNCMRV-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- RLRBAKQRPZRHGH-UHFFFAOYSA-N N1C(CCC1)=O.C(=C)N1CC=CC=C1 Chemical compound N1C(CCC1)=O.C(=C)N1CC=CC=C1 RLRBAKQRPZRHGH-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- JDZJVWAHZYIHFA-UHFFFAOYSA-N [Br].C1(=CC=CC=C1)O Chemical compound [Br].C1(=CC=CC=C1)O JDZJVWAHZYIHFA-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- FYIBPWZEZWVDQB-UHFFFAOYSA-N dicyclohexyl carbonate Chemical class C1CCCCC1OC(=O)OC1CCCCC1 FYIBPWZEZWVDQB-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- JMPVESVJOFYWTB-UHFFFAOYSA-N dipropan-2-yl carbonate Chemical class CC(C)OC(=O)OC(C)C JMPVESVJOFYWTB-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- -1 ethylene, propylene Chemical group 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F26/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F26/06—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
- C08F26/10—N-Vinyl-pyrrolidone
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The present invention discloses self-supported salicylic alidehyde imine metal titanium complex, synthetic method and the application method of a kind of novel high polymer.The self-supported salicylic alidehyde imine metal titanium complex D of a kind of novel high polymer has been prepared as raw material, by copolymerization in the salicylic alidehyde imine metal titanium complex and ethylene that the present invention is replaced using allyl1~D6, obtained titanium complex D1~D6Can efficient catalytic n-vinyl pyrrolidone homopolymerization, monomer NVP, catalyst residual rate are extremely low, can satisfy the quality requirement of the pharmaceutical grade PVP of high quality.Obtained titanium complex D1~D6It is also dispersible in the solution of n-vinyl pyrrolidone, is catalyzed the polymerisation in solution of n-vinyl pyrrolidone.Titanium complex D1~D6It can be used as catalyst circulation use.It polymerize compared to existing catalysis n-vinyl pyrrolidone, the self-supported salicylic alidehyde imine Titanium composition catalyst polymerization of this kind of macromolecule is efficient, noresidue after catalyst recycling, can preferably meet requirement of the pharmaceutical grade PVP of high quality to impurity contents such as monomer, catalyst.
Description
Technical field
The invention belongs to Nonmetallocene titanium complex catalyst technical fields.It is self-supported to be related to a kind of novel macromolecule
Salicylic alidehyde imine metal titanium complex, synthetic method and the application method that allyl replaces.
Background knowledge
Poly- (n-vinyl pyrrolidone) (polyvinyl pyrrolidone, abbreviation PVP) is a kind of non-ionic high score
Sub- fine chemicals, wherein pharmaceutical grade PVP is widely used in drug production.Pharmacopoeia of each country especially North America, Europe, Japan is right
There is very high quality standard in medicinal PVP, has particularly with the residual quantity of n-vinyl pyrrolidone monomer and initiator
Stringent limitation.
PVP is obtained for raw material by the methods of bulk polymerization, polymerisation in solution with monomers vinylpyrrolidone (NVP).
Industrially it is generally used solution polymerization process synthesis PVP.(solvent can be ethyl alcohol, benzene etc.), which is added, in the solution of NVP causes
Agent is the most common method of NVP homopolymerization by free radical solution polymerization, and most done using AIBN is caused in the polymerization of PVP
Agent has no that useful water-soluble azo class initiator cause the document of synthesis PVP.Since NVP monomer and PVP are dissolved in water
, AIBN contains the group cyano being harmful to the human body, and PVP is the product being mostly used for direct body contact again, so not adopting
It is catalyzed the homopolymerization of NVP with the initiator containing the group cyano being harmful to the human body or catalyst, is the development side of pharmaceutical grade PVP
To.
ZL 201210410071.X discloses the preparation method of a kind of poly- (n-vinyl pyrrolidone), and this method uses
Azodiisobutyronitrile, azo-bis-iso-dimethyl, azobis methylbutyronitrile, benzoyl peroxide, isopropyl benzene hydroperoxide, mistake
Aoxidize di-t-butyl, cumyl peroxide, methyl ethyl ketone peroxide or di-cyclohexylperoxy di-carbonate, cyclohexanone peroxide,
Peroxidized t-butyl perbenzoate, peroxidized t-butyl perbenzoate, di-isopropyl peroxydicarbonate or lauroyl peroxide composition
PVP is prepared in composite initiator.But the residual rate of NVP monomer is high in the PVP that the method is prepared, initiator (catalysis
Agent) residual quantity height, it is not able to satisfy field of medicaments PVP standard.And this method preparation efficiency is low, the reaction time is long, and energy consumption is high, unfavorable
In the industrialized production of PVP.
The self-supported salicylic alidehyde imine metal titanium complex D of novel high polymer obtained by the present patent application1~D630
To the homopolymerization of monomer N-vinyl pyrrolidones within the scope of~100 DEG C, have superelevation catalytic activity (more than 1000,
000g·PVP mol-1·Ti-1·h-1).Compared to the loads such as magnesium chloride, silica, kaolin transient metal complex not
It is dissolved in for the monomers containing vinyl such as ethylene, propylene, n-vinyl pyrrolidone, macromolecule obtained by the application is self-supported
Salicylic alidehyde imine metal titanium complex D1~D6It can preferably mix with various vinyl monomers, so that this kind of macromolecule is certainly
The salicylic alidehyde imine metal titanium complex D of load1~D6It is capable of the homopolymerization of homogeneous catalysis vinyl monomer, therefore, such is
The efficiency of phase catalytic reaction is more much higher than the catalytic efficiency of heterogeneous salicylic alidehyde imine Titanium composition catalyst.Specifically
From the point of view of application angle, compared with the polymerization reaction that initiator used by prior art causes monomer NVP, such macromolecule
Self-supported titanium complex catalyst is capable of the homopolymerization of efficient catalytic NVP in a short time, obtains the poly- of high molecular weight
(n-vinyl pyrrolidone).It is catalyzed the significant increase of reaction efficiency, so that the conversion ratio of monomer NVP greatly improves, monomer NVP
Residual rate in polymerizate greatly reduces, the residual quantity of catalyst and co-catalyst is few, can meet height well
Requirement of the pharmaceutical grade PVP of quality to impurity contents such as monomer, catalyst.
Invention additionally discloses the self-supported salicylic alidehyde imine metal titanium complexes of a kind of novel high polymer as catalyst, urges
Change the polymerization reaction of the aqueous solution of NVP.The self-supported salicylic alidehyde imine metal titanium complex D of macromolecule is not soluble in water, Yi Yurong
Poly- (n-vinyl pyrrolidone) in water is separated and is recycled after being recovered by filtration.Compared to existing azodiisobutyronitrile,
Azo-bis-iso-dimethyl, azobis methylbutyronitrile, benzoyl peroxide, isopropyl benzene hydroperoxide, di-t-butyl peroxide,
Cumyl peroxide, methyl ethyl ketone peroxide or di-cyclohexylperoxy di-carbonate, cyclohexanone peroxide, perbenzoic acid uncle
The initiators such as butyl ester, peroxidized t-butyl perbenzoate, di-isopropyl peroxydicarbonate or lauroyl peroxide are catalyzed N- ethylene
The polymerization of base pyrrolidone solution, the self-supported salicylic alidehyde imine metal titanium complex D of this kind of macromolecule1~D6It is catalyzed N- vinyl
The polymerization reaction of pyrrolidones is more efficient, catalyst noresidue and is recycled for multiple times after can recycling.Catalyzed polymerization process is green
Color is efficient, can preferably meet requirement of the pharmaceutical grade PVP of high quality to impurity contents such as monomer, catalyst.
Summary of the invention
The self-supported salicylic alidehyde imine metal titanium complex of a kind of novel high polymer, it is characterised in that the novel height of one kind
The self-supported salicylic alidehyde imine metal titanium complex of molecule is denoted as D, structural formula are as follows:
Wherein: R1Selected from one of following substances: hydrogen, bromine, chlorine；R2And R3To be each independently selected from following substances
One kind: hydrogen, isopropyl.Work as R1=chlorine and R2=R3When=isopropyl, D is D1；Work as R1=bromine and R2=R3=isopropyl
When, D is D2；Work as R1=hydrogen and R2=R3When=isopropyl, D is D3；Work as R1=chlorine and R2=R3When=hydrogen, D is D4；When
R1=bromine and R2=R3When=hydrogen, D is D5；Work as R1=hydrogen and R2=R3When=hydrogen, D is D6。
" → ", indicates coordinate bond.
Indicate the macromolecule chain section that allyl and ethylene copolymer are formed.
