CN109053935B - Novel macromolecular self-supported salicylaldimine metal titanium complex, and synthesis method and use method thereof - Google Patents
Novel macromolecular self-supported salicylaldimine metal titanium complex, and synthesis method and use method thereof Download PDFInfo
- Publication number
- CN109053935B CN109053935B CN201810748868.8A CN201810748868A CN109053935B CN 109053935 B CN109053935 B CN 109053935B CN 201810748868 A CN201810748868 A CN 201810748868A CN 109053935 B CN109053935 B CN 109053935B
- Authority
- CN
- China
- Prior art keywords
- titanium complex
- metal titanium
- allyl
- supported
- salicylaldimine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 205
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 205
- 239000010936 titanium Substances 0.000 title claims abstract description 205
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 156
- 239000002184 metal Substances 0.000 title claims abstract description 156
- BPELEZSCHIEMAE-UHFFFAOYSA-N salicylaldehyde imine Chemical compound OC1=CC=CC=C1C=N BPELEZSCHIEMAE-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 43
- 238000001308 synthesis method Methods 0.000 title description 15
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims abstract description 112
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 72
- 239000005977 Ethylene Substances 0.000 claims abstract description 72
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 71
- 239000000178 monomer Substances 0.000 claims abstract description 48
- 239000003054 catalyst Substances 0.000 claims abstract description 45
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 25
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims abstract description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 72
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 66
- 239000003446 ligand Substances 0.000 claims description 59
- 238000001914 filtration Methods 0.000 claims description 55
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 claims description 50
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 49
- 239000000047 product Substances 0.000 claims description 48
- 238000006243 chemical reaction Methods 0.000 claims description 47
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 37
- 238000005406 washing Methods 0.000 claims description 37
- 238000003756 stirring Methods 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 31
- 239000007787 solid Substances 0.000 claims description 31
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 30
- 229920000642 polymer Polymers 0.000 claims description 28
- 238000003760 magnetic stirring Methods 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 25
- 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
- 229910052757 nitrogen Inorganic materials 0.000 claims description 24
- 230000015572 biosynthetic process Effects 0.000 claims description 22
- 238000003786 synthesis reaction Methods 0.000 claims description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- 238000012662 bulk polymerization Methods 0.000 claims description 17
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 17
- 230000002194 synthesizing effect Effects 0.000 claims description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- 239000009566 Mao-to 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
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 16
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical class OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims description 16
- 238000001694 spray drying Methods 0.000 claims description 16
- 229910001220 stainless steel Inorganic materials 0.000 claims description 16
- 239000010935 stainless steel Substances 0.000 claims description 16
- 239000012190 activator Substances 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- WKBALTUBRZPIPZ-UHFFFAOYSA-N 2,6-di(propan-2-yl)aniline Chemical class CC(C)C1=CC=CC(C(C)C)=C1N WKBALTUBRZPIPZ-UHFFFAOYSA-N 0.000 claims description 13
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000002262 Schiff base Substances 0.000 claims description 9
- 150000004753 Schiff bases Chemical class 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000002904 solvent Substances 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
- 125000001246 bromo group Chemical group Br* 0.000 claims description 8
- 239000000460 chlorine Substances 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- 238000001816 cooling 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
- 239000000463 material Substances 0.000 claims description 8
- 239000003208 petroleum Substances 0.000 claims description 8
- 230000000379 polymerizing effect Effects 0.000 claims description 8
- 239000012716 precipitator Substances 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 4
- 229920002866 paraformaldehyde Polymers 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- XWKFPIODWVPXLX-UHFFFAOYSA-N 2-methyl-5-methylpyridine Natural products CC1=CC=C(C)N=C1 XWKFPIODWVPXLX-UHFFFAOYSA-N 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- 229920002521 macromolecule Polymers 0.000 abstract description 10
- 238000010189 synthetic method Methods 0.000 abstract description 8
- 150000003608 titanium Chemical class 0.000 abstract description 5
- 239000012535 impurity Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical class NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 20
- 239000001257 hydrogen Substances 0.000 description 19
- 229910052739 hydrogen Inorganic materials 0.000 description 19
- 239000003921 oil Substances 0.000 description 14
- 239000000843 powder Substances 0.000 description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 12
- 239000003999 initiator Substances 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 9
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 description 8
- 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 7
- 229910003074 TiCl4 Inorganic materials 0.000 description 7
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 7
- 125000001309 chloro group Chemical group Cl* 0.000 description 6
- 241000894007 species Species 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 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
- 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
- INLWEXRRMUMHKB-UHFFFAOYSA-N 2-hydroxy-3-prop-2-enylbenzaldehyde Chemical compound OC1=C(CC=C)C=CC=C1C=O INLWEXRRMUMHKB-UHFFFAOYSA-N 0.000 description 3
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-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
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- BLCKNMAZFRMCJJ-UHFFFAOYSA-N cyclohexyl cyclohexyloxycarbonyloxy carbonate Chemical compound C1CCCCC1OC(=O)OOC(=O)OC1CCCCC1 BLCKNMAZFRMCJJ-UHFFFAOYSA-N 0.000 description 3
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 3
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 3
- 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 3
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-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
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- -1 ethylene, propylene, N-vinyl pyrrolidone Chemical class 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229920000831 ionic polymer Polymers 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
- 235000011147 magnesium chloride Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Images
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 invention discloses a novel macromolecular self-supported salicylaldiminium metal titanium complex, a synthetic method and a using method. The invention takes allyl-substituted salicylaldiminato metal titanium complex and ethylene as raw materials, and prepares a novel macromolecular self-supported salicylaldiminato metal titanium complex D by copolymerization1～D6The resulting titanium complex D1～D6The catalyst can efficiently catalyze the homopolymerization of the N-vinyl pyrrolidone, has extremely low monomer NVP and catalyst residue rate, and can meet the quality requirement of high-quality pharmaceutical grade PVP. The resulting titanium complex D1～D6Can also be dispersed in the solution of N-vinyl pyrrolidone to catalyze the solution polymerization of N-vinyl pyrrolidone. Titanium complexes D1～D6Can be used as a catalyst for recycling. Compared with the existing method for catalyzing the polymerization of N-vinyl pyrrolidone, the macromolecule self-supported salicylaldehyde imine metal titanium complex catalyst has high polymerization efficiency, no residue is generated after the catalyst is recovered, and the requirements of high-quality medical grade PVP on the contents of monomers, catalysts and other impurities can be better met.
Description
Technical Field
The invention belongs to the technical field of non-metallocene titanium complex catalysts. Relates to a novel macromolecular self-supported allyl-substituted salicylaldiminium metal titanium complex, a synthetic method and a using method.
Background
Poly (N-vinyl pyrrolidone, PVP for short) is a non-ionic polymer fine chemical, wherein the pharmaceutical grade PVP is widely applied in the production of medicines. The pharmacopoeias of various countries, particularly north america, europe, japan, have very high quality standards for pharmaceutical PVP, and in particular, there are severe limitations on the residual amounts of N-vinylpyrrolidone monomer and initiator.
PVP is obtained by bulk polymerization, solution polymerization, or the like using a monomer, vinyl pyrrolidone (NVP), as a raw material. PVP is generally synthesized by solution polymerization in industry. Adding an initiator into a solution of NVP (a solvent can be ethanol, benzene and the like) to carry out free radical solution polymerization is the most common method for NVP homopolymerization, AIBN is mostly used as the initiator in PVP polymerization, and no document for initiating the synthesis of PVP by using a water-soluble azo initiator is found. Because NVP monomer and PVP are both soluble in water, AIBN contains a group cyano group harmful to human bodies, and PVP is a product which is mostly used for being in direct contact with human bodies, an initiator or a catalyst containing the group cyano group harmful to human bodies is not adopted to catalyze the homopolymerization of NVP, and the development direction of the pharmaceutical grade PVP is provided.
ZL 201210071. X discloses a preparation method of poly (N-vinyl pyrrolidone), which uses azodiisobutyronitrile, dimethyl azodiisobutyrate, azodimethylbutyronitrile, benzoyl peroxide, cumene hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, methyl ethyl ketone peroxide or dicyclohexyl peroxydicarbonate, cyclohexanone peroxide, tert-butyl peroxybenzoate, diisopropyl peroxydicarbonate or lauroyl peroxide as a composite initiator to prepare PVP. However, the residual rate of NVP monomer in PVP prepared by the method is high, the residual amount of initiator (catalyst) is high, and the PVP standard in the field of medicine can not be met. And the method has low preparation efficiency, long reaction time and high energy consumption, and is not beneficial to the industrial production of PVP.
