CN106008185A - Tetramine monomer and preparation method and application thereof - Google Patents

Tetramine monomer and preparation method and application thereof Download PDF

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CN106008185A
CN106008185A CN201610389172.1A CN201610389172A CN106008185A CN 106008185 A CN106008185 A CN 106008185A CN 201610389172 A CN201610389172 A CN 201610389172A CN 106008185 A CN106008185 A CN 106008185A
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phenoxy group
benzophenone
hours
dianhydride
trifluoromethyl
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关绍巍
檀海维
关尔佳
祝世洋
宋颖
于华轩
石凯祥
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Jilin University
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Jilin University
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/64—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of functional groups containing oxygen only in singly bound form
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06—Preparation of nitro compounds
    • C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/27—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups
    • C07C205/35—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C205/36—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton to carbon atoms of the same non-condensed six-membered aromatic ring or to carbon atoms of six-membered aromatic rings being part of the same condensed ring system
    • C07C205/38—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton to carbon atoms of the same non-condensed six-membered aromatic ring or to carbon atoms of six-membered aromatic rings being part of the same condensed ring system the oxygen atom of at least one of the etherified hydroxy groups being further bound to a carbon atom of a six-membered aromatic ring, e.g. nitrodiphenyl ethers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
    • C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
    • C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/78—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
    • C07C217/80—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings
    • C07C217/82—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring
    • C07C217/84—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring the oxygen atom of at least one of the etherified hydroxy groups being further bound to an acyclic carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
    • C07C49/84—Ketones containing a keto group bound to a six-membered aromatic ring containing ether groups, groups, groups, or groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain

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Abstract

The invention provides a tetramine monomer for synthesis of hyperbranched polyimide, and is used for solving the problems that a conventional polyimide has relatively poor thermal stability, film formation performance and other thermal properties and mechanical properties; through introduction of carbonyl and an ether chain into the tetraamine monomer, an obtained polymer has good solubility, thermal performance and mechanical properties. In addition, due to long synthesis route and large difficulty of a new electric-activity monomer, the characteristic that the hyperbranched polymer has a large number of end groups is utilized, a ferrocene group with electrochemical activity is introduced, the tetraamine monomer is subjected to a reaction with dianhydride and (4-amino)phenyl ferrocene, and the hyperbranched polyimide having ferrocene terminated and having the electrical activity can be easily prepared; the polymer can be used as an electrical storage material to be applied in the field of information storage.

Description

A kind of tetramine monomers and its preparation method and application
Technical field
The invention belongs to technical field of polymer materials.
Background technology
Polyimides is the polymer on molecular backbone containing imide ring structure, and it has the thermostability of excellence, thoroughly Photosensitiveness, electric property, mechanical performance and solvent resistance and chemical stability.The combination of these excellent properties makes polyamides sub- Amine has a wide range of applications, and thin film and the gas of the engineering plastics from aircraft industry to fuel cell separate film with solvent., Along with science and technology and the progress of people's life, polyimides is widely used in optics and electricity material, and has high light transmittance, low Dielectric, highly dissoluble, low refractive index, the polyimides of low hydroscopicity low thermal coefficient of expansion also causes everybody to study widely.
The dissolubility of linear polyimide is poor so that it is processing difficulties, and in the application by a definite limitation, branched polyamides is sub- Amine solvent is good, and melt viscosity is low, it is easy to processing, its terminal functional group carries out modification and can obtain having electroactive polymerization Thing, has good application prospect at following Organic Electricity storage Material Field.
That close with the present invention is (the Fluorinated Hyper branched Polyimide for such as Hong Gao Optical Waveguides, Macromolecular Rapid Communications 28 (2007) 252-259) synthesize A kind of novel Triamine monomer 1,3,5-tri-(2-trifluoromethyl-4-amido phenoxy group) benzene, three introduced in Triamine monomer Methyl fluoride increases the randomness of strand, hinders intensive chain and piles up, and then reduce Interchain interaction, hence it is evident that improves The dissolubility of polymer.But prior art yet suffers from the hot property such as heat stability, film property and poor the asking of mechanical property Topic.
Summary of the invention
In order to solve the hot propertys such as existing polyimides heat stability, film property and the poor problem of mechanical property, this Invention provides a kind of tetramine monomers for synthesis of polyimides, named 4,4 '-two [3,5-bis-(the 2-fluoroforms of IUPAC Base-4-amido phenoxy group) phenoxy group] benzophenone.