The self-supported salicylic alidehyde imine metal titanium complex D (D of a kind of novel high polymer1Or D2Or D3Or D4Or D5Or D6),
It is the salicylic alidehyde imine metal titanium complex A (A replaced by a kind of novel allyl1Or A2Or A3Or A4Or A5Or A6) and ethylene it is logical
It crosses copolymerization process to be prepared, reaction is as follows:
Indicate the macromolecule chain section that allyl and ethylene copolymer are formed；
Synthetic method comprises the concrete steps that: 250mL polymeric kettle being vacuumized water removal deoxygenation, after nitrogen is sufficiently displaced from, then is led to
Enter ethylene displacement nitrogen, and the toluene solvant of 100mL is added under the protection of ethylene, it is full to dissolving to be passed through normal pressure ethylene gas
With, a kind of salicylic alidehyde imine metal titanium complex A of novel allyl substitution of 1~100 μm of ol is added as major catalyst, and
The methylaluminoxane MAO of corresponding proportion is added as co-catalyst, wherein the substance of co-catalyst MAO and metal titanium complex A
Amount ratio be 10~1000:1.It then proceedes to be passed through ethylene, and in 0~100 DEG C and 0.1~10MPa and magnetic agitation condition
0.5~1h of lower polymerization reaction, closes the inlet valve of ethylene, and polymeric kettle is vented to normal pressure, and material, mistake are released from polymeric kettle
Filter, obtains polymer crude product, ethanol washing, and obtained solid is dried in vacuo at 60 DEG C, obtains a kind of novel high polymer and thinks highly of oneself
The salicylic alidehyde imine metal titanium complex D of load, the content of Titanium therein are between 4.1 μm of ol/g~60.0 μm ol/g.
The synthetic method for the salicylic alidehyde imine metal titanium complex A that a kind of novel allyl replaces, it is characterised in that described
Synthetic method comprises the concrete steps that:
Step 1: the synthesis of ligand.
The structural formula of ligand E are as follows:
Wherein: R1Selected from one of following substances: hydrogen, bromine, chlorine；R2And R3To be each independently selected from following substances
One kind: hydrogen, isopropyl.
Work as R1=chlorine and R2=R3When=isopropyl, E is E1；Work as R1=bromine and R2=R3When=isopropyl, E is E2；
Work as R1=hydrogen and R2=R3When=isopropyl, E is E3；Work as R1=chlorine and R2=R3When=hydrogen, E is E4；Work as R1=bromine and R2
=R3When=hydrogen, E is E5；Work as R1=hydrogen and R2=R3When=hydrogen, E is E6。
The synthesis of ligand E includes two stages: first stage is the synthesis of allyl substituted salicylic aldehydes；Second stage
It is condensed for allyl substituted salicylic aldehydes and aniline or 2,6-DIPA through schiff alkali, obtains ligand E.
The synthesis of allyl substituted salicylic aldehydes: vacuumizing logical nitrogen for the reaction flask of 250mL, after nitrogen is replaced 3 times,
The dry toluene of 100mL is added under the protection of nitrogen, the 2- allyl parachlorophenol or 2- allyl of 0.2~1.1mmol is to bromine
Phenol, the anhydrous SnCl of 0.01~0.04mmol4, 2, the 6- lutidines of 0.8~4.4mmol, magnetic agitation flows back at room temperature
After reacting 20min, the paraformaldehyde of 1~5mmol is added, temperature is increased to 80 DEG C, reacts 2h.Product separation, purifying, drying
Afterwards, 3- allyl -5- chloro-salicylic aldehyde, 3- allyl -5- bromosalicylaldehyde are respectively obtained.
Allyl substituted salicylic aldehydes and aniline or or 2,6-DIPA be condensed through schiff alkali, obtain ligand E: will
The 3- allyl salicylide of 10mmol or 3- allyl -5- chloro-salicylic aldehyde or 3- allyl -5- bromosalicylaldehyde are respectively with 10
The aniline or 2,6-DIPA of~11mmol is added in the methanol solvate of 50mL, and the formic acid of 0.1~0.2mmol is added
As catalyst, after magnetic agitation reacts 1~2h at 20~50 DEG C, in -10~0 DEG C of cooling precipitation solid, filtering, filter residue
It after about 5 DEG C of cold ethanol washings, refilters, after recrystallization, about 5 DEG C of cold ethyl alcohol are washed again, filtered in ethanol, solid is dry
Obtain ligand E1~E6。
Step 2: the salicylic alidehyde imine metal titanium complex A that a kind of novel allyl replaces1~A6Synthesis, wherein A1With
E1It is corresponding, A2With E2It is corresponding, A3With E3It is corresponding, A4With E4It is corresponding, A5With E5It is corresponding, A6With E6It is corresponding.
By ligand E (E described in 1.0~2.0mmol1Or E2Or E3Or E4Or E5Or E6) be dissolved in 50mL methylene chloride, -30
DEG C and good stirring condition under, be added dropwise in 1h by 0.5~1.0mmolTiCl4With the solution of 30mL methylene chloride composition, rise
Height reacts 2h to 30~45 DEG C of magnetic agitations, and the triethylamine of 1.0~2.0mmol is then injected with syringe, is continued at 30~45 DEG C
Be stirred to react 2h, then concentration of reaction solution to about 40mL, 30-50mL petroleum ether be added as filtering after precipitating reagent, filter residue with 3 ×
After the cold methylene chloride of 10mL washs 3 times, resulting solid recrystallizes in methylene chloride, filters, is dried to obtain a kind of novel alkene
The salicylic alidehyde imine metal titanium complex A that propyl replaces1~A6。
Step 2 is carried out under the conditions of anhydrous and oxygen-free.
The self-supported salicylic alidehyde imine metal titanium complex D of a kind of novel high polymer can be catalyzed monomer N-vinyl pyrroles
The bulk polymerization of alkanone (NVP), can also be catalyzed the polymerisation in solution of monomer N-vinyl pyrrolidones (NVP).Titanium complex D
The bulk polymerization of catalysis monomer N-vinyl pyrrolidones (NVP) is characterized in that the specific steps of the application method are such as
Under:
Stainless steel polymeric kettle is heated and vacuumized deoxygenation, pure argon is passed through and is sufficiently displaced from completely.The NVP of addition 30g,
The Ti content of 0.1~0.5g is the self-supported salicylic alidehyde imine Titanium of the novel high polymer of 4.1 μm of ol/g~60.0 μm ol/g
Complex D (D1Or D2Or D3Or D4Or D5Or D6) and the methylaluminoxane (MAO) of corresponding proportion be used as activator, wherein activator
The ratio of the amount of the substance of MAO and metal titanium complex D is 10~100:1.Magnetic agitation is poly- in 30~100 DEG C of constant temperature oil baths
0.5~1h of reaction is closed, 10g~20g deionized water, which is added, inactivates system, finally spray-dried to obtain poly- (N- vinylpyridine
Pyrrolidone) powder product.
The self-supported salicylic alidehyde imine metal titanium complex D of a kind of novel high polymer can also be catalyzed monomer N-vinyl pyrrole
The application method of the polymerisation in solution of pyrrolidone.It is characterized in that specific step is as follows for the application method:
NVP, the 60~90g deionized water of 30g is added in stainless steel polymeric kettle, the Ti content of 3~5g is 4.1~60.0 μ
The self-supported salicylic alidehyde imine metal titanium complex D (D of the novel high polymer of mol/g1Or D2Or D3Or D4Or D5Or D6).30~
In 100 DEG C of constant temperature oil baths after 0.5~1h of magnetic agitation polymerization reaction, filtering, gained filter residue is insoluble in aqueous solutions of polymers body
The titanium complex D of system, the catalyst circulation that can be used as the aqueous solution polymerization of catalysis NVP after multiple water washing is dry make
With.Filtrate systems are spray-dried to obtain poly- (N- vinyl pyrrolidone) powder product.