The novel macromolecular self-supported salicylaldiminato metal titanium complex D1-D6 prepared by the invention has ultrahigh catalytic activity (more than 1000,000g PVP mol-1. Ti-1. h-1) for homopolymerization of monomer N-vinyl pyrrolidone within the temperature range of 30-100 ℃. Compared with the condition that the supported transition metal complexes such as magnesium chloride, silicon dioxide, kaolin and the like are insoluble in vinyl-containing monomers such as ethylene, propylene, N-vinyl pyrrolidone and the like, the macromolecular self-supported salicylaldiminato metal titanium complexes D1-D6 prepared by the method can be well dissolved with various vinyl monomers, so that the macromolecular self-supported salicylaldiminato metal titanium complexes D1-D6 can catalyze homopolymerization of the vinyl monomers in a homogeneous phase manner, and the efficiency of the homogeneous catalysis reaction is higher than that of the heterogeneous catalysis reaction
The catalytic efficiency of the salicylaldimine metal titanium complex catalyst is much higher. Specifically, from the application perspective, compared with the polymerization reaction of monomer NVP initiated by an initiator adopted in the prior art, the macromolecular self-supported titanium complex catalyst can efficiently catalyze the homopolymerization reaction of NVP in a short time to obtain the high-molecular-weight poly (N-vinyl pyrrolidone). The catalytic reaction efficiency is greatly improved, so that the conversion rate of the monomer NVP is greatly improved, the residual rate of the monomer NVP in a polymerization product is greatly reduced, the residual quantity of the catalyst and the cocatalyst is extremely small, and the requirements of high-quality medical grade PVP on the contents of impurities such as the monomer, the catalyst and the like can be well met.
The invention also discloses a novel macromolecular self-supported salicylaldiminato metal titanium complex as a catalyst for catalyzing the polymerization reaction of the aqueous solution of NVP. The macromolecular self-supported salicylaldiminato metal titanium complex D is insoluble in water, is easy to separate from water-soluble poly (N-vinyl pyrrolidone), and is recycled after being filtered and recovered. Compared with the conventional initiators such as azobisisobutyronitrile, dimethyl azobisisobutyrate, azobismethylbutyronitrile, benzoyl peroxide, cumene hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, methyl ethyl ketone peroxide or dicyclohexyl peroxydicarbonate, cyclohexanone peroxide, tert-butyl peroxybenzoate, diisopropyl peroxydicarbonate or lauroyl peroxide and the like, the high-molecular self-supported salicylaldiminium metal titanium complex D1-D6 has higher efficiency in catalyzing the polymerization reaction of N-vinyl pyrrolidone, and the catalyst has no residue and can be recycled for multiple times. The catalytic polymerization process is green and efficient, and can better meet the requirements of high-quality pharmaceutical grade PVP on the content of impurities such as monomers, catalysts and the like.
Disclosure of Invention
A novel macromolecule self-supported salicylaldiminato metal titanium complex is characterized in that the novel macromolecule self-supported salicylaldiminato metal titanium complex is marked as D, and the structural formula of the complex is as follows:
wherein: r1 is selected from one of the following: hydrogen, bromine, chlorine; r2 and R3 are each independently selected from one of the following: hydrogen and isopropyl. D is D1 when R1= chloro and R2= R3= isopropyl; d is D2 when R1= bromo and R2= R3= isopropyl; d is D3 when R1= hydrogen and R2= R3= isopropyl;
d is D4 when R1= chloro and R2= R3= hydrogen; d is D5 when R1= bromo and R2= R3= hydrogen; d is D6 when R1= hydrogen and R2= R3= hydrogen.
"→" indicates a coordinate bond.
“
"denotes a polymer chain formed by copolymerization of allyl and ethylene.
A novel macromolecular self-supported salicylaldiminato metal titanium complex D (D1 or D2 or D3 or D4 or D5 or D6) is prepared from a novel allyl-substituted salicylaldiminato metal titanium complex A (A1 or A2 or A3 or A4 or A5 or A6) and ethylene by a copolymerization method, and the reaction is shown as follows:
“
"represents a polymer chain formed by copolymerization of allyl and ethylene;
the synthesis method comprises the following specific steps: vacuumizing a 250mL polymerization kettle to remove water and oxygen, fully replacing nitrogen, then replacing nitrogen with ethylene, adding 100mL of toluene solvent under the protection of ethylene, introducing normal-pressure ethylene gas until the ethylene is dissolved to saturation, adding 1-100 mu mol of novel allyl-substituted salicylaldimine metal titanium complex A serving as a main catalyst, and adding methylaluminoxane MAO serving as a cocatalyst in a corresponding proportion, wherein the mass ratio of the cocatalyst MAO to the metal titanium complex A is 10-1000: 1. Then continuously introducing ethylene, carrying out polymerization reaction for 0.5-1 h under the conditions of 0-100 ℃ and 0.1-10 MPa under the condition of magnetic stirring, closing a feed valve of the ethylene, emptying the polymerization kettle to normal pressure, discharging materials from the polymerization kettle, filtering to obtain a crude polymer product, washing with ethanol, and drying the obtained solid in vacuum at 60 ℃ to obtain a novel high-polymer self-supported salicylaldehyde imine metallic titanium complex D, wherein the content of metallic titanium is 4.1 mu mol/g
60.0 mu mol/g.
A synthesis method of a novel allyl substituted salicylaldimine metal titanium complex A is characterized by comprising the following specific steps:
the method comprises the following steps: and (4) synthesizing a ligand. The structural formula of the ligand E is as follows:
wherein: r1 is selected from one of the following: hydrogen, bromine, chlorine; r2 and R3 are each independently selected from one of the following: hydrogen and isopropyl.
E is E1 when R1= chloro and R2= R3= isopropyl; e is E2 when R1= bromo and R2= R3= isopropyl; e is E3 when R1= hydrogen and R2= R3= isopropyl; e is E4 when R1= chloro and R2= R3= hydrogen; e is E5 when R1= bromo and R2= R3= hydrogen; e is E6 when R1= hydrogen and R2= R3= hydrogen.
The synthesis of ligand E involves two stages: the first stage is the synthesis of allyl substituted salicylaldehyde; the second stage is the condensation of allyl substituted salicylaldehyde and aniline or 2, 6-diisopropylaniline with Schiff's base to obtain ligand E.
Synthesis of allyl substituted salicylaldehyde: vacuumizing a 250mL reaction bottle, introducing nitrogen, replacing for 3 times, adding 100mL dry toluene, 0.2-1.1 mmol of 2-allyl-p-chlorophenol or 2-allyl-p-bromophenol, 0.01-0.04 mmol of anhydrous SnCl4, 0.8-4.4 mmol of 2, 6-dimethyl pyridine under the protection of nitrogen, carrying out magnetic stirring reflux reaction at room temperature for 20min, adding 1-5 mmol of paraformaldehyde, raising the temperature to 80 ℃, and reacting for 2 h. Separating, purifying and drying the product to respectively obtain 3-allyl-5-chlorosalicylaldehyde and 3-allyl-5-bromosalicylaldehyde.
Condensing allyl substituted salicylaldehyde and aniline or 2, 6-diisopropylaniline by using Schiff base to obtain ligand E: adding 10mmol of 3-allyl salicylaldehyde or 3-allyl-5-chlorosalicylaldehyde or 3-allyl-5-bromosalicylaldehyde and 10-11 mmol of aniline or 2, 6-diisopropylaniline into 50mL of methanol solvent, adding 0.1-0.2 mmol of formic acid as a catalyst, reacting for 1-2 hours at 20-50 ℃ under magnetic stirring, and reacting
Cooling at the temperature of minus 10-0 ℃ to separate out a solid, filtering, washing filter residues by using cold ethanol at the temperature of about 5 ℃, filtering again, recrystallizing in ethanol, washing again by using cold ethanol at the temperature of about 5 ℃, filtering, and drying the solid to obtain the ligands E1-E6.
And step two, synthesizing novel allyl-substituted salicylaldiminato metal titanium complexes A1-A6, wherein A1 corresponds to E1, A2 corresponds to E2, A3 corresponds to E3, A4 corresponds to E4, A5 corresponds to E5, and A6 corresponds to E6.
Dissolving 1.0-2.0 mmol of the ligand E (E1 or E2 or E3 or E4 or E5 or E6) in 50mL of dichloromethane, dropwise adding a solution consisting of 0.5-1.0 mmol of TiCl4 and 30mL of dichloromethane at-30 ℃ under a good stirring condition for 1h, raising the temperature to 30-45 ℃, magnetically stirring for reaction for 2h, injecting 1.0-2.0 mmol of triethylamine into a syringe, continuously stirring for reaction for 2h at 30-45 ℃, concentrating the reaction liquid to about 40mL, adding 30-50mL of petroleum ether as a precipitator, filtering, washing filter residues with 3 x 10mL of cold dichloromethane for 3 times, recrystallizing the obtained solid in dichloromethane, filtering, and drying to obtain the novel allyl-substituted salicylaldiminium metal titanium complex A1-6.
The second step is carried out under the anhydrous and anaerobic condition.