The technical solution used in the present invention is, carbonyl and ether chain is introduced in tetramine monomers, obtains 4,4 '-two [3,5-bis- (2-trifluoromethyl-4-amido phenoxy group) phenoxy group] benzophenone, and with described 4,4 '-two [3,5-bis-(2-trifluoromethyl-4-amine Phenoxyl) phenoxy group] benzophenone and two anhydride reactants, the hyperbranched polyamides of A2+B4 type preparing anhydride end-blocking or amido end-blocking is sub- Amine, introduces carbonyl and makes the heat stability of polymer improve, and ehter bond can strengthen chain entanglement, improves film property, introduces trifluoromethyl Can make polymer dissolubility be improved significantly, make the polymer obtained have well dissolving by the introducing of above group Performance, hot property and mechanical property.
Designing the new synthetic route having an electroactive monomer long, difficulty is big, and the present invention utilizes dissaving polymer to hold in a large number The feature of base, introduces the ferrocene group with electro-chemical activity, utilizes described 4,4 '-two [3,5-bis-(2-trifluoromethyl-4- Amido phenoxy group) phenoxy group] benzophenone reacts with dianhydride and (4-amino) diphenylphosphino ferrocene, and can be easy to prepare and there is electricity live The hyperbranched branched polyimide of the Ferrocene-blocked of property.
Tetramine monomers 4,4 '-two [3,5-bis-(2-trifluoromethyl-4-amido phenoxy group) phenoxy group] benzophenone in the present invention Structural formula as follows:
The synthetic route of 4,4 '-two [3,5-bis-(2-trifluoromethyl-4-amido phenoxy group) phenoxy group] benzophenone is as follows:
Concrete preparation method is as follows:
The first step: by 3,5-syringol, 4,4 '-difluoro benzophenone, potassium carbonate, DMAC N,N' dimethyl acetamide, first Benzene is put in reaction vessel, band water back flow reaction 2～3 hours, and toluene is then distilled off；With DMAC N,N' dimethyl acetamide (DMAc) make solvent, with 4,4 '-difluoro benzophenone react under the conditions of 130～150 DEG C 18～24 hours prepare 4,4 '-two [(3, 5-dimethoxy) phenoxy group] benzophenone, in deionized water, washing is colourless to filtrate in discharging, dried water and acetone Mixed solvent recrystallization purifies；Wherein, 3,5-syringol, 4,4-difluoro benzophenone, potassium carbonate, N, N-dimethylacetamide The mol ratio of amine and toluene is 1:(0.35～0.5): (0.525～0.75): (11.2～16): (4～6)；Rubbing of water and acetone That ratio is 1:(4～6)；
Second step: 4,4 '-two [(3,5-dimethoxy) phenoxy group] benzophenone is dissolved in dichloromethane and obtains reaction solution, Liquid nitrogen-acetone/ethanol system is utilized to control reaction temperature between-40～-20 DEG C；Separately Boron tribromide is dissolved in dichloromethane to obtain To the solution of 1mol/L, in 2～4 hours, this solution is added dropwise in reaction solution, after dropping, is transferred to ice bath Under the conditions of continue reaction 3～5 hours after, be stirred at room temperature more than 12 hours, in 1～2 hour, be then added dropwise over methanol quencher, Obtaining 4,4 '-two (3,5-dihydroxy benzenes epoxide) benzophenone, discharging, in substantial amounts of frozen water, is filtered and washs to filtrate colourless, Dried again with the mixed solvent recrystallization purification of ethanol and distilled water；Described 4,4 '-two (3,5-dimethoxy phenoxy groups) two The mol ratio of benzophenone, dichloromethane, Boron tribromide and methanol is 1:(110～190): (6～10): (18～30)；Second alcohol and water Mol ratio be 1:(0.5～0.1).
3rd step: by 4,4 '-two (3,5-dihydroxy benzenes epoxide) benzophenone, 2-chloro-5-nitro-trifluoromethyl toluene, potassium carbonate, N,N-dimethylacetamide and toluene add in reaction vessel, refluxing toluene band water 2～toluene is distilled off, then after 3 hours It is that solvent continues reaction 18～24 hours under the conditions of 130～150 DEG C with N,N-dimethylacetamide (DMAc), prepares 4, 4 '-two [3,5-bis-(2-trifluoromethyl-4-nitrophenoxy) phenoxy group] benzophenone, after cooling, discharging is in ethanol, uses ethanol Washing is colourless to filtrate, uses chromatography separating-purifying after drying；Described 4,4 '-two (3,5-dihydroxy benzenes epoxide) benzophenone, The mol ratio of 2-chloro-5-nitro-trifluoromethyl toluene, potassium carbonate, DMAC N,N' dimethyl acetamide and toluene is 1:(4～4.2): (2.4～ 3): (60～90): (20～30).