Compared with prior art, the present invention having following obvious advantages:
The present invention proposes the self-supported salicylic alidehyde imine metal titanium complex of the excellent novel high polymer of a kind of catalytic performance
Catalyst compares and uses azodiisobutyronitrile, azo-bis-iso-dimethyl, azo dimethyl butyrate in current PVP preparation process
Nitrile, benzoyl peroxide, isopropyl benzene hydroperoxide, di-t-butyl peroxide, cumyl peroxide, methyl ethyl ketone peroxide or mistake
Aoxidize two dicyclohexyl carbonates, cyclohexanone peroxide, peroxidized t-butyl perbenzoate, peroxidized t-butyl perbenzoate, peroxidating
The initiators system such as two diisopropyl carbonates or lauroyl peroxide, the self-supported salicylic alidehyde imine Titanium of novel high polymer are matched
Mixture catalyst catalytic activity is higher.When therefore, using catalyst preparation PVP of the invention, needed for the preparation of unit polymer
The amount for the catalyst wanted can greatly reduce, moreover, the self-supported titanium complex catalyst of the macromolecule does not dissolve in monomer NVP
Aqueous solution, after the completion of polymerization, catalyst D can be recycled for multiple times after being recovered by filtration, therefore the unit consumption and cost of catalyst
It can greatly reduce, and polymerization process is environmentally protective, poisonous and hazardous initiator and organic solvent not used in polymerization, is urged
Change and polymerize efficient, good product quality, monomer-free can satisfy field of medicaments PVP and answer also without the residual of catalyst in resulting PVP
With requiring.
Detailed description of the invention
Fig. 1 is the ligand E of the embodiment of the present invention 11's1H NMR figure；
Fig. 2 is the infrared figure of poly- (n-vinyl pyrrolidone) product of the embodiment of the present invention 1；
Fig. 3 is poly- (n-vinyl pyrrolidone) product of the embodiment of the present invention 11H NMR figure；
Fig. 4 is poly- (n-vinyl pyrrolidone) product of the embodiment of the present invention 112C NMR figure.
Example is embodied
Below by specific implementation example, the invention will be further described, but it needs to be emphasized that the present invention is never only
The example for being only limitted to act listed below.In following cases:
Work as R1=chlorine, R2=R3When=isopropyl, corresponding ligand E1, the salicylide Asia of corresponding novel allyl substitution
Amine metal titanium complex is A1, the self-supported salicylic alidehyde imine metal titanium complex of corresponding novel high polymer is D1；
Work as R1=bromine, R2=R3When=isopropyl, corresponding ligand E2, the salicylide Asia of corresponding novel allyl substitution
Amine metal titanium complex is A2, the self-supported salicylic alidehyde imine metal titanium complex of corresponding novel high polymer is D2；
Work as R1=hydrogen, R2=R3When=isopropyl, corresponding ligand E3, the salicylide Asia of corresponding novel allyl substitution
Amine metal titanium complex is A3, the self-supported salicylic alidehyde imine metal titanium complex of corresponding novel high polymer is D3；
Work as R1=chlorine, R2=R3When=hydrogen, corresponding ligand E4, the salicylic alidehyde imine gold of corresponding novel allyl substitution
Category titanium complex is A4, the self-supported salicylic alidehyde imine metal titanium complex of corresponding novel high polymer is D4；
Work as R1=bromine, R2=R3When=hydrogen, corresponding ligand E5, the salicylic alidehyde imine gold of corresponding novel allyl substitution
Category titanium complex is A5, the self-supported salicylic alidehyde imine metal titanium complex of corresponding novel high polymer is D5；
Work as R1=hydrogen, R2=R3When=hydrogen, corresponding ligand E6, the salicylic alidehyde imine gold of corresponding novel allyl substitution
Category titanium complex is A6, the self-supported salicylic alidehyde imine metal titanium complex of corresponding novel high polymer is D6；
Embodiment 1
A kind of salicylic alidehyde imine metal titanium complex D that novel high polymer is self-supported1, synthetic method and application method.One
The self-supported salicylic alidehyde imine metal titanium complex of kind novel high polymer is denoted as D1Structural formula are as follows:
Wherein: " → " indicates coordinate bond；
Indicate the macromolecule chain section that allyl and ethylene copolymer are formed.
A kind of salicylic alidehyde imine metal titanium complex D that novel high polymer is self-supported1It is to be replaced by a kind of novel allyl
Salicylic alidehyde imine metal titanium complex A1It is prepared with ethylene by copolymerization process.Schematically as follows:
Wherein: " → " indicates coordinate bond；
Indicate the macromolecule chain section that allyl and ethylene copolymer are formed.
Synthetic method comprises the concrete steps that: 250mL polymeric kettle being vacuumized water removal deoxygenation, after nitrogen is sufficiently displaced from, then is led to
Enter ethylene displacement nitrogen, and the toluene solvant of 100mL is added under the protection of ethylene, it is full to dissolving to be passed through normal pressure ethylene gas
With, be added 10 μm of ol a kind of novel allyl replace salicylic alidehyde imine metal titanium complex A1As major catalyst, and add
Enter the methylaluminoxane MAO of corresponding proportion as co-catalyst, wherein co-catalyst MAO and metal titanium complex A1Substance
The ratio of amount is 100:1.It then proceedes to be passed through ethylene, and polymerization reaction 0.5h under the conditions of 30 DEG C and 3MPa and magnetic agitation, close
Polymeric kettle is vented to normal pressure by the inlet valve for closing ethylene, and material is released from polymeric kettle, and filtering obtains polymer crude product, second
Alcohol washing, obtained solid is dried in vacuo at 60 DEG C, obtains a kind of salicylic alidehyde imine Titanium that novel high polymer is self-supported and matches
Close object D1, the content of Titanium therein is 4.5 μm of ol/g.
A kind of salicylic alidehyde imine metal titanium complex A that novel allyl replaces1Synthetic method, comprise the concrete steps that:
Step 1: the synthesis of ligand.
Ligand E1Structural formula are as follows:
Ligand E1Synthesis include two stages: first stage be 3- allyl -5- chloro-salicylic aldehyde synthesis；Second
Stage is that 3- allyl -5- chloro-salicylic aldehyde and 2,6-DIPA are condensed through schiff alkali, obtains ligand E1。
The synthesis of 3- allyl -5- chloro-salicylic aldehyde: vacuumizing logical nitrogen for the reaction flask of 250mL, after nitrogen is replaced 3 times,
The dry toluene of addition 100mL, the 2- allyl parachlorophenol of 0.2mmol, 0.01mmol are anhydrous under the protection of nitrogen
SnCl4, the poly of 1.1mmol is added at room temperature after magnetic agitation back flow reaction 20min in 2, the 6- lutidines of 0.8mmol
Formaldehyde, temperature are increased to 80 DEG C, react 2h.After product separation, purifying, drying, 3- allyl -5- chloro-salicylic aldehyde is obtained.
3- allyl -5- chloro-salicylic aldehyde and 2,6-DIPA are condensed through schiff alkali, obtain ligand E1: it will
3- allyl -5- the chloro-salicylic aldehyde of 10mmol and the 2,6- diisopropyl aniline of 10.1mmol are added to the methanol solvate of 50mL
In, the formic acid of 0.1mmol is added as catalyst, at 30 DEG C after magnetic agitation reaction 1h, solids are precipitated in -10 DEG C of coolings,
Filtering, filter residue are refiltered using after about 5 DEG C of cold ethanol washings, in ethanol recrystallization, about 5 DEG C of cold ethyl alcohol wash, filter again,
Ligand E is obtained after solid is dry1。
Step 2: the salicylic alidehyde imine metal titanium complex A that a kind of novel allyl replaces1Synthesis.
By ligand E described in 1.0mmol1Be dissolved in 50mL methylene chloride, at -30 DEG C and under good stirring condition, in 1h by
It is added dropwise to the TiCl by 0.5mmol4With the solution of 30mL methylene chloride composition, 30 DEG C of magnetic agitation reaction 2h are increased to, then
The triethylamine of 1.0mmol is injected with syringe, continues to be stirred to react 2h at 35 DEG C, then concentration of reaction solution to about 40mL, is added
30mL petroleum ether after precipitating reagent as filtering, and after filter residue washs 3 times with the cold methylene chloride of 3 × 10mL, resulting solid is in dichloro
It is recrystallized in methane, filters, is dried to obtain a kind of salicylic alidehyde imine metal titanium complex A that novel allyl replaces1。
Step 2 is carried out under the conditions of anhydrous and oxygen-free.
A kind of salicylic alidehyde imine metal titanium complex D that novel high polymer is self-supported1Monomer N-vinyl pyrrole can be catalyzed
The bulk polymerization of pyrrolidone (NVP).Titanium complex D1It is catalyzed the bulk polymerization of monomer N-vinyl pyrrolidones (NVP), specifically
Steps are as follows:
Stainless steel polymeric kettle is heated and vacuumized deoxygenation, pure argon is passed through and is sufficiently displaced from completely.The NVP of addition 30g,
The Ti content of 0.3g is the self-supported salicylic alidehyde imine metal titanium complex D of the novel high polymer of 4.5 μm of ol/g1And corresponding proportion
Methylaluminoxane (MAO) be used as activator, wherein activator MAO and metal titanium complex D1Substance amount ratio be 50:
1.The magnetic agitation polymerization reaction 1h in 60 DEG C of constant temperature oil baths, 20g deionized water, which is added, inactivates system, last spray-dried
Obtain poly- (N- vinylpyrrolidone) powder product.Data are shown in Table 1 after products therefrom is detected by pharmacopeia.