A novel macromolecular self-supported salicylaldiminato metal titanium complex D can catalyze the bulk polymerization of a monomer N-vinyl pyrrolidone (NVP) and can catalyze the solution polymerization of the monomer N-vinyl pyrrolidone (NVP). The titanium complex D is characterized in that the titanium complex D catalyzes the bulk polymerization of monomer N-vinyl pyrrolidone (NVP) in the following steps:
heating a stainless steel polymerization kettle, vacuumizing to remove oxygen, and introducing pure argon to fully displace. Adding 30g of NVP, 0.1-0.5 g of novel macromolecular self-supported salicylaldehyde imine metal titanium complex D (D1 or D2 or D3 or D4 or D5 or D6) with the titanium content of 4.1-60.0 mu mol/g and Methyl Aluminoxane (MAO) in a corresponding proportion as an activator, wherein the mass ratio of the MAO to the metal titanium complex D is 10-100: 1. Magnetically stirring and polymerizing for 0.5-1 h in a constant-temperature oil bath at 30-100 ℃, adding 10-20 g of deionized water to inactivate the system, and finally spray drying to obtain a poly (N-vinyl pyrrolidone) powder product.
A novel macromolecular self-supported salicylaldiminato metal titanium complex D can also be used for catalyzing the solution polymerization of a monomer N-vinyl pyrrolidone. The method is characterized by comprising the following specific steps:
adding 30g of NVP and 60-90 g of deionized water into a stainless steel polymerization kettle, wherein the titanium content is 3-5 g and 4.1
60.0 mu mol/g of novel macromolecular self-supported salicylaldiminato metal titanium complex D (D1 or D2 or D3 or D4 or D5 or D6). And (3) performing magnetic stirring polymerization reaction for 0.5-1 h in a constant-temperature oil bath at 30-100 ℃, filtering, wherein the obtained filter residue is a titanium complex D insoluble in a polymer aqueous solution system, and the filter residue can be recycled as a catalyst for catalyzing aqueous solution polymerization of NVP after being washed and dried for multiple times. And spray drying the filtrate system to obtain a poly (N-vinyl pyrrolidone) powder product.
Compared with the prior art, the invention has the following obvious advantages:
compared with the conventional PVP preparation process in which initiator systems such as azobisisobutyronitrile, dimethyl azodiisobutyrate, azobismethylbutyronitrile, benzoyl peroxide, cumene hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, methyl ethyl ketone peroxide or dicyclohexyl peroxydicarbonate, cyclohexanone peroxide, tert-butyl peroxybenzoate, diisopropyl peroxydicarbonate or lauroyl peroxide and the like are used, the novel macromolecular self-supported salicylaldimine metal titanium complex catalyst has higher catalytic activity. Therefore, when the catalyst of the invention is used for preparing PVP, the amount of the catalyst required by the preparation of unit polymer can be greatly reduced, moreover, the macromolecule self-supported titanium complex catalyst is insoluble in a monomer NVP aqueous solution, and after polymerization is finished, the catalyst D can be recycled for a plurality of times after being filtered and recovered, so that the unit consumption and the cost of the catalyst can be greatly reduced, the polymerization process is green and environment-friendly, toxic and harmful initiators and organic solvents are not used in polymerization, the catalytic polymerization is efficient, the product quality is good, the obtained PVP has no monomer or catalyst residue, and the application requirements of PVP in the medical field can be met.
Drawings
FIG. 1 is a 1H NMR chart of ligand E1 of example 1 of the present invention;
FIG. 2 is an infrared image of the poly (N-vinylpyrrolidone) product of example 1 of this invention;
FIG. 3 is a 1H NMR chart of the poly (N-vinylpyrrolidone) product of example 1 of this invention;
FIG. 4 is a C NMR chart of a poly (N-vinylpyrrolidone) product of example 1 of the present invention.
Detailed description of the preferred embodiment
The invention is further described below by means of specific implementation examples, but it is to be stressed that the invention is in no way limited to the examples listed below. In the following cases:
when R1= chlorine and R2= R3= isopropyl, the corresponding ligand is E1, the corresponding novel allyl substituted salicylaldimine metal titanium complex is A1, and the corresponding novel macromolecule self-supported salicylaldimine metal titanium complex is D1;
when R1= bromine and R2= R3= isopropyl, the corresponding ligand is E2, the corresponding novel allyl substituted salicylaldimine metal titanium complex is A2, and the corresponding novel macromolecule self-supported salicylaldimine metal titanium complex is D2;
when R1= hydrogen and R2= R3= isopropyl, the corresponding ligand is E3, the corresponding novel allyl substituted salicylaldimine metal titanium complex is A3, and the corresponding novel macromolecule self-supported salicylaldimine metal titanium complex is D3;
when R1= chlorine and R2= R3= hydrogen, the corresponding ligand is E4, the corresponding novel allyl substituted salicylaldimine metal titanium complex is A4, and the corresponding novel macromolecule self-supported salicylaldimine metal titanium complex is D4;
when R1= bromine and R2= R3= hydrogen, the corresponding ligand is E5, the corresponding novel allyl substituted salicylaldimine metal titanium complex is A5, and the corresponding novel macromolecule self-supported salicylaldimine metal titanium complex is D5;
when R1= hydrogen and R2= R3= hydrogen, the corresponding ligand is E6, the corresponding novel allyl substituted salicylaldimine metal titanium complex is A6, and the corresponding novel macromolecule self-supported salicylaldimine metal titanium complex is D6;
example 1
A novel macromolecular self-supported salicylaldiminato metal titanium complex D1, a synthetic method and a using method. A novel macromolecular self-supported salicylaldiminato metal titanium complex is marked as D1 and has the structural formula as follows:
wherein: "→" indicates a coordination bond;
“
"denotes a polymer chain formed by copolymerization of allyl and ethylene.
A novel macromolecular self-supported salicylaldiminato metal titanium complex D1 is prepared from a novel allyl-substituted salicylaldiminato metal titanium complex A1 and ethylene by a copolymerization method. The schematic is as follows:
wherein: "→" indicates a coordination bond;
“
"denotes a polymer chain formed by copolymerization of allyl and ethylene.
The synthesis method comprises the following specific steps: vacuumizing a 250mL polymerization kettle to remove water and oxygen, fully replacing nitrogen, then replacing nitrogen with ethylene, adding 100mL of toluene solvent under the protection of ethylene, introducing normal-pressure ethylene gas until the ethylene is dissolved to saturation, adding 10 mu mol of novel allyl-substituted salicylaldimine metal titanium complex A1 serving as a main catalyst, and adding methylaluminoxane MAO serving as a cocatalyst in a corresponding proportion, wherein the mass ratio of the cocatalyst MAO to the metal titanium complex A1 is 100: 1. And then continuously introducing ethylene, carrying out polymerization reaction for 0.5h under the conditions of 30 ℃ and 3MPa and magnetic stirring, closing a feed valve of the ethylene, emptying the polymerization kettle to normal pressure, discharging the materials from the polymerization kettle, filtering to obtain a crude polymer product, washing with ethanol, and carrying out vacuum drying on the obtained solid at 60 ℃ to obtain the novel macromolecular self-supported salicylaldiminato metal titanium complex D1, wherein the content of metal titanium is 4.5 mu mol/g.
A synthesis method of a novel allyl-substituted salicylaldimine metal titanium complex A1 comprises the following specific steps:
the method comprises the following steps: and (4) synthesizing a ligand.
Ligand E1 has the structural formula:
the synthesis of ligand E1 involves two stages: the first stage is the synthesis of 3-allyl-5-chlorosalicylaldehyde; the second stage is the condensation of 3-allyl-5-chlorosalicylaldehyde and 2, 6-diisopropylaniline by Schiff base to obtain ligand E1.
3-allyl-5-chlorosalicylaldehyde synthesis: a250 mL reaction flask was evacuated and purged with nitrogen
After 3 times, 100mL of dry toluene, 0.2mmol of 2-allyl-p-chlorophenol, 0.01 mmol of anhydrous SnCl4 and 0.8 mmol of 2, 6-lutidine are added under the protection of nitrogen, and after the reaction of magnetic stirring reflux at room temperature for 20min, 1.1 mmol of paraformaldehyde is added, the temperature is raised to 80 ℃ and the reaction is carried out for 2 h. Separating, purifying and drying the product to obtain the 3-allyl-5-chlorosalicylaldehyde.
Condensing 3-allyl-5-chlorosalicylaldehyde and 2, 6-diisopropylaniline by using Schiff base to obtain ligand E1: adding 10mmol of 3-allyl-5-chlorosalicylaldehyde and 10.1mmol of 2, 6-diisopropylaniline into 50mL of methanol solvent, adding 0.1mmol of formic acid as a catalyst, performing magnetic stirring reaction at 30 ℃ for 1h, cooling at-10 ℃ to separate out a solid, filtering, washing filter residues with cold ethanol at about 5 ℃, filtering again, recrystallizing in ethanol, washing with cold ethanol at about 5 ℃, filtering, and drying the solid to obtain the ligand E1.