4th step: with 4,4 '-two [3,5-bis-(2-trifluoromethyl-4-nitrophenoxy) phenoxy group] benzophenone, concentrated hydrochloric acid And two hydrated stannous chloride 1:(60 in molar ratio～67): (20～22) are raw material, and dehydrated alcohol makees solvent, back flow reaction 8～ 10 hours, prepare 4,4 '-two [3,5-bis-(2-trifluoromethyl-4-amido phenoxy group) phenoxy group] benzophenone.
In 3rd step, described chromatography can use column chromatography, with the SiO of 200-300 mesh2For fixing phase, dichloromethane is Eluant, collects second some product.
After four-step reaction completes, question response system is cooled to room temperature, and discharging, in deionized water, regulates pH to 11～12, It is extracted with ethyl acetate again and washs with sodium chloride saturated solution, remove solvent, purify 4,4 '-two [3,5-bis-(2-tri-further Methyl fluoride-4-amido phenoxy group) phenoxy group] benzophenone.
, can make for raw material with described 4,4 '-two [3,5-bis-(2-trifluoromethyl-4-amido phenoxy group) phenoxy group] benzophenone Must have anhydride end-blocking or amido end-blocking A2+B4 type super-branched polyimide, (4-amino) diphenylphosphino ferrocene end-blocking branched Polyimides and the super-branched polyimide of 9-aminocarbazole end-blocking.
The A2+B4 type super-branched polyimide of anhydride end-blocking, structural formula is as shown in formula II；
The A2+B4 type super-branched polyimide of amido end-blocking, structural formula is as shown in formula III；
The branched polyimide of (4-amino) diphenylphosphino ferrocene end-blocking, structural formula is as shown in formula IV；
In formula I, (II), (III) and (IV), n is chain hop count (2 < n < 200)；
For
For In any one.
The method of the A2+B4 type super-branched polyimide preparing anhydride end-blocking is as follows: dianhydride is dissolved in N, N-dimethyl Acetamide forms two anhydride solutions, at room temperature by 4,4 '-two [3,5-bis-(2-trifluoromethyl-4-amido phenoxy group) phenoxy groups] Benzophenone is dissolved in the solution of N,N-dimethylacetamide formation and was added dropwise in 1～2 hour in above-mentioned two anhydride solutions, reaction Add pyridine and acetic anhydride after 20～24 hours, react 10～12 hours after being heated to 60～80 DEG C, discharging in dehydrated alcohol, Then with absolute ethanol washing, through filtering and dried, the A2+B4 type super-branched polyimide of anhydride end-blocking is obtained.
Wherein, 4,4 '-two [3,5-bis-(2-trifluoromethyl-4-amido phenoxy group) phenoxy group] benzophenone, dianhydride, N, N-bis- The mol ratio of methylacetamide, pyridine and acetic anhydride is 1:3:(360～440): 50:128；Described dianhydride monomer is biphenyl dianhydride (BPDA), any one in hexafluorodianhydride (6FDA) (6FDA), monoether dianhydride (ODPA), ketone acid anhydride (BTDA) and four benzene three ether dianhydride (QBTE) Kind.
The method of the A2+B4 type super-branched polyimide preparing amido end-blocking is as follows: by 4,4 '-two [3,5-bis-(2-trifluoros Methyl-4-amido phenoxy group) phenoxy group] benzophenone be dissolved in N,N-dimethylacetamide prepare four amine aqueous solutions, by dianhydride monomer It is dissolved in DMAC N,N' dimethyl acetamide and forms two anhydride solutions；At ambient temperature, by described two anhydride solutions in 1～2 hour It is added drop-wise in four amine aqueous solutions, after reacting 20～24 hours, adds dimethylbenzene, reflux after being heated to 170 DEG C band water 6～7 hours, steam Evaporating except dimethylbenzene, discharging, in dehydrated alcohol, with absolute ethanol washing, through filtering and dried, obtains the A2+ of amido end-blocking B4 type super-branched polyimide.
Wherein, 4,4 '-two [3,5-bis-(2-trifluoromethyl-4-amido phenoxy group) phenoxy group] benzophenone, dianhydride, N, N-bis- Methylacetamide, the mol ratio of dimethylbenzene are 1:1:(180～220): (200～300)；Described dianhydride monomer is biphenyl dianhydride (BPDA), any one in monoether dianhydride (ODPA), hexafluorodianhydride (6FDA) (6FDA), ketone acid anhydride (BTDA) or four benzene three ether dianhydride (QBTE) Kind.