A kind of salicylic alidehyde imine metal titanium complex D that novel high polymer is self-supported1It is catalyzed monomer N-vinyl pyrrolidines
The application method of the polymerisation in solution of ketone.Specific step is as follows:
The water of NVP, 60g of 30g is added in stainless steel polymeric kettle, the Ti content of 3g is the novel high polymer of 4.5 μm of ol/g
Self-supported salicylic alidehyde imine metal titanium complex D1.It in 60 DEG C of constant temperature oil baths after magnetic agitation polymerization reaction 1h, filters, returns
Receive titanium complex D1, after the washing of multiple deionized water is dry, titanium complex D1It can be recycled.Filtrate systems are through spraying
It is dried to obtain poly- (n-vinyl pyrrolidone) powder product.Data are shown in Table 1 after products therefrom is detected by pharmacopeia.
Embodiment 2
A kind of salicylic alidehyde imine metal titanium complex D that novel high polymer is self-supported2, synthetic method and application method.One
The self-supported salicylic alidehyde imine metal titanium complex of kind novel high polymer is denoted as D2Structural formula are as follows:
Wherein: " → " indicates coordinate bond；
Indicate the macromolecule chain section that allyl and ethylene copolymer are formed.
A kind of salicylic alidehyde imine metal titanium complex D that novel high polymer is self-supported2It is to be replaced by a kind of novel allyl
Salicylic alidehyde imine metal titanium complex A2It is prepared with ethylene by copolymerization process.Schematically as follows:
Wherein: " → " indicates coordinate bond；
Indicate the macromolecule chain section that allyl and ethylene copolymer are formed.
Synthetic method comprises the concrete steps that: 250mL polymeric kettle being vacuumized water removal deoxygenation, after nitrogen is sufficiently displaced from, then is led to
Enter ethylene displacement nitrogen, and the toluene solvant of 100mL is added under the protection of ethylene, it is full to dissolving to be passed through normal pressure ethylene gas
With, be added 10 μm of ol a kind of novel allyl replace salicylic alidehyde imine metal titanium complex A2As major catalyst, and add
Enter the methylaluminoxane MAO of corresponding proportion as co-catalyst, wherein co-catalyst MAO and metal titanium complex A2Substance
The ratio of amount is 100:1.It then proceedes to be passed through ethylene, and polymerization reaction 0.5h under the conditions of 30 DEG C and 3MPa and magnetic agitation, close
Polymeric kettle is vented to normal pressure by the inlet valve for closing ethylene, and material is released from polymeric kettle, and filtering obtains polymer crude product, second
Alcohol washing, obtained solid is dried in vacuo at 60 DEG C, obtains a kind of salicylic alidehyde imine Titanium that novel high polymer is self-supported and matches
Close object D2, the content of Titanium therein is 5.3 μm of ol/g.
A kind of salicylic alidehyde imine metal titanium complex A that novel allyl replaces2Synthetic method, comprise the concrete steps that:
Step 1: the synthesis of ligand.
Ligand E2Structural formula are as follows:
Ligand E2Synthesis include two stages: first stage be 3- allyl -5- bromosalicylaldehyde synthesis；Second
Stage is that 3- allyl -5- bromosalicylaldehyde and 2,6-DIPA are condensed through schiff alkali, obtains ligand E2。
The synthesis of 3- allyl -5- bromosalicylaldehyde: vacuumizing logical nitrogen for the reaction flask of 250mL, after nitrogen is replaced 3 times,
The dry toluene of addition 100mL, the 2- allyl p bromophenol of 0.2mmol, 0.01mmol are anhydrous under the protection of nitrogen
SnCl4, the poly of 1.1mmol is added at room temperature after magnetic agitation back flow reaction 20min in 2, the 6- lutidines of 0.8mmol
Formaldehyde, temperature are increased to 80 DEG C, react 2h.After product separation, purifying, drying, 3- allyl -5- bromosalicylaldehyde is obtained.
3- allyl -5- bromosalicylaldehyde and 2,6-DIPA are condensed through schiff alkali, obtain ligand E2: it will
3- allyl -5- the chloro-salicylic aldehyde of 10mmol and the 2,6- diisopropyl aniline of 10.1mmol are added to the methanol solvate of 50mL
In, the formic acid of 0.1mmol is added as catalyst, at 30 DEG C after magnetic agitation reaction 1h, solids are precipitated in -10 DEG C of coolings,
Filtering, filter residue are refiltered using after about 5 DEG C of cold ethanol washings, in ethanol recrystallization, about 5 DEG C of cold ethyl alcohol wash, filter again,
Ligand E is obtained after solid is dry2。
Step 2: the salicylic alidehyde imine metal titanium complex A that a kind of novel allyl replaces2Synthesis.
By ligand E described in 1.0mmol2Be dissolved in 50mL methylene chloride, at -30 DEG C and under good stirring condition, in 1h by
It is added dropwise to the TiCl by 0.5mmol4With the solution of 30mL methylene chloride composition, 30 DEG C of magnetic agitation reaction 2h are increased to, then
The triethylamine of 1.0mmol is injected with syringe, continues to be stirred to react 2h at 35 DEG C, then concentration of reaction solution to about 40mL, is added
30mL petroleum ether after precipitating reagent as filtering, and after filter residue washs 3 times with the cold methylene chloride of 3 × 10mL, resulting solid is in dichloro
It is recrystallized in methane, filters, is dried to obtain a kind of salicylic alidehyde imine metal titanium complex A that novel allyl replaces2。
Step 2 is carried out under the conditions of anhydrous and oxygen-free.
A kind of salicylic alidehyde imine metal titanium complex D that novel high polymer is self-supported2Monomer N-vinyl pyrrole can be catalyzed
The bulk polymerization of pyrrolidone (NVP).Titanium complex D2It is catalyzed the tool of the bulk polymerization of monomer N-vinyl pyrrolidones (NVP)
Steps are as follows for body:
Stainless steel polymeric kettle is heated and vacuumized deoxygenation, pure argon is passed through and is sufficiently displaced from completely.The NVP of addition 30g,
The Ti content of 0.3g is the self-supported salicylic alidehyde imine metal titanium complex D of the novel high polymer of 5.3 μm of ol/g2And corresponding proportion
Methylaluminoxane (MAO) be used as activator, wherein activator MAO and metal titanium complex D2Substance amount ratio be 50:
1.The magnetic agitation polymerization reaction 1h in 60 DEG C of constant temperature oil baths, 20g deionized water, which is added, inactivates system, last spray-dried
Obtain poly- (N- vinylpyrrolidone) powder product.Data are shown in Table 1 after products therefrom is detected by pharmacopeia.
A kind of salicylic alidehyde imine metal titanium complex D that novel high polymer is self-supported2It is catalyzed monomer N-vinyl pyrrolidines
The application method of the polymerisation in solution of ketone, the specific steps are as follows:
The water of NVP, 60g of 30g is added in stainless steel polymeric kettle, the Ti content of 3g is the novel high polymer of 5.3 μm of ol/g
Self-supported salicylic alidehyde imine metal titanium complex D2.It in 60 DEG C of constant temperature oil baths after magnetic agitation polymerization reaction 1h, filters, returns
Receive titanium complex D2, after the washing of multiple deionized water is dry, titanium complex D2It can be recycled.Filtrate systems are through spraying
It is dried to obtain poly- (n-vinyl pyrrolidone) powder product.Data are shown in Table 1 after products therefrom is detected by pharmacopeia.
Embodiment 3
A kind of salicylic alidehyde imine metal titanium complex D that novel high polymer is self-supported3, synthetic method and application method.One
The self-supported salicylic alidehyde imine metal titanium complex of kind novel high polymer is denoted as D3Structural formula are as follows:
Wherein: " → " indicates coordinate bond；
Indicate the macromolecule chain section that allyl and ethylene copolymer are formed.
A kind of salicylic alidehyde imine metal titanium complex D that novel high polymer is self-supported3It is to be replaced by a kind of novel allyl
Salicylic alidehyde imine metal titanium complex A3It is prepared with ethylene by copolymerization process.Schematically as follows:
Wherein: " → " indicates coordinate bond；
Indicate the macromolecule chain section that allyl and ethylene copolymer are formed.