Step two, synthesizing a novel allyl substituted salicylaldimine metal titanium complex A1.
Dissolving 1.0 mmol of the ligand E1 in 50mL of dichloromethane, dropwise adding a solution consisting of 0.5 mmol of TiCl4 and 30mL of dichloromethane within 1h under the conditions of-30 ℃ and good stirring, raising the temperature to 30 ℃, magnetically stirring for reaction for 2h, then injecting 1.0 mmol of triethylamine into a syringe, continuously stirring for reaction for 2h at 35 ℃, then concentrating the reaction solution to about 40mL, adding 30mL of petroleum ether as a precipitator, filtering, washing filter residues with 3X 10mL of cold dichloromethane for 3 times, recrystallizing the obtained solid in dichloromethane, filtering, and drying to obtain the novel allyl-substituted salicylaldimine metal titanium complex A1.
The second step is carried out under the anhydrous and anaerobic condition.
A novel macromolecular self-supported salicylaldiminato metal titanium complex D1 can catalyze the bulk polymerization of monomer N-vinyl pyrrolidone (NVP). Titanium complexes D1Catalyzing the bulk polymerization of monomer N-vinyl pyrrolidone (NVP), and the method comprises the following steps:
heating a stainless steel polymerization kettle, vacuumizing to remove oxygen, and introducing pure argon to fully displace. 30g of NVP, 0.3g of a novel polymeric self-supported salicylaldiminato metal titanium complex having a titanium content of 4.5. mu. mol/g D1 and a corresponding proportion of Methylaluminoxane (MAO) were added as activators, the ratio of the amount of activator MAO to the amount of species of the metal titanium complex D1 being 50: 1. Magnetically stirring and polymerizing for 1h in a constant-temperature oil bath at 60 ℃, adding 20g of deionized water to inactivate the system, and finally spray drying to obtain a poly (N-vinyl pyrrolidone) powder product. The data of the obtained product detected according to pharmacopoeia are shown in table 1.
A method for using a novel macromolecular self-supported salicylaldiminato metal titanium complex D1 to catalyze the solution polymerization of monomer N-vinyl pyrrolidone. The method comprises the following specific steps:
30g of NVP, 60g of water and 3g of novel macromolecular self-supported salicylaldimine metal titanium complex D1 with the titanium content of 4.5 mu mol/g are added into a stainless steel polymerization kettle. And (3) carrying out magnetic stirring polymerization reaction for 1h in a constant-temperature oil bath at 60 ℃, filtering, recovering the titanium complex D1, and washing and drying the titanium complex D1 by deionized water for multiple times to recycle the titanium complex. And spray drying the filtrate system to obtain a poly (N-vinyl pyrrolidone) powder product. The data of the obtained product detected according to pharmacopoeia are shown in table 1.
Example 2
A novel macromolecular self-supported salicylaldiminato metal titanium complex D2, a synthetic method and a using method. A novel macromolecular self-supported salicylaldiminato metal titanium complex is marked as D2 and has the structural formula as follows:
wherein: "→" indicates a coordination bond;
“
"denotes a polymer chain formed by copolymerization of allyl and ethylene.
A novel macromolecular self-supported salicylaldiminato metal titanium complex D2 is prepared from a novel allyl-substituted salicylaldiminato metal titanium complex A2 and ethylene by a copolymerization method. The schematic is as follows:
wherein: "→" indicates a coordination bond;
“
"denotes a polymer chain formed by copolymerization of allyl and ethylene.
The synthesis method comprises the following specific steps: vacuumizing a 250mL polymerization kettle to remove water and oxygen, fully replacing nitrogen, then replacing nitrogen with ethylene, adding 100mL of toluene solvent under the protection of ethylene, introducing normal-pressure ethylene gas until the ethylene is dissolved to saturation, adding 10 mu mol of novel allyl-substituted salicylaldimine metal titanium complex A2 serving as a main catalyst, and adding methylaluminoxane MAO serving as a cocatalyst in a corresponding proportion, wherein the mass ratio of the cocatalyst MAO to the metal titanium complex A2 is 100: 1. Then continuously introducing ethylene, carrying out polymerization reaction for 0.5h under the conditions of 30 ℃ and 3MPa and magnetic stirring, closing a feed valve of the ethylene, emptying the polymerization kettle to normal pressure, discharging materials from the polymerization kettle, filtering to obtain a crude polymer product, washing with ethanol, and drying the obtained solid in vacuum at 60 ℃ to obtain the novel macromolecular self-supported salicylaldiminato metal titanium complex D2, wherein the content of metal titanium is 5.3 mu mol/g.
A synthesis method of a novel allyl-substituted salicylaldimine metal titanium complex A2 comprises the following specific steps:
the method comprises the following steps: and (4) synthesizing a ligand. Ligand E2 has the structural formula:
the synthesis of ligand E2 involves two stages: the first stage is the synthesis of 3-allyl-5-bromosalicylaldehyde; the second stage is condensation of 3-allyl-5-bromosalicylaldehyde and 2, 6-diisopropylaniline by Schiff base to obtain ligand E2.
3-allyl-5-bromosalicylaldehyde synthesis: a250 mL reaction bottle is vacuumized, nitrogen is introduced, nitrogen is replaced for 3 times, 100mL of dry toluene, 0.2mmol of 2-allyl-p-bromophenol, 0.01 mmol of anhydrous SnCl4 and 0.8 mmol of 2, 6-lutidine are added under the protection of nitrogen, magnetic stirring reflux reaction is carried out for 20min at room temperature, 1.1 mmol of paraformaldehyde is added, the temperature is raised to 80 ℃, and reaction is carried out for 2 h. Separating, purifying and drying the product to obtain the 3-allyl-5-bromosalicylaldehyde.
Condensing 3-allyl-5-bromosalicylaldehyde and 2, 6-diisopropylaniline by using Schiff base to obtain a ligand E2: adding 10mmol of 3-allyl-5-chlorosalicylaldehyde and 10.1mmol of 2, 6-diisopropylaniline into 50mL of methanol solvent, adding 0.1mmol of formic acid as a catalyst, performing magnetic stirring reaction at 30 ℃ for 1h, cooling at-10 ℃ to separate out a solid, filtering, washing filter residues with cold ethanol at about 5 ℃, filtering again, recrystallizing in ethanol, washing with cold ethanol at about 5 ℃, filtering, and drying the solid to obtain the ligand E2.
Step two, synthesizing a novel allyl substituted salicylaldimine metal titanium complex A2.
Dissolving 1.0 mmol of the ligand E2 in 50mL of dichloromethane, dropwise adding a solution consisting of 0.5 mmol of TiCl4 and 30mL of dichloromethane within 1h under the conditions of-30 ℃ and good stirring, raising the temperature to 30 ℃, magnetically stirring for reaction for 2h, then injecting 1.0 mmol of triethylamine into a syringe, continuously stirring for reaction for 2h at 35 ℃, then concentrating the reaction solution to about 40mL, adding 30mL of petroleum ether as a precipitator, filtering, washing filter residues with 3X 10mL of cold dichloromethane for 3 times, recrystallizing the obtained solid in dichloromethane, filtering, and drying to obtain the novel allyl-substituted salicylaldimine metal titanium complex A2.
The second step is carried out under the anhydrous and anaerobic condition.
A novel macromolecular self-supported salicylaldiminato metal titanium complex D2 can catalyze the bulk polymerization of monomer N-vinyl pyrrolidone (NVP). The titanium complex D2 is used for catalyzing the bulk polymerization of monomer N-vinyl pyrrolidone (NVP) and comprises the following specific steps:
heating a stainless steel polymerization kettle, vacuumizing to remove oxygen, and introducing pure argon to fully displace. 30g of NVP, 0.3g of a novel polymeric self-supported salicylaldiminato metal titanium complex having a titanium content of 5.3. mu. mol/g D2 and a corresponding proportion of Methylaluminoxane (MAO) were added as activators, the ratio of the amount of activator MAO to the amount of species of the metal titanium complex D2 being 50: 1. Magnetically stirring and polymerizing for 1h in a constant-temperature oil bath at 60 ℃, adding 20g of deionized water to inactivate the system, and finally spray drying to obtain a poly (N-vinyl pyrrolidone) powder product. The data of the obtained product detected according to pharmacopoeia are shown in table 1.
A use method of a novel macromolecular self-supported salicylaldiminato metal titanium complex D2 for catalyzing solution polymerization of monomer N-vinyl pyrrolidone comprises the following specific steps:
30g of NVP, 60g of water and 3g of novel macromolecular self-supported salicylaldimine metal titanium complex D2 with the titanium content of 5.3 mu mol/g are added into a stainless steel polymerization kettle. And (3) carrying out magnetic stirring polymerization reaction for 1h in a constant-temperature oil bath at 60 ℃, filtering, recovering the titanium complex D2, and washing and drying the titanium complex D2 by deionized water for multiple times to recycle the titanium complex. And spray drying the filtrate system to obtain a poly (N-vinyl pyrrolidone) powder product. The data of the obtained product detected according to pharmacopoeia are shown in table 1.