The method of the branched polyimide of preparation (4-amino) diphenylphosphino ferrocene end-blocking is as follows: dianhydride is dissolved in N, N-diformazan In yl acetamide, obtain two anhydride solutions, by described 4,4 '-two [3,5-bis-(2-trifluoromethyl-4-amido phenoxy group) phenoxy groups] Benzophenone is dissolved in N,N-dimethylacetamide, obtains four amine aqueous solutions；Under room temperature by described four amine aqueous solutions in 4～6 hours by Instill in described two anhydride solutions；Solution viscosity is gradually increased in the course of the polymerization process, continues reaction 24 hours, adds (4-amino) Diphenylphosphino ferrocene, room temperature reaction 10～12 hours, it is subsequently adding pyridine and acetic anhydride, will heat up 60～80 DEG C and continue reaction 20 ～24 hours, discharging is in dehydrated alcohol, with absolute ethanol washing 3 times, in 80 DEG C of dry vacuum 4～8 hours after filtration, then uses Dehydrated alcohol extracts more than 48 hours, dries the super-branched polyimide obtaining (4-amino) diphenylphosphino ferrocene end-blocking；
Wherein, 4,4 '-two [3,5-bis-(2-trifluoromethyl-4-amido phenoxy group) phenoxy group] benzophenone, dianhydride monomer, The mol ratio of (4-amino) diphenylphosphino ferrocene, DMAC N,N' dimethyl acetamide, pyridine and acetic anhydride is 1:3:2:(360～440): 128:50；Described dianhydride monomer is biphenyl dianhydride (BPDA), monoether dianhydride (ODPA), hexafluorodianhydride (6FDA) (6FDA), ketone acid anhydride (BTDA) With any one in four benzene three ether dianhydride (QBTE).
Beneficial effects of the present invention:
The invention provides a kind of tetramine monomers 4,4 '-two [3,5-bis-(2-trifluoromethyl-4-amido phenoxy group) benzene oxygen Base] benzophenone monomer and preparation method thereof, and with 4,4 '-two [3,5-bis-(2-trifluoromethyl-4-amido phenoxy group) phenoxy groups] Benzophenone monomer is raw material, has synthesized the super-branched polyimide polymer that novel main chain contains trifluoromethyl group.
4,4 '-two [3,5-bis-(2-trifluoromethyl-4-amido phenoxy group) phenoxy group] benzophenone monomer introduces carbonyl and makes to gather The heat stability of compound improves, and ehter bond can strengthen chain entanglement, improves film property, and the introducing of trifluoromethyl improves hyperbranched poly Imido fluorinated volume, can affect the multiple performances such as the heat stability of polymer, dissolubility and optical property, by with The introducing of upper group makes the polymer obtained have good solubility property, hot property and mechanical property.This super-branched polyimide Being the fire resistant resin of a kind of high comprehensive performance, particularly in electricity field of storage, the introducing of trifluoromethyl can increase polymerization Owner's chain electron-withdrawing, and the end group of substantial amounts can use (4-amino) phenyl by further functionalization After Ferrocene-blocked, end has to electro, and ferrocene has oxidation-reduction quality simultaneously so that polymer is the most permissible Forming charge transferring channel and improve electric conductivity, polymer can be as electricity storage materials application in area information storage.
Accompanying drawing explanation
4,4 '-two [(3,5-dimethoxy) phenoxy group] benzophenone prepared by Fig. 1 embodiment of the present invention 1 first step1HNMR spectrogram.
4,4 '-two [(3,5-dihydroxy) phenoxy group] benzophenone prepared by Fig. 2 embodiment of the present invention 1 second step1HNMR Spectrogram.
4,4 '-two [3,5-bis-(2-trifluoromethyl-4-nitrophenoxy) benzene prepared by Fig. 3 embodiment of the present invention 1 the 3rd step Epoxide] benzophenone1HNMR spectrogram.
4,4 '-two [3,5-bis-(2-trifluoromethyl-4-amido phenoxy group) benzene prepared by Fig. 4 embodiment of the present invention 1 the 4th step Epoxide] benzophenone1HNMR spectrogram.
The infrared spectrum of the super-branched polyimide of the dianhydride end-blocking of Fig. 5 embodiment of the present invention 4 preparation.