Synthetic method comprises the concrete steps that: 250mL polymeric kettle being vacuumized water removal deoxygenation, after nitrogen is sufficiently displaced from, then is led to
Enter ethylene displacement nitrogen, and the toluene solvant of 100mL is added under the protection of ethylene, it is full to dissolving to be passed through normal pressure ethylene gas
With, be added 10 μm of ol a kind of novel allyl replace salicylic alidehyde imine metal titanium complex A3As major catalyst, and add
Enter the methylaluminoxane MAO of corresponding proportion as co-catalyst, wherein co-catalyst MAO and metal titanium complex A3Substance
The ratio of amount is 100:1.It then proceedes to be passed through ethylene, and polymerization reaction 0.5h under the conditions of 30 DEG C and 3MPa and magnetic agitation, close
Polymeric kettle is vented to normal pressure by the inlet valve for closing ethylene, and material is released from polymeric kettle, and filtering obtains polymer crude product, second
Alcohol washing, obtained solid is dried in vacuo at 60 DEG C, obtains a kind of salicylic alidehyde imine Titanium that novel high polymer is self-supported and matches
Close object D3, the content of Titanium therein is 4.9 μm of ol/g.
A kind of salicylic alidehyde imine metal titanium complex A that novel allyl replaces3Synthetic method, comprise the concrete steps that:
Step 1: the synthesis of ligand.
Ligand E3Structural formula are as follows:
Ligand E3Synthesis: the 10mmol 3- allyl salicylide ordered and the 2,6- diisopropyl aniline of 11mmol are added
Enter into the methanol solvate of 50mL, the formic acid of 0.1mmol is added as catalyst, at 30 DEG C after magnetic agitation reaction 1h ,-
10 DEG C cooling to be precipitated solids, and filtering refilters after filter residue is using about 5 DEG C of cold ethanol washings, in ethanol recrystallization, about 5 DEG C it is cold
Ligand E is obtained after ethyl alcohol is washed again, filtered, solid is dry3。
Step 2: the salicylic alidehyde imine metal titanium complex A that a kind of novel allyl replaces3Synthesis.
By ligand E described in 1.0mmol3Be dissolved in 50mL methylene chloride, at -30 DEG C and under good stirring condition, in 1h by
It is added dropwise to the TiCl by 0.5mmol4With the solution of 30mL methylene chloride composition, 30 DEG C of magnetic agitation reaction 2h are increased to, then
The triethylamine of 1.0mmol is injected with syringe, continues to be stirred to react 2h at 35 DEG C, then concentration of reaction solution to about 40mL, is added
30mL petroleum ether after precipitating reagent as filtering, and after filter residue washs 3 times with the cold methylene chloride of 3 × 10mL, resulting solid is in dichloro
It is recrystallized in methane, filters, is dried to obtain a kind of salicylic alidehyde imine metal titanium complex A that novel allyl replaces3。
Step 2 is carried out under the conditions of anhydrous and oxygen-free.
A kind of salicylic alidehyde imine metal titanium complex D that novel high polymer is self-supported3Monomer N-vinyl pyrrole can be catalyzed
The bulk polymerization of pyrrolidone (NVP).Titanium complex D3It is catalyzed the tool of the bulk polymerization of monomer N-vinyl pyrrolidones (NVP)
Steps are as follows for body:
Stainless steel polymeric kettle is heated and vacuumized deoxygenation, pure argon is passed through and is sufficiently displaced from completely.The NVP of addition 30g,
The Ti content of 0.3g is the self-supported salicylic alidehyde imine metal titanium complex D of the novel high polymer of 4.9 μm of ol/g3And corresponding proportion
Methylaluminoxane (MAO) be used as activator, wherein activator MAO and metal titanium complex D3Substance amount ratio be 50:
1.The magnetic agitation polymerization reaction 1h in 60 DEG C of constant temperature oil baths, 20g deionized water, which is added, inactivates system, last spray-dried
Obtain poly- (N- vinylpyrrolidone) powder product.Data are shown in Table 1 after products therefrom is detected by pharmacopeia.
A kind of salicylic alidehyde imine metal titanium complex D that novel high polymer is self-supported3It is catalyzed monomer N-vinyl pyrrolidines
Specific step is as follows for the application method of the polymerisation in solution of ketone:
The water of NVP, 60g of 30g is added in stainless steel polymeric kettle, the Ti content of 3g is the novel high polymer of 4.9 μm of ol/g
Self-supported salicylic alidehyde imine metal titanium complex D3.It in 60 DEG C of constant temperature oil baths after magnetic agitation polymerization reaction 1h, filters, returns
Receive titanium complex D3, after the washing of multiple deionized water is dry, titanium complex D3It can be recycled.Filtrate systems are through spraying
It is dried to obtain poly- (N-N- vinyl pyrrolidone) powder product.Data are shown in Table 1 after products therefrom is detected by pharmacopeia.
Embodiment 4
A kind of salicylic alidehyde imine metal titanium complex D that novel high polymer is self-supported4, synthetic method and application method.One
The self-supported salicylic alidehyde imine metal titanium complex of kind novel high polymer is denoted as D4Structural formula are as follows:
Wherein: " → " indicates coordinate bond；
Indicate the macromolecule chain section that allyl and ethylene copolymer are formed.
A kind of salicylic alidehyde imine metal titanium complex D that novel high polymer is self-supported4It is to be replaced by a kind of novel allyl
Salicylic alidehyde imine metal titanium complex A4It is prepared with ethylene by copolymerization process.Schematically as follows:
Wherein: " → " indicates coordinate bond；
Indicate the macromolecule chain section that allyl and ethylene copolymer are formed.
Synthetic method comprises the concrete steps that: 250mL polymeric kettle being vacuumized water removal deoxygenation, after nitrogen is sufficiently displaced from, then is led to
Enter ethylene displacement nitrogen, and the toluene solvant of 100mL is added under the protection of ethylene, it is full to dissolving to be passed through normal pressure ethylene gas
With, be added 10 μm of ol a kind of novel allyl replace salicylic alidehyde imine metal titanium complex A4As major catalyst, and add
Enter the methylaluminoxane MAO of corresponding proportion as co-catalyst, wherein co-catalyst MAO and metal titanium complex A4Substance
The ratio of amount is 100:1.It then proceedes to be passed through ethylene, and polymerization reaction 0.5h under the conditions of 30 DEG C and 3MPa and magnetic agitation, close
Polymeric kettle is vented to normal pressure by the inlet valve for closing ethylene, and material is released from polymeric kettle, and filtering obtains polymer crude product, second
Alcohol washing, obtained solid is dried in vacuo at 60 DEG C, obtains a kind of salicylic alidehyde imine Titanium that novel high polymer is self-supported and matches
Close object D4, the content of Titanium therein is 4.3 μm of ol/g.
A kind of salicylic alidehyde imine metal titanium complex A that novel allyl replaces4Synthetic method, comprise the concrete steps that:
Step 1: the synthesis of ligand.
Ligand E4Structural formula are as follows:
Ligand E4Synthesis include two stages: first stage be 3- allyl -5- chloro-salicylic aldehyde synthesis；Second
Stage is that 3- allyl -5- chloro-salicylic aldehyde and aniline are condensed through schiff alkali, obtains ligand E4。
The synthesis of 3- allyl -5- chloro-salicylic aldehyde: see embodiment 1.
3- allyl -5- chloro-salicylic aldehyde and aniline are condensed through schiff alkali, obtain ligand E4: by the 3- allyl-of 10mmol
The aniline of 5- chloro-salicylic aldehyde and 10.1mmol are added in the methanol solvate of 50mL, and the formic acid of 0.1mmol is added as catalysis
Agent, at 30 DEG C after magnetic agitation reaction 1h, in -10 DEG C of cooling precipitation solids, filtering, filter residue uses about 5 DEG C of cold ethanol washings
Afterwards, it refilters, obtains ligand E after recrystallization, about 5 DEG C of cold ethyl alcohol are washed again, filtered in ethanol, solid is dry4。
Step 2: the salicylic alidehyde imine metal titanium complex A that a kind of novel allyl replaces4Synthesis.
By ligand E described in 1.0mmol4Be dissolved in 50mL methylene chloride, at -30 DEG C and under good stirring condition, in 1h by
It is added dropwise to the TiCl by 0.5mmol4With the solution of 30mL methylene chloride composition, 30 DEG C of magnetic agitation reaction 2h are increased to, then
The triethylamine of 1.0mmol is injected with syringe, continues to be stirred to react 2h at 35 DEG C, then concentration of reaction solution to about 40mL, is added
30mL petroleum ether after precipitating reagent as filtering, and after filter residue washs 3 times with the cold methylene chloride of 3 × 10mL, resulting solid is in dichloro
It is recrystallized in methane, filters, is dried to obtain a kind of salicylic alidehyde imine metal titanium complex A that novel allyl replaces4。
Step 2 is carried out under the conditions of anhydrous and oxygen-free.