Example 3
A novel macromolecular self-supported salicylaldiminato metal titanium complex D3, a synthetic method and a using method. A novel macromolecular self-supported salicylaldiminato metal titanium complex is marked as D3 and has the structural formula as follows:
wherein: "→" indicates a coordination bond;
“
"denotes a polymer chain formed by copolymerization of allyl and ethylene.
A novel macromolecular self-supported salicylaldiminato metal titanium complex D3 is prepared from a novel allyl-substituted salicylaldiminato metal titanium complex A3 and ethylene by a copolymerization method. The schematic is as follows:
wherein: "→" indicates a coordination bond;
“
"denotes a polymer chain formed by copolymerization of allyl and ethylene.
The synthesis method comprises the following specific steps: vacuumizing a 250mL polymerization kettle to remove water and oxygen, fully replacing nitrogen, then replacing nitrogen with ethylene, adding 100mL of toluene solvent under the protection of ethylene, introducing normal-pressure ethylene gas until the ethylene is dissolved to saturation, adding 10 mu mol of novel allyl-substituted salicylaldimine metal titanium complex A3 serving as a main catalyst, and adding methylaluminoxane MAO serving as a cocatalyst in a corresponding proportion, wherein the mass ratio of the cocatalyst MAO to the metal titanium complex A3 is 100: 1. Then continuously introducing ethylene, carrying out polymerization reaction for 0.5h under the conditions of 30 ℃ and 3MPa and magnetic stirring, closing an ethylene feeding valve, and carrying out
The polymerization kettle is vented to normal pressure, the materials are discharged from the polymerization kettle and filtered to obtain a polymer crude product, the polymer crude product is washed by ethanol,
vacuum drying the obtained solid at 60 ℃ to obtain the novel macromolecular self-supported salicylaldiminato metallic titanium
The complex D3, wherein the content of metallic titanium is 4.9 mu mol/g.
A synthesis method of a novel allyl-substituted salicylaldimine metal titanium complex A3 comprises the following specific steps:
the method comprises the following steps: and (4) synthesizing a ligand. Ligand E3 has the structural formula:
synthesis of ligand E3: adding 10mmol of 3-allyl salicylaldehyde and 11mmol of 2, 6-diisopropylaniline into 50mL of methanol solvent, adding 0.1mmol of formic acid as a catalyst, carrying out magnetic stirring reaction at 30 ℃ for 1h, cooling at-10 ℃ to separate out a solid, filtering, washing filter residues with cold ethanol at about 5 ℃, filtering again, recrystallizing in ethanol, washing with cold ethanol at about 5 ℃, filtering, and drying the solid to obtain the ligand E3.
Step two, synthesizing a novel allyl substituted salicylaldimine metal titanium complex A3.
Dissolving 1.0 mmol of the ligand E3 in 50mL of dichloromethane, dropwise adding a solution consisting of 0.5 mmol of TiCl4 and 30mL of dichloromethane within 1h under the conditions of-30 ℃ and good stirring, raising the temperature to 30 ℃, magnetically stirring for reaction for 2h, then injecting 1.0 mmol of triethylamine into a syringe, continuously stirring for reaction for 2h at 35 ℃, then concentrating the reaction solution to about 40mL, adding 30mL of petroleum ether as a precipitator, filtering, washing filter residues with 3X 10mL of cold dichloromethane for 3 times, recrystallizing the obtained solid in dichloromethane, filtering, and drying to obtain the novel allyl-substituted salicylaldimine metal titanium complex A3.
The second step is carried out under the anhydrous and anaerobic condition.
A novel macromolecular self-supported salicylaldiminato metal titanium complex D3 can catalyze the bulk polymerization of monomer N-vinyl pyrrolidone (NVP). The titanium complex D3 is used for catalyzing the bulk polymerization of monomer N-vinyl pyrrolidone (NVP) and comprises the following specific steps:
heating a stainless steel polymerization kettle, vacuumizing to remove oxygen, and introducing pure argon to fully displace. 30g of NVP, 0.3g of a novel polymeric self-supported salicylaldiminato metal titanium complex having a titanium content of 4.9. mu. mol/g D3 and a corresponding proportion of Methylaluminoxane (MAO) were added as activators, the ratio of the amount of activator MAO to the amount of species of the metal titanium complex D3 being 50: 1. Magnetically stirring and polymerizing for 1h in a constant-temperature oil bath at 60 ℃, adding 20g of deionized water to inactivate the system, and finally spray drying to obtain a poly (N-vinyl pyrrolidone) powder product. The data of the obtained product detected according to pharmacopoeia are shown in table 1.
The use method of the novel macromolecular self-supported salicylaldiminato metal titanium complex D3 for catalyzing solution polymerization of monomer N-vinyl pyrrolidone comprises the following specific steps:
30g of NVP, 60g of water and 3g of novel macromolecular self-supported salicylaldimine metal titanium complex D3 with the titanium content of 4.9 mu mol/g are added into a stainless steel polymerization kettle. And (3) carrying out magnetic stirring polymerization reaction for 1h in a constant-temperature oil bath at 60 ℃, filtering, recovering the titanium complex D3, and washing and drying the titanium complex D3 by deionized water for multiple times to recycle the titanium complex. And spray drying the filtrate system to obtain a poly (N-N-vinyl pyrrolidone) powder product. The data of the obtained product detected according to pharmacopoeia are shown in table 1.
Example 4
A novel macromolecular self-supported salicylaldiminato metal titanium complex D4, a synthetic method and a using method. A novel macromolecular self-supported salicylaldiminato metal titanium complex is marked as D4 and has the structural formula as follows:
wherein: "→" indicates a coordination bond;
“
"denotes a polymer chain formed by copolymerization of allyl and ethylene.
A novel macromolecular self-supported salicylaldiminato metal titanium complex D4 is prepared from a novel allyl-substituted salicylaldiminato metal titanium complex A4 and ethylene by a copolymerization method. The schematic is as follows:
wherein: "→" indicates a coordination bond;
“
"denotes a polymer chain formed by copolymerization of allyl and ethylene.
The synthesis method comprises the following specific steps: vacuumizing a 250mL polymerization kettle to remove water and oxygen, fully replacing nitrogen, then replacing nitrogen with ethylene, adding 100mL of toluene solvent under the protection of ethylene, introducing normal-pressure ethylene gas until the ethylene is dissolved to saturation, adding 10 mu mol of novel allyl-substituted salicylaldimine metal titanium complex A4 serving as a main catalyst, and adding methylaluminoxane MAO serving as a cocatalyst in a corresponding proportion, wherein the mass ratio of the cocatalyst MAO to the metal titanium complex A4 is 100: 1. Then continuously introducing ethylene, carrying out polymerization reaction for 0.5h under the conditions of 30 ℃ and 3MPa and magnetic stirring, closing a feed valve of the ethylene, emptying the polymerization kettle to normal pressure, discharging materials from the polymerization kettle, filtering to obtain a crude polymer product, washing with ethanol, and drying the obtained solid in vacuum at 60 ℃ to obtain the novel macromolecular self-supported salicylaldiminato metal titanium complex D4, wherein the content of metal titanium is 4.3 mu mol/g.
A method for synthesizing a novel allyl-substituted salicylaldimine metal titanium complex A4 comprises the following specific steps:
the method comprises the following steps: and (4) synthesizing a ligand. Ligand E4 has the structural formula:
the synthesis of ligand E4 involves two stages: the first stage is the synthesis of 3-allyl-5-chlorosalicylaldehyde; the second stage is the condensation of 3-allyl-5-chlorosalicylaldehyde and aniline with Schiff's base to obtain ligand E4.
3-allyl-5-chlorosalicylaldehyde synthesis: see example 1.
Condensing 3-allyl-5-chlorosalicylaldehyde and aniline through Schiff base to obtain a ligand E4: adding 10mmol of 3-allyl-5-chlorosalicylaldehyde and 10.1mmol of aniline into 50mL of methanol solvent, adding 0.1mmol of formic acid as a catalyst, magnetically stirring at 30 ℃ for reaction for 1h, cooling at-10 ℃ to separate out a solid, filtering, washing filter residues with cold ethanol at about 5 ℃, filtering again, recrystallizing in ethanol, washing with cold ethanol at about 5 ℃, filtering, and drying the solid to obtain the ligand E4.
Step two, synthesizing a novel allyl substituted salicylaldimine metal titanium complex A4.