A kind of salicylic alidehyde imine metal titanium complex D that novel high polymer is self-supported4Monomer N-vinyl pyrrole can be catalyzed
The bulk polymerization of pyrrolidone (NVP).Titanium complex D4It is catalyzed making for the bulk polymerization of monomer N-vinyl pyrrolidones (NVP)
With method, specific step is as follows:
Stainless steel polymeric kettle is heated and vacuumized deoxygenation, pure argon is passed through and is sufficiently displaced from completely.The NVP of addition 30g,
The Ti content of 0.3g is the self-supported salicylic alidehyde imine metal titanium complex D of the novel high polymer of 4.3 μm of ol/g4And corresponding proportion
Methylaluminoxane (MAO) be used as activator, wherein activator MAO and metal titanium complex D4Substance amount ratio be 50:
1.The magnetic agitation polymerization reaction 1h in 60 DEG C of constant temperature oil baths, 20g deionized water, which is added, inactivates system, last spray-dried
Obtain poly- (N- vinylpyrrolidone) powder product.Data are shown in Table 1 after products therefrom is detected by pharmacopeia.
A kind of salicylic alidehyde imine metal titanium complex D that novel high polymer is self-supported4It is catalyzed monomer N-vinyl pyrrolidines
Specific step is as follows for the application method of the polymerisation in solution of ketone:
The water of NVP, 60g of 30g is added in stainless steel polymeric kettle, the Ti content of 3g is the novel high polymer of 4.3 μm of ol/g
Self-supported salicylic alidehyde imine metal titanium complex D4.It in 60 DEG C of constant temperature oil baths after magnetic agitation polymerization reaction 1h, filters, returns
Receive titanium complex D4, after the washing of multiple deionized water is dry, titanium complex D4It can be recycled.Filtrate systems are through spraying
It is dried to obtain poly- (n-vinyl pyrrolidone) powder product.Data are shown in Table 1 after products therefrom is detected by pharmacopeia.
Embodiment 5
A kind of salicylic alidehyde imine metal titanium complex D that novel high polymer is self-supported5, synthetic method and application method.One
The self-supported salicylic alidehyde imine metal titanium complex of kind novel high polymer is denoted as D5Structural formula are as follows:
Wherein: " → " indicates coordinate bond；
Indicate the macromolecule chain section that allyl and ethylene copolymer are formed.
A kind of salicylic alidehyde imine metal titanium complex D that novel high polymer is self-supported5It is to be replaced by a kind of novel allyl
Salicylic alidehyde imine metal titanium complex A5It is prepared with ethylene by copolymerization process.Schematically as follows:
Wherein: " → " indicates coordinate bond；
Indicate the macromolecule chain section that allyl and ethylene copolymer are formed.
Synthetic method comprises the concrete steps that: 250mL polymeric kettle being vacuumized water removal deoxygenation, after nitrogen is sufficiently displaced from, then is led to
Enter ethylene displacement nitrogen, and the toluene solvant of 100mL is added under the protection of ethylene, it is full to dissolving to be passed through normal pressure ethylene gas
With, be added 10 μm of ol a kind of novel allyl replace salicylic alidehyde imine metal titanium complex A5As major catalyst, and add
Enter the methylaluminoxane MAO of corresponding proportion as co-catalyst, wherein co-catalyst MAO and metal titanium complex A5Substance
The ratio of amount is 100:1.It then proceedes to be passed through ethylene, and polymerization reaction 0.5h under the conditions of 30 DEG C and 3MPa and magnetic agitation, close
Polymeric kettle is vented to normal pressure by the inlet valve for closing ethylene, and material is released from polymeric kettle, and filtering obtains polymer crude product, second
Alcohol washing, obtained solid is dried in vacuo at 60 DEG C, obtains a kind of salicylic alidehyde imine Titanium that novel high polymer is self-supported and matches
Close object D5, the content of Titanium therein is 5.1 μm of ol/g.
A kind of salicylic alidehyde imine metal titanium complex A that novel allyl replaces5Synthetic method, comprise the concrete steps that:
Step 1: the synthesis of ligand.
Ligand E5Structural formula are as follows:
Ligand E5Synthesis include two stages: first stage be 3- allyl -5- bromosalicylaldehyde synthesis；Second
Stage is that 3- allyl -5- bromosalicylaldehyde and aniline are condensed through schiff alkali, obtains ligand E5。
The synthesis of 3- allyl -5- bromosalicylaldehyde: see embodiment 2.
3- allyl -5- bromosalicylaldehyde and aniline are condensed through schiff alkali, obtain ligand E5: by the 3- allyl-of 10mmol
The aniline of 5- bromosalicylaldehyde and 10.1mmol are added in the methanol solvate of 50mL, and the formic acid of 0.1mmol is added as catalysis
Agent, at 30 DEG C after magnetic agitation reaction 1h, in -10 DEG C of cooling precipitation solids, filtering, filter residue uses about 5 DEG C of cold ethanol washings
Afterwards, it refilters, obtains ligand E after recrystallization, about 5 DEG C of cold ethyl alcohol are washed again, filtered in ethanol, solid is dry5。
Step 2: the salicylic alidehyde imine metal titanium complex A that a kind of novel allyl replaces5Synthesis.
By ligand E described in 1.0mmol5Be dissolved in 50mL methylene bromide, at -30 DEG C and under good stirring condition, in 1h by
It is added dropwise to the TiCl by 0.5mmol4With the solution of 30mL methylene bromide composition, 30 DEG C of magnetic agitation reaction 2h are increased to, then
The triethylamine of 1.0mmol is injected with syringe, continues to be stirred to react 2h at 35 DEG C, then concentration of reaction solution to about 40mL, is added
30mL petroleum ether after precipitating reagent as filtering, and after filter residue washs 3 times with the cold methylene bromide of 3 × 10mL, resulting solid is in dibromo
It is recrystallized in methane, filters, is dried to obtain a kind of salicylic alidehyde imine metal titanium complex A that novel allyl replaces5。
Step 2 is carried out under the conditions of anhydrous and oxygen-free.
A kind of salicylic alidehyde imine metal titanium complex D that novel high polymer is self-supported5Monomer N-vinyl pyrrole can be catalyzed
The bulk polymerization of pyrrolidone (NVP).Titanium complex D5It is catalyzed the tool of the bulk polymerization of monomer N-vinyl pyrrolidones (NVP)
Steps are as follows for body:
Stainless steel polymeric kettle is heated and vacuumized deoxygenation, pure argon is passed through and is sufficiently displaced from completely.The NVP of addition 30g,
The Ti content of 0.3g is the self-supported salicylic alidehyde imine metal titanium complex D of the novel high polymer of 5.1 μm of ol/g5And corresponding proportion
Methylaluminoxane (MAO) be used as activator, wherein activator MAO and metal titanium complex D5Substance amount ratio be 50:
1.The magnetic agitation polymerization reaction 1h in 60 DEG C of constant temperature oil baths, 20g deionized water, which is added, inactivates system, last spray-dried
Obtain poly- (N- vinylpyrrolidone) powder product.Data are shown in Table 1 after products therefrom is detected by pharmacopeia.
A kind of salicylic alidehyde imine metal titanium complex D that novel high polymer is self-supported5It is catalyzed monomer N-vinyl pyrrolidines
Specific step is as follows for the application method of the polymerisation in solution of ketone:
The water of NVP, 60g of 30g is added in stainless steel polymeric kettle, the Ti content of 3g is the novel high polymer of 5.1 μm of ol/g
Self-supported salicylic alidehyde imine metal titanium complex D5.It in 60 DEG C of constant temperature oil baths after magnetic agitation polymerization reaction 1h, filters, returns
Receive titanium complex D5, after the washing of multiple deionized water is dry, titanium complex D5It can be recycled.Filtrate systems are through spraying
It is dried to obtain poly- (n-vinyl pyrrolidone) powder product.Data are shown in Table 1 after products therefrom is detected by pharmacopeia.
Embodiment 6
A kind of salicylic alidehyde imine metal titanium complex D that novel high polymer is self-supported6, synthetic method and application method.One
The self-supported salicylic alidehyde imine metal titanium complex of kind novel high polymer is denoted as D6Structural formula are as follows:
Wherein: " → " indicates coordinate bond；
Indicate the macromolecule chain section that allyl and ethylene copolymer are formed.