Dissolving 1.0 mmol of the ligand E4 in 50mL of dichloromethane, dropwise adding a solution consisting of 0.5 mmol of TiCl4 and 30mL of dichloromethane within 1h under the conditions of-30 ℃ and good stirring, raising the temperature to 30 ℃, magnetically stirring for reaction for 2h, then injecting 1.0 mmol of triethylamine into a syringe, continuously stirring for reaction for 2h at 35 ℃, then concentrating the reaction solution to about 40mL, adding 30mL of petroleum ether as a precipitator, filtering, washing filter residues with 3X 10mL of cold dichloromethane for 3 times, recrystallizing the obtained solid in dichloromethane, filtering, and drying to obtain the novel allyl-substituted salicylaldimine metal titanium complex A4.
The second step is carried out under the anhydrous and anaerobic condition.
A novel macromolecular self-supported salicylaldiminato metal titanium complex D4 can catalyze the bulk polymerization of monomer N-vinyl pyrrolidone (NVP). The titanium complex D4 is used for catalyzing the bulk polymerization of monomer N-vinyl pyrrolidone (NVP) and comprises the following specific steps:
heating a stainless steel polymerization kettle, vacuumizing to remove oxygen, and introducing pure argon to fully displace. 30g of NVP, 0.3g of a novel polymeric self-supported salicylaldiminato metal titanium complex having a titanium content of 4.3. mu. mol/g D4 and a corresponding proportion of Methylaluminoxane (MAO) were added as activators, the ratio of the amount of activator MAO to the amount of species of the metal titanium complex D4 being 50: 1. Magnetically stirring and polymerizing for 1h in a constant-temperature oil bath at 60 ℃, adding 20g of deionized water to inactivate the system, and finally spray drying to obtain a poly (N-vinyl pyrrolidone) powder product. The data of the obtained product detected according to pharmacopoeia are shown in Table 1
The use method of the novel macromolecular self-supported salicylaldiminato metal titanium complex D4 for catalyzing solution polymerization of monomer N-vinyl pyrrolidone comprises the following specific steps:
30g of NVP, 60g of water and 3g of novel macromolecular self-supported salicylaldimine metal titanium complex D4 with the titanium content of 4.3 mu mol/g are added into a stainless steel polymerization kettle. And (3) carrying out magnetic stirring polymerization reaction for 1h in a constant-temperature oil bath at 60 ℃, filtering, recovering the titanium complex D4, and washing and drying the titanium complex D4 by deionized water for multiple times to recycle the titanium complex. And spray drying the filtrate system to obtain a poly (N-vinyl pyrrolidone) powder product. The data of the obtained product detected according to pharmacopoeia are shown in table 1.
Example 5
A novel macromolecular self-supported salicylaldiminato metal titanium complex D5, a synthetic method and a using method. A novel macromolecular self-supported salicylaldiminato metal titanium complex is marked as D5 and has the structural formula as follows:
wherein: "→" indicates a coordination bond;
“
"denotes a polymer chain formed by copolymerization of allyl and ethylene.
A novel macromolecular self-supported salicylaldiminato metal titanium complex D5 is prepared from a novel allyl-substituted salicylaldiminato metal titanium complex A5 and ethylene by a copolymerization method. The schematic is as follows:
wherein: "→" indicates a coordination bond;
“
"denotes a polymer chain formed by copolymerization of allyl and ethylene.
The synthesis method comprises the following specific steps: vacuumizing a 250mL polymerization kettle to remove water and oxygen, fully replacing nitrogen, then replacing nitrogen with ethylene, adding 100mL of toluene solvent under the protection of ethylene, introducing normal-pressure ethylene gas until the ethylene is dissolved to saturation, adding 10 mu mol of novel allyl-substituted salicylaldimine metal titanium complex A5 serving as a main catalyst, and adding methylaluminoxane MAO serving as a cocatalyst in a corresponding proportion, wherein the mass ratio of the cocatalyst MAO to the metal titanium complex A5 is 100: 1. Then continuously introducing ethylene, carrying out polymerization reaction for 0.5h under the conditions of 30 ℃ and 3MPa and magnetic stirring, closing a feed valve of the ethylene, emptying the polymerization kettle to normal pressure, discharging materials from the polymerization kettle, filtering to obtain a crude polymer product, washing with ethanol, and drying the obtained solid in vacuum at 60 ℃ to obtain the novel macromolecular self-supported salicylaldiminato metal titanium complex D5, wherein the content of metal titanium is 5.1 mu mol/g.
A synthesis method of a novel allyl-substituted salicylaldimine metal titanium complex A5 comprises the following specific steps:
the method comprises the following steps: and (4) synthesizing a ligand. Ligand E5 has the structural formula:
the synthesis of ligand E5 involves two stages: the first stage is the synthesis of 3-allyl-5-bromosalicylaldehyde; the second stage is the condensation of 3-allyl-5-bromosalicylaldehyde and aniline with Schiff's base to obtain ligand E5.
3-allyl-5-bromosalicylaldehyde synthesis: see example 2.
Condensing 3-allyl-5-bromosalicylaldehyde and aniline through a Schiff base to obtain a ligand E5: 10mmol of 3-
Adding allyl-5-bromosalicylaldehyde and 10.1mmol of aniline into 50mL of methanol solvent, adding 0.1mmol of formic acid as a catalyst, carrying out magnetic stirring reaction at 30 ℃ for 1h, cooling at-10 ℃ to separate out a solid, filtering, washing filter residues with cold ethanol at about 5 ℃, filtering again, recrystallizing in ethanol, washing with cold ethanol at about 5 ℃, filtering, and drying the solid to obtain the ligand E5.
Step two, synthesizing a novel allyl substituted salicylaldimine metal titanium complex A5.
Dissolving 1.0 mmol of the ligand E5 in 50mL of dibromomethane, dropwise adding a solution consisting of 0.5 mmol of TiCl4 and 30mL of dibromomethane into the solution at the temperature of minus 30 ℃ within 1h under good stirring, raising the temperature to 30 ℃, magnetically stirring the solution for reaction for 2h, injecting 1.0 mmol of triethylamine into the solution by using a syringe, continuously stirring the solution for reaction for 2h at the temperature of 35 ℃, concentrating the reaction solution to about 40mL, adding 30mL of petroleum ether as a precipitator, filtering the solution, washing filter residues by 3 x 10mL of cold dibromomethane for 3 times, recrystallizing the obtained solid in the dibromomethane, filtering and drying the recrystallized product to obtain the novel allyl-substituted salicylaldiminium metal titanium complex A5.
The second step is carried out under the anhydrous and anaerobic condition.
A novel macromolecular self-supported salicylaldiminato metal titanium complex D5 can catalyze the bulk polymerization of monomer N-vinyl pyrrolidone (NVP). The titanium complex D5 is used for catalyzing the bulk polymerization of monomer N-vinyl pyrrolidone (NVP) and comprises the following specific steps:
heating a stainless steel polymerization kettle, vacuumizing to remove oxygen, and introducing pure argon to fully displace. 30g of NVP, 0.3g of a novel polymeric self-supported salicylaldiminato metal titanium complex having a titanium content of 5.1. mu. mol/g D5 and a corresponding proportion of Methylaluminoxane (MAO) were added as activators, the ratio of the amount of activator MAO to the amount of species of the metal titanium complex D5 being 50: 1. Magnetically stirring and polymerizing for 1h in a constant-temperature oil bath at 60 ℃, adding 20g of deionized water to inactivate the system, and finally spray drying to obtain a poly (N-vinyl pyrrolidone) powder product. The data of the obtained product detected according to pharmacopoeia are shown in table 1.
The use method of the novel macromolecular self-supported salicylaldiminato metal titanium complex D5 for catalyzing solution polymerization of monomer N-vinyl pyrrolidone comprises the following specific steps:
30g of NVP, 60g of water and 3g of novel macromolecular self-supported salicylaldimine metal titanium complex D5 with the titanium content of 5.1 mu mol/g are added into a stainless steel polymerization kettle. And (3) carrying out magnetic stirring polymerization reaction for 1h in a constant-temperature oil bath at 60 ℃, filtering, recovering the titanium complex D5, and washing and drying the titanium complex D5 by deionized water for multiple times to recycle the titanium complex. And spray drying the filtrate system to obtain a poly (N-vinyl pyrrolidone) powder product. The data of the obtained product detected according to pharmacopoeia are shown in table 1.
Example 6
A novel macromolecular self-supported salicylaldiminato metal titanium complex D6, a synthetic method and a using method. A novel macromolecular self-supported salicylaldiminato metal titanium complex is marked as D6 and has the structural formula as follows:
wherein: "→" indicates a coordination bond;
“
"denotes a polymer chain formed by copolymerization of allyl and ethylene.
A novel macromolecular self-supported salicylaldiminato metal titanium complex D6 is prepared from a novel allyl-substituted salicylaldiminato metal titanium complex A6 and ethylene by a copolymerization method. The schematic is as follows:
wherein: "→" indicates a coordination bond;
“
"denotes a polymer chain formed by copolymerization of allyl and ethylene.