A kind of salicylic alidehyde imine metal titanium complex D that novel high polymer is self-supported6It is to be replaced by a kind of novel allyl
Salicylic alidehyde imine metal titanium complex A6It is prepared with ethylene by copolymerization process.Schematically as follows:
Wherein: " → " indicates coordinate bond；
Indicate the macromolecule chain section that allyl and ethylene copolymer are formed.
Synthetic method comprises the concrete steps that: 250mL polymeric kettle being vacuumized water removal deoxygenation, after nitrogen is sufficiently displaced from, then is led to
Enter ethylene displacement nitrogen, and the toluene solvant of 100mL is added under the protection of ethylene, it is full to dissolving to be passed through normal pressure ethylene gas
With, be added 10 μm of ol a kind of novel allyl replace salicylic alidehyde imine metal titanium complex A6As major catalyst, and add
Enter the methylaluminoxane MAO of corresponding proportion as co-catalyst, wherein co-catalyst MAO and metal titanium complex A6Substance
The ratio of amount is 100:1.It then proceedes to be passed through ethylene, and polymerization reaction 0.5h under the conditions of 30 DEG C and 3MPa and magnetic agitation, close
Polymeric kettle is vented to normal pressure by the inlet valve for closing ethylene, and material is released from polymeric kettle, and filtering obtains polymer crude product, second
Alcohol washing, obtained solid is dried in vacuo at 60 DEG C, obtains a kind of salicylic alidehyde imine Titanium that novel high polymer is self-supported and matches
Close object D6, the content of Titanium therein is 5.9 μm of ol/g.
A kind of salicylic alidehyde imine metal titanium complex A that novel allyl replaces6Synthetic method, comprise the concrete steps that:
Step 1: the synthesis of ligand.
Ligand E6Structural formula are as follows:
Ligand E6Synthesis: the 10mmol 3- allyl salicylide ordered and the aniline of 10.1mmol are added to 50mL's
In methanol solvate, the formic acid of 0.1mmol is added as catalyst, at 30 DEG C after magnetic agitation reaction 1h, in -10 DEG C of cooling analysis
Solid out, filtering refilter after filter residue is using about 5 DEG C of cold ethanol washings, and recrystallization, about 5 DEG C of cold ethyl alcohol are washed again in ethanol
It washs, filter, obtaining ligand E after solid drying6。
Step 2: the salicylic alidehyde imine metal titanium complex A that a kind of novel allyl replaces6Synthesis.
By ligand E described in 1.0mmol6Be dissolved in 50mL methylene bromide, at -30 DEG C and under good stirring condition, in 1h by
It is added dropwise to the TiCl by 0.5mmol4With the solution of 30mL methylene bromide composition, 30 DEG C of magnetic agitation reaction 2h are increased to, then
The triethylamine of 1.0mmol is injected with syringe, continues to be stirred to react 2h at 35 DEG C, then concentration of reaction solution to about 40mL, is added
30mL petroleum ether after precipitating reagent as filtering, and after filter residue washs 3 times with the cold methylene bromide of 3 × 10mL, resulting solid is in dibromo
It is recrystallized in methane, filters, is dried to obtain a kind of salicylic alidehyde imine metal titanium complex A that novel allyl replaces6。
Step 2 is carried out under the conditions of anhydrous and oxygen-free.
A kind of salicylic alidehyde imine metal titanium complex D that novel high polymer is self-supported6Monomer N-vinyl pyrrole can be catalyzed
The bulk polymerization of pyrrolidone (NVP).Titanium complex D6It is catalyzed the tool of the bulk polymerization of monomer N-vinyl pyrrolidones (NVP)
Steps are as follows for body:
Stainless steel polymeric kettle is heated and vacuumized deoxygenation, pure argon is passed through and is sufficiently displaced from completely.The NVP of addition 30g,
The Ti content of 0.3g is the self-supported salicylic alidehyde imine metal titanium complex D of the novel high polymer of 5.9 μm of ol/g6And corresponding proportion
Methylaluminoxane (MAO) be used as activator, wherein activator MAO and metal titanium complex D6Substance amount ratio be 50:
1.The magnetic agitation polymerization reaction 1h in 60 DEG C of constant temperature oil baths, 20g deionized water, which is added, inactivates system, last spray-dried
Obtain poly- (N- vinylpyrrolidone) powder product.Data are shown in Table 1 after products therefrom is detected by pharmacopeia.
A kind of salicylic alidehyde imine metal titanium complex D that novel high polymer is self-supported6It is catalyzed monomer N-vinyl pyrrolidines
Specific step is as follows for the application method of the polymerisation in solution of ketone:
The water of NVP, 60g of 30g is added in stainless steel polymeric kettle, the Ti content of 3g is the novel high polymer of 5.9 μm of ol/g
Self-supported salicylic alidehyde imine metal titanium complex D6.It in 60 DEG C of constant temperature oil baths after magnetic agitation polymerization reaction 1h, filters, returns
Receive titanium complex D6, after the washing of multiple deionized water is dry, titanium complex D6It can be recycled.Filtrate systems are through spraying
It is dried to obtain poly- (n-vinyl pyrrolidone) powder product.Data are shown in Table 1 after products therefrom is detected by pharmacopeia.
1 example detection data of table
Comparative example derives from: ZL 201210410071.X
By the reaction time and the comparison of K value of 1 example 1~6 of table and comparative example it is found that one kind macromolecule proposed by the present invention is born
The salicylic alidehyde imine Titanium composition catalyst that the novel allyl of load replaces, it is more living than the catalysis of the catalyst system in comparative example
Property is higher, and poly- (n-vinyl pyrrolidone) of K30 just can be obtained within the shorter time.By 1 example 1~6 of table and comparative example
Monomer residue rate comparison it is found that the self-supported salicylic alidehyde imine metal titanium complex conduct of novel high polymer proposed by the present invention
The catalyst of NVP polymerization, it is resulting poly- when than catalyst system catalyzed preparation of poly (n-vinyl pyrrolidone) in comparative example
NVP monomer residue rate in (n-vinyl pyrrolidone) is lower.
In conclusion the salicylic alidehyde imine metal titanium complex D that novel high polymer obtained by the present patent application is self-supported1
~D6To the homopolymerization of monomer N-vinyl pyrrolidones within the scope of 30~100 DEG C, (it is more than with superelevation catalytic activity
1000,000g·PVPmol-1·Ti-1·h-1).Cause the polymerization reaction phase of monomer NVP with initiator used by prior art
Compare, the self-supported titanium complex catalyst of such macromolecule, is capable of the homopolymerization of efficient catalytic NVP in a short time, obtains
To poly- (n-vinyl pyrrolidone) (PVP) of high molecular weight.It is catalyzed the significant increase of reaction efficiency, so that monomer NVP's turns
Rate greatly improves, and residual rate of the monomer NVP in polymerizate greatly reduces, and can meet the doctor of high quality well
Requirement of the medicine grade PVP to impurity contents such as monomer, catalyst.
Although preferred embodiments of the present invention have been described, it is created once a person skilled in the art knows basic
Property concept, then additional changes and modifications may be made to these embodiments.So it includes excellent that the following claims are intended to be interpreted as
It selects embodiment and falls into all change and modification of the scope of the invention.Obviously, those skilled in the art can be to the present invention
Carry out various modification and variations without departing from the spirit and scope of the present invention.If in this way, these modifications and changes of the present invention
Within the scope of the claims of the present invention and its equivalent technology, then the present invention is also intended to encompass these modification and variations and exists
It is interior.
Claims (5)
1. the self-supported salicylic alidehyde imine metal titanium complex of a kind of novel high polymer, it is characterised in that the novel high score of one kind
The self-supported salicylic alidehyde imine metal titanium complex of son is denoted as D, structural formula are as follows:
Wherein: R1Selected from one of following substances: hydrogen, bromine, chlorine；R2And R3To be each independently selected from one in following substances
Kind: hydrogen, isopropyl.Work as R1=chlorine and R2=R3When=isopropyl, D is D1；Work as R1=bromine and R2=R3When=isopropyl, D is
For D2；Work as R1=hydrogen and R2=R3When=isopropyl, D is D3；Work as R1=chlorine and R2=R3When=hydrogen, D is D4；Work as R1=bromine
And R2=R3When=hydrogen, D is D5；Work as R1=hydrogen and R2=R3When=hydrogen, D is D6。
" → ", indicates coordinate bond.
Indicate the macromolecule chain section that allyl and ethylene copolymer are formed.
2. the self-supported salicylic alidehyde imine metal titanium complex D (D of a kind of novel high polymer according to claim 11Or D2Or
D3Or D4Or D5Or D6), it is the salicylic alidehyde imine metal titanium complex A (A replaced by a kind of novel allyl1Or A2Or A3Or A4Or
A5Or A6) and ethylene be prepared by copolymerization process, it is as follows:
Indicate the macromolecule chain section that allyl and ethylene copolymer are formed；
Synthetic method comprises the concrete steps that: 250mL polymeric kettle being vacuumized water removal deoxygenation, after nitrogen is sufficiently displaced from, then is passed through second
Alkene displacement nitrogen, and under the protection of ethylene be added 100mL toluene solvant, be passed through normal pressure ethylene gas to dissolve saturation, add
Enter a kind of salicylic alidehyde imine metal titanium complex A of novel allyl substitution of 1~100 μm of ol as major catalyst, and is added
The methylaluminoxane MAO of corresponding proportion is as co-catalyst, the wherein amount of the substance of co-catalyst MAO and metal titanium complex A
Ratio be 10~1000:1.It then proceedes to be passed through ethylene, and gathers under the conditions of 0~100 DEG C and 0.1~10MPa and magnetic agitation
0.5~1h of reaction is closed, the inlet valve of ethylene is closed, polymeric kettle is vented to normal pressure, material is released from polymeric kettle, filters, obtains
To polymer crude product, ethanol washing, obtained solid is dried in vacuo at 60 DEG C, obtains the self-supported water of a kind of novel high polymer
Poplar aldimine metal titanium complex D, the content of Titanium therein are between 4.1 μm of ol/g~60.0 μm ol/g.
3. the synthetic method for the salicylic alidehyde imine metal titanium complex A that a kind of novel allyl replaces according to claim 2,
It is characterized in that the synthetic method comprises the concrete steps that:
Step 1: the synthesis of ligand.
The structural formula of ligand E are as follows:
Wherein: R1Selected from one of following substances: hydrogen, bromine, chlorine；R2And R3To be each independently selected from one in following substances
Kind: hydrogen, isopropyl.
Work as R1=chlorine and R2=R3When=isopropyl, E is E1；Work as R1=bromine and R2=R3When=isopropyl, E is E2；Work as R1=
Hydrogen and R2=R3When=isopropyl, E is E3；Work as R1=chlorine and R2=R3When=hydrogen, E is E4；Work as R1=bromine and R2=R3=hydrogen
When, E is E5；Work as R1=hydrogen and R2=R3When=hydrogen, E is E6。
The synthesis of ligand E includes two stages: first stage is the synthesis of allyl substituted salicylic aldehydes；Second stage is alkene
Propyl substituted salicylic aldehydes and aniline or 2,6-DIPA are condensed through schiff alkali, obtain ligand E.
The synthesis of allyl substituted salicylic aldehydes: the reaction flask of 250mL is vacuumized into logical nitrogen, after nitrogen is replaced 3 times, in nitrogen
The lower dry toluene that 100mL is added of protection, the 2- allyl parachlorophenol or 2- allyl p bromophenol of 0.2~1.1mmol,
The anhydrous SnCl of 0.01~0.04mmol4, 2, the 6- lutidines of 0.8~4.4mmol, magnetic agitation back flow reaction at room temperature
After 20min, the paraformaldehyde of 1~5mmol is added, temperature is increased to 80 DEG C, reacts 2h.After product separation, purifying, drying, point
3- allyl -5- chloro-salicylic aldehyde, 3- allyl -5- bromosalicylaldehyde are not obtained.
Allyl substituted salicylic aldehydes and aniline or or 2,6-DIPA be condensed through schiff alkali, obtain ligand E: by 10mmol
3- allyl salicylide or 3- allyl -5- chloro-salicylic aldehyde or 3- allyl -5- bromosalicylaldehyde respectively with 10~
The aniline or 2,6-DIPA of 11mmol is added in the methanol solvate of 50mL, and the formic acid that 0.1~0.2mmol is added is made
For catalyst, after magnetic agitation reacts 1~2h at 20~50 DEG C, in -10~0 DEG C of cooling precipitation solid, filtering, filter residue is used
It after about 5 DEG C of cold ethanol washings, refilters, is obtained after recrystallization, about 5 DEG C of cold ethyl alcohol are washed again, filtered in ethanol, solid is dry
Ligand E1~E6。
Step 2: the salicylic alidehyde imine metal titanium complex A that a kind of novel allyl replaces1~A6Synthesis, wherein A1With E1It is right
It answers, A2With E2It is corresponding, A3With E3It is corresponding, A4With E4It is corresponding, A5With E5It is corresponding, A6With E6It is corresponding.
By ligand E (E described in 1.0~2.0mmol1Or E2Or E3Or E4Or E5Or E6) be dissolved in 50mL methylene chloride, at -30 DEG C and
Under good stirring condition, it is added dropwise in 1h by 0.5~1.0mmolTiCl4With the solution of 30mL methylene chloride composition, it is increased to
30~45 DEG C of magnetic agitations react 2h, and the triethylamine of 1.0~2.0mmol is then injected with syringe, continues to stir at 30~45 DEG C
React 2h, 30-50mL petroleum ether is added as filtering after precipitating reagent in then concentration of reaction solution to about 40mL, 3 × 10mL of filter residue
After cold methylene chloride washs 3 times, resulting solid recrystallizes in methylene chloride, filters, is dried to obtain a kind of novel allyl
Substituted salicylic alidehyde imine metal titanium complex A1~A6。
Step 2 is carried out under the conditions of anhydrous and oxygen-free.
4. the self-supported salicylic alidehyde imine metal titanium complex D of a kind of novel high polymer can be catalyzed monomer N-vinyl pyrrolidines
The bulk polymerization of ketone (NVP).Titanium complex D catalysis monomer N-vinyl pyrrolidones (NVP) bulk polymerization be characterized in that,
Specific step is as follows for the application method:
Stainless steel polymeric kettle is heated and vacuumized deoxygenation, pure argon is passed through and is sufficiently displaced from completely.Be added 30g NVP, 0.1~
The Ti content of 0.5g is the self-supported salicylic alidehyde imine metal titanium complex of the novel high polymer of 4.1 μm of ol/g~60.0 μm ol/g
D(D1Or D2Or D3Or D4Or D5Or D6) and corresponding proportion methylaluminoxane (MAO) be used as activator, wherein activator MAO with
The ratio of the amount of the substance of metal titanium complex D is 10~100:1.The magnetic agitation polymerization reaction in 30~100 DEG C of constant temperature oil baths
0.5~1h, 10g~20g deionized water, which is added, inactivates system, finally spray-dried to obtain poly- (n-vinyl pyrrolidone)
(abbreviation PVP) powder product.
5. the self-supported salicylic alidehyde imine metal titanium complex D catalysis monomer N-vinyl pyrrolidones of a kind of novel high polymer
The application method of aqueous solution polymerization.It is characterized in that the specific steps difference of the application method is as follows:
NVP, the 60~90g deionized water of 30g are added in stainless steel polymeric kettle, the Ti content of 3~5g is 4.1~60.0 μ
The self-supported salicylic alidehyde imine metal titanium complex D (D of the novel high polymer of mol/g1Or D2Or D3Or D4Or D5Or D6).30~
In 100 DEG C of constant temperature oil baths after 0.5~1h of magnetic agitation polymerization reaction, filtering, gained filter residue is insoluble in aqueous solutions of polymers body
The titanium complex D of system, the catalyst circulation that can be used as the aqueous solution polymerization of catalysis NVP after multiple water washing is dry make
With.Filtrate systems are spray-dried to obtain poly- (n-vinyl pyrrolidone) (PVP) powder product.
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| JP2004331965A (en) * | 2003-04-18 | 2004-11-25 | Mitsui Chemicals Inc | Catalyst for olefin polymerization and process for producing olefin polymer |
| CN1721452A (en) * | 2004-07-16 | 2006-01-18 | 中国石油化工股份有限公司 | Olefin copolymer catalyst consist of transition metal complex and use thereof |
| CN102863575A (en) * | 2012-10-24 | 2013-01-09 | 四川化工控股（集团）有限责任公司 | Preparation method of polyvinylpyrrolidone |
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| JP2004331965A (en) * | 2003-04-18 | 2004-11-25 | Mitsui Chemicals Inc | Catalyst for olefin polymerization and process for producing olefin polymer |
| CN1721452A (en) * | 2004-07-16 | 2006-01-18 | 中国石油化工股份有限公司 | Olefin copolymer catalyst consist of transition metal complex and use thereof |
| CN102863575A (en) * | 2012-10-24 | 2013-01-09 | 四川化工控股（集团）有限责任公司 | Preparation method of polyvinylpyrrolidone |
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| ZYGMUNTFLISAK: "Theoretical study of isomerism in phenoxyimine-based precursors of coordinative olefin polymerization catalysts", 《JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL》 * |
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