The synthesis method comprises the following specific steps: vacuumizing a 250mL polymerization kettle to remove water and oxygen, fully replacing nitrogen, then replacing nitrogen with ethylene, adding 100mL of toluene solvent under the protection of ethylene, introducing normal-pressure ethylene gas until the ethylene is dissolved to saturation, adding 10 mu mol of novel allyl-substituted salicylaldimine metal titanium complex A6 serving as a main catalyst, and adding methylaluminoxane MAO serving as a cocatalyst in a corresponding proportion, wherein the mass ratio of the cocatalyst MAO to the metal titanium complex A6 is 100: 1. Then continuously introducing ethylene, carrying out polymerization reaction for 0.5h under the conditions of 30 ℃ and 3MPa and magnetic stirring, closing a feed valve of the ethylene, emptying the polymerization kettle to normal pressure, discharging materials from the polymerization kettle, filtering to obtain a crude polymer product, washing with ethanol, and drying the obtained solid in vacuum at 60 ℃ to obtain the novel macromolecular self-supported salicylaldiminato metal titanium complex D6, wherein the content of metal titanium is 5.9 mu mol/g.
A synthesis method of a novel allyl-substituted salicylaldimine metal titanium complex A6 comprises the following specific steps:
the method comprises the following steps: and (4) synthesizing a ligand. Ligand E6 has the structural formula:
synthesis of ligand E6: adding 10mmol of ordered 3-allyl salicylaldehyde and 10.1mmol of aniline into 50mL of methanol solvent, adding 0.1mmol of formic acid as a catalyst, performing magnetic stirring reaction at 30 ℃ for 1h, cooling at-10 ℃ to separate out a solid, filtering, washing filter residues with cold ethanol at about 5 ℃, filtering again, recrystallizing in ethanol, washing with cold ethanol at about 5 ℃, filtering, and drying the solid to obtain ligand E6.
Step two, synthesizing a novel allyl substituted salicylaldimine metal titanium complex A6.
Dissolving 1.0 mmol of the ligand E6 in 50mL of dibromomethane, dropwise adding a solution consisting of 0.5 mmol of TiCl4 and 30mL of dibromomethane into the solution at the temperature of minus 30 ℃ within 1h under good stirring, raising the temperature to 30 ℃, magnetically stirring the solution for reaction for 2h, injecting 1.0 mmol of triethylamine into the solution by using a syringe, continuously stirring the solution for reaction for 2h at the temperature of 35 ℃, concentrating the reaction solution to about 40mL, adding 30mL of petroleum ether as a precipitator, filtering the solution, washing filter residues by 3 x 10mL of cold dibromomethane for 3 times, recrystallizing the obtained solid in the dibromomethane, filtering and drying the recrystallized product to obtain the novel allyl-substituted salicylaldiminium metal titanium complex A6.
The second step is carried out under the anhydrous and anaerobic condition.
A novel macromolecular self-supported salicylaldiminato metal titanium complex D6 can catalyze the bulk polymerization of monomer N-vinyl pyrrolidone (NVP). The titanium complex D6 is used for catalyzing the bulk polymerization of monomer N-vinyl pyrrolidone (NVP) and comprises the following specific steps:
heating a stainless steel polymerization kettle, vacuumizing to remove oxygen, and introducing pure argon to fully displace. 30g of NVP, 0.3g of a novel polymeric self-supported salicylaldiminato metal titanium complex having a titanium content of 5.9. mu. mol/g D6 and a corresponding proportion of Methylaluminoxane (MAO) were added as activators, the ratio of the amount of activator MAO to the amount of species of the metal titanium complex D6 being 50: 1. Magnetically stirring and polymerizing for 1h in a constant-temperature oil bath at 60 ℃, adding 20g of deionized water to inactivate the system, and finally spray drying to obtain a poly (N-vinyl pyrrolidone) powder product. The data of the obtained product detected according to pharmacopoeia are shown in table 1.
The use method of the novel macromolecular self-supported salicylaldiminato metal titanium complex D6 for catalyzing solution polymerization of monomer N-vinyl pyrrolidone comprises the following specific steps:
30g of NVP, 60g of water and 3g of novel macromolecular self-supported salicylaldimine metal titanium complex D6 with the titanium content of 5.9 mu mol/g are added into a stainless steel polymerization kettle. Magnetically stirring in 60 deg.C constant temperature oil bath for polymerization reaction for 1 hr, filtering, recovering titanium complex D6, washing with deionized water for several times, and drying
The D6 can be recycled. And spray drying the filtrate system to obtain a poly (N-vinyl pyrrolidone) powder product. The data of the obtained product detected according to pharmacopoeia are shown in table 1.
Table 1 example test data
The comparative examples are derived from: ZL 201210410071.X
As shown by comparison of the reaction time and the K value of examples 1-6 and the comparative example in Table 1, the novel allyl-substituted salicylaldimine metal titanium complex catalyst provided by the invention has higher catalytic activity than that of the catalytic system in the comparative example, and can obtain the poly (N-vinylpyrrolidone) of K30 in a shorter time. As shown by comparison of monomer residual rates of examples 1-6 and comparative examples in Table 1, the NVP monomer residual rate of the poly (N-vinylpyrrolidone) obtained by using the novel macromolecular self-supported salicylaldimine metal titanium complex as a catalyst for NVP polymerization is lower than that of the poly (N-vinylpyrrolidone) prepared by using the catalytic system in the comparative example.
In conclusion, the novel macromolecular self-supported salicylaldiminato metal titanium complex D1-D6 prepared by the invention has ultrahigh catalytic activity (more than 1000,000 g. PVP mol-1. Ti-1. h-1) for homopolymerization of monomer N-vinyl pyrrolidone within the temperature range of 30-100 ℃. Compared with the polymerization reaction of monomer NVP initiated by an initiator adopted in the prior art, the macromolecular self-supported titanium complex catalyst can efficiently catalyze the homopolymerization reaction of NVP in a short time to obtain high-molecular-weight poly (N-vinyl pyrrolidone) (PVP). The catalytic reaction efficiency is greatly improved, so that the conversion rate of the monomer NVP is greatly improved, the residual rate of the monomer NVP in a polymerization product is greatly reduced, and the requirements of high-quality medical grade PVP on the contents of impurities such as the monomer, the catalyst and the like can be well met.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention. It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, it is intended that the present invention cover the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents.
Claims (4)
1. A preparation method of a macromolecular self-supported salicylaldiminato metal titanium complex D is characterized in that the macromolecular self-supported salicylaldiminato metal titanium complex D is prepared from an allyl-substituted salicylaldiminato metal titanium complex A and ethylene by a copolymerization method, and is as follows:
wherein: r1One selected from the following: bromine, chlorine; r2And R3Is isopropyl; when R is1= chlorine and R2=R3When the isopropyl group is not substituted, D is D1(ii) a When R is1= bromo and R2=R3When the isopropyl group is not substituted, D is D2(ii) a "→" indicates a coordination bond;
“
"represents a polymer chain formed by copolymerization of allyl and ethylene,
the copolymerization method comprises the following specific steps: vacuumizing a 250mL polymerization kettle to remove water and oxygen, fully replacing nitrogen, then replacing nitrogen with ethylene, adding 100mL of toluene solvent under the protection of ethylene, introducing normal-pressure ethylene gas until the ethylene is dissolved to saturation, adding 1-100 mu mol of allyl-substituted salicylaldimine metal titanium complex A serving as a main catalyst, and adding methylaluminoxane MAO serving as a cocatalyst in a corresponding proportion, wherein the mass ratio of the cocatalyst MAO to the metal titanium complex A is 10-1000: 1; and then continuously introducing ethylene, carrying out polymerization reaction for 0.5-1 h under the conditions of 0-100 ℃ and 0.1-10 MPa and magnetic stirring, closing a feed valve of the ethylene, emptying the polymerization kettle to normal pressure, discharging materials from the polymerization kettle, filtering to obtain a crude polymer product, washing with ethanol, and carrying out vacuum drying on the obtained solid at 60 ℃ to obtain a macromolecular self-supported salicylaldimine metal titanium complex D, wherein the content of metal titanium is 4.1-60.0 mu mol/g.
2. The preparation method of the macromolecular self-supported salicylaldimine metal titanium complex D according to claim 1, wherein the specific steps for synthesizing the allyl-substituted salicylaldimine metal titanium complex A are as follows:
the method comprises the following steps: synthesizing a ligand E, wherein the structural formula of the ligand E is as follows:
wherein: r1One selected from the following: bromine, chlorine; r2And R3Is isopropyl;
when R is1= chlorine and R2=R3When the isopropyl group is not substituted, E is E1(ii) a When R is1= bromo and R2=R3When the isopropyl group is not substituted, E is E2；
The synthesis of ligand E involves two stages: the first stage is the synthesis of allyl substituted salicylaldehyde; the second stage is that allyl substituted salicylaldehyde and 2, 6-diisopropylaniline are condensed by Schiff base to obtain a ligand E;
synthesis of allyl substituted salicylaldehyde: vacuumizing a 250mL reaction bottle, introducing nitrogen, replacing for 3 times, adding 100mL dry toluene, 0.2-1.1 mmol 2-allyl-p-chlorophenol or 2-allyl-p-bromophenol and 0.01-0.04 mmol anhydrous SnCl under the protection of nitrogen40.8-4.4 mmol of 2, 6-lutidine, performing magnetic stirring reflux reaction at room temperature for 20min, adding 1-5 mmol of paraformaldehyde, raising the temperature to 80 ℃, and reacting for 2 h; separating, purifying and drying the product to respectively obtain 3-allyl-5-chlorosalicylaldehyde and 3-allyl-5-bromosalicylaldehyde;
and (3) condensing allyl substituted salicylaldehyde and 2, 6-diisopropylaniline by using Schiff base to obtain a ligand E: adding 10mmol of 3-allyl-5-chlorosalicylaldehyde or 3-allyl-5-bromosalicylaldehyde and 10-11 mmol of 2, 6-diisopropylaniline into 50mL of methanol solvent, adding 0.1-0.2 mmol of formic acid as a catalyst, performing magnetic stirring reaction at 20-50 ℃ for 1-2 h, cooling at-10-0 ℃ to separate out a solid, filtering, washing filter residues with 5 ℃ cold ethanol, filtering, recrystallizing in ethanol, washing with 5 ℃ cold ethanol, filtering, and drying the obtained filter residues to obtain a ligand E1 or E2;
step two, synthesis of an allyl substituted salicylaldimine metal titanium complex A, wherein A comprises A1And A2，Wherein A is1And E1Corresponds to, A2And E2Corresponding;
1.0-2.0 mmol of the ligand E, including E1Or E2Dissolving the mixture in 50mL of dichloromethane, and dropwise adding 0.5-1.0 mmol TiCl into the mixture at the temperature of-30 ℃ within 1h under the stirring condition4And 30mL of dichloromethane, raising the temperature to 30-45 ℃, performing magnetic stirring reaction for 2 hours, injecting 1.0-2.0 mmol of triethylamine by using a needle cylinder, continuing stirring reaction for 2 hours at 30-45 ℃, concentrating the reaction solution to 40.0mL, adding 30-50mL of petroleum ether as a precipitator, filtering, washing filter residues with 3 x 10mL of cold dichloromethane for 3 times, recrystallizing the obtained solid in dichloromethane, filtering, and drying to obtain an allyl-substituted salicylaldimine metal titanium complex A1 or A2;
the second step is carried out under the anhydrous and anaerobic condition.
3. The macromolecular self-supported salicylaldiminato metal titanium complex D prepared by the preparation method of any one of claims 1 to 2 is used for catalyzing the bulk polymerization of monomer N-vinyl pyrrolidone NVP, and is characterized in that the bulk polymerization comprises the following specific steps:
heating a stainless steel polymerization kettle, vacuumizing and deoxidizing, and introducing pure argon to fully displace; adding 30g of NVP and 0.1-0.5 g of macromolecular self-supported salicylaldimine metal titanium complex D with the titanium content of 4.1-60.0 mu mol/g, wherein the macromolecular self-supported salicylaldimine metal titanium complex D comprises D1Or D2And methylaluminoxane MAO in a corresponding proportion is taken as an activator, wherein the mass ratio of the activator MAO to the metal titanium complex D is 10-100: 1; magnetically stirring and polymerizing for 0.5-1 h in a constant-temperature oil bath at 30-100 ℃, adding 10-20 g of deionized water to inactivate the system, and finally spray drying to obtain a powdery poly (N-vinyl pyrrolidone) product.
4. The use method of the macromolecular self-supported salicylaldimine metal titanium complex D prepared by the preparation method of any one of claims 1 to 2 for catalyzing aqueous solution polymerization of monomer N-vinyl pyrrolidone comprises the following steps:
heating a stainless steel polymerization kettle, vacuumizing and deoxidizing, and introducing pure argon to fully displace; adding 30g of NVP (N-vinyl pyrrolidone), 60-90 g of deionized water, 3-5 g of a macromolecular self-supported salicylaldimine metal titanium complex D with the titanium content of 4.1-60.0 mu mol/g, wherein the macromolecular self-supported salicylaldimine metal titanium complex D comprises D1Or D2；After magnetic stirring polymerization reaction is carried out for 0.5-1 h in a constant-temperature oil bath at 30-100 ℃, filter residue obtained by filtering is a titanium complex D insoluble in a polymer aqueous solution system, and the titanium complex D can be recycled as a catalyst for catalyzing aqueous solution polymerization of NVP after being washed and dried for multiple times; and spray drying the filtrate system to obtain a powdery product of the poly (N-vinyl pyrrolidone).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810748868.8A CN109053935B (en) | 2018-07-10 | 2018-07-10 | Novel macromolecular self-supported salicylaldimine metal titanium complex, and synthesis method and use method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810748868.8A CN109053935B (en) | 2018-07-10 | 2018-07-10 | Novel macromolecular self-supported salicylaldimine metal titanium complex, and synthesis method and use method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109053935A CN109053935A (en) | 2018-12-21 |
| CN109053935B true CN109053935B (en) | 2022-02-01 |
Family
ID=64819327
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810748868.8A Active CN109053935B (en) | 2018-07-10 | 2018-07-10 | Novel macromolecular self-supported salicylaldimine metal titanium complex, and synthesis method and use method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109053935B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2018
- 2018-07-10 CN CN201810748868.8A patent/CN109053935B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Non-Patent Citations (2)
| Title |
|---|
| Theoretical study of isomerism in phenoxyimine-based precursors of coordinative olefin polymerization catalysts;ZygmuntFlisak;《Journal of Molecular Catalysis A: Chemical》;20100228;第316卷(第1-2期);第83-89页 * |
| 含烯丙基席夫碱ⅣB族的金属烯烃聚合催化剂的合成、结构、高分子化及其催化乙烯聚合反应;陈正军 等;《无机化学学报》;20041231;第20卷(第12期);第1383-1389页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109053935A (en) | 2018-12-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPS6366843B2 (en) | ||
| US6562973B1 (en) | Method for making late transition metal catalysts for olefin polymerization | |
| CN1353723A (en) | Method for polymerising olefins | |
| JPS633010A (en) | Catalyst for polymerization of olefin | |
| CN109053935B (en) | Novel macromolecular self-supported salicylaldimine metal titanium complex, and synthesis method and use method thereof | |
| CN108467445A (en) | A kind of annular polystyrene and preparation method thereof | |
| EP2268651B1 (en) | Sterically emcumbered bidentate and tridentate naphthoxy-imine metallic complexes | |
| US3117111A (en) | Process for producing linear high polymers of acrylonitrile using cocatalyst of metal alkyl with metal alcoholate or acetylacetonate | |
| EP2003125A1 (en) | New tridentate ligand compounds with imino furan units, method for manufacturing said compounds, and their use in the preparation of catalysts for the homopolymerisation and copolymerisation of ethylene and alpha-olefins | |
| US20080306226A1 (en) | Polymerization Catalyst System Based on Monooxime Ligands | |
| CN110655597A (en) | MgCl2Preparation method and application of metallocene catalyst loaded on silica gel carrier | |
| US20220274098A1 (en) | Methods for producing step dienes | |
| JPH0725833B2 (en) | Method for producing propylene homopolymer and copolymer | |
| WO2006065714A2 (en) | Diketonate complex-derived catalysts useful for preparing polyolefins | |
| JP2772978B2 (en) | Solid catalyst component for ultra high molecular weight polyethylene production | |
| CN108264594B (en) | Copolymerization method of ethylene and vinyl ester | |
| JPS58136611A (en) | Production of ethylene/propylene block copolymer | |
| JPS5812282B2 (en) | Olefuinno Jiyuugohouhou | |
| JPS59142206A (en) | Production of catalyst component for alpha-olefin polymerization | |
| JP2797445B2 (en) | Method for producing polypropylene | |
| CN106459249A (en) | Method for preparing transition metal complex | |
| JPS62177003A (en) | Catalytic component for olefin polymerization and catalyst therefrom | |
| CN117700585A (en) | Main catalyst for preparing ethylene copolymerization modified poly (4-methyl-1-pentene) and application thereof | |
| CN117986411A (en) | Olefin polymerization catalyst, preparation method and application | |
| JPS58109506A (en) | Polymerization of olefin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240304 Address after: 431700 West of Road 1 and South of Road 8 in Yuekou Industrial Park, Tianmen City, Hubei Province Patentee after: Hubei Keyuan Biopharmaceutical Co.,Ltd. Country or region after: China Address before: 430081 Wuhan University of science and technology, 947 Heping Avenue, Qingshan District, Wuhan City, Hubei Province Patentee before: WUHAN University OF SCIENCE AND TECHNOLOGY Country or region before: China |
|
| TR01 | Transfer of patent right |