The means of differential scanning calorimetry (DSC) of the super-branched polyimide of the hexafluorodianhydride (6FDA) end-blocking of Fig. 6 embodiment of the present invention 4 preparation Spectrogram.
Thermal weight loss (TGA) spectrogram of the super-branched polyimide of the hexafluorodianhydride (6FDA) end-blocking of Fig. 7 embodiment of the present invention 4 preparation.
The nuclear magnetic spectrogram of the B4-6FDA-ph-Fc of Fig. 8 embodiment of the present invention 14 preparation.
Means of differential scanning calorimetry (DSC) spectrogram of the B4-6FDA-ph-Fc of Fig. 9 embodiment of the present invention 14 preparation.
Thermal weight loss (TGA) spectrogram of the B4-6FDA-ph-Fc of Figure 10 embodiment of the present invention 14 preparation.
The ultraviolet visible absorption spectra figure of the polymer of Figure 11 embodiment of the present invention 4 and 14～18 preparation.
The cyclic voltammetry curve of the polymer of Figure 12 embodiment of the present invention 14～18 preparation.
The cyclic voltammetry curve of the polymer of Figure 13 embodiment of the present invention 4 preparation.
Detailed description of the invention
With the form of specific embodiment, technical solution of the present invention is further explained below.
Embodiment 1
The first step: by 0.10mol (15.4g) 3,5-syringol, 0.045mol (9.81g) 4,4 '-difluorodiphenyl Ketone, 0.06mol (8.28g) potassium carbonate, 1.3mol (121mL) DMAC N,N' dimethyl acetamide, 0.4mol (42mL) toluene join In reaction vessel equipped with water-taker and reflux condensing tube, after being heated to reflux band water 2 hours under mechanical agitation and nitrogen are protected, Be warming up to 150 DEG C and steam toluene, 130 DEG C continue reaction 20 hours, after being cooled to room temperature, discharging is in deionized water, and spend from It is colourless to filtrate that sub-water washs 3～4 times, with the water that mol ratio is 1:4 and acetone after 80 DEG C of vacuum drying 6～12 hours Mixed solvent recrystallization, obtains lurid 4,4 '-two (3,5-dimethoxy phenoxy group) benzophenone；
Second step: described 0.03mol (14.68g) 4,4 '-two [(3,5-dimethoxy) phenoxy group] benzophenone is added 0.6mol (38mL) dichloromethane obtains reaction solution, under mechanical agitation and nitrogen are protected, uses liquid nitrogen-acetone system control 0.18mol (45.10g) Boron tribromide, at-40 DEG C, is dissolved in 2.7mol (173mL) dichloromethane under room temperature by reaction temperature processed Obtain the 1mol/L solution of dichloromethane, in 2 hours, this solution is added dropwise in reaction solution, system after dropping It is placed in ice bath, after continuing reaction 3 hours, in 1 hour, is added dropwise over 0.54mol (22mL) methanol quencher reaction, question response Solution no longer has gas generation to show that quencher is complete, and discharging is in a large amount of deionized waters and is washed with deionized three times, sucking filtration After solid, again with the mixed solvent recrystallization of the second alcohol and water that mol ratio is 1:0.5 after 80 DEG C of vacuum drying 6 hours, To wine-colored 4,4 '-two (3,5-dihydroxy benzenes epoxide) benzophenone；
3rd step: by 0.9mol (84mL) DMAC N,N' dimethyl acetamide, 0.015mol (6.45g) 4,4 '-two (3,5-dihydroxy Phenoxyl) benzophenone, 0.06mol (13.53g) 2-chloro-5-nitro-trifluoromethyl toluene, 0.036mol (4.97g) potassium carbonate and 0.3mol (32mL) toluene joins in the reaction vessel equipped with water-taker and reflux condensing tube, protects in mechanical agitation and nitrogen Under be heated to reflux band water 2 hours after, be warming up to 150 DEG C steam described toluene after be cooled to 130 DEG C, continue reaction 20 hours, cold But after, discharging is in ethanol, is colourless with washing with alcohol 3～4 times to filtrate, separates with column chromatography after 80 DEG C of vacuum drying Purifying, fixing is the SiO of 200-300 mesh mutually2, eluant is dichloromethane, collects second some product, obtains pure faint yellow 4,4 '-two [3,5-bis-(2-trifluoromethyl-4-nitrophenoxy) phenoxy group] benzophenone；
4th step: by 0.01mol (11.86g) 4,4 '-two [3,5-bis-(2-trifluoromethyl-4-nitrophenoxy) benzene oxygen Base] benzophenone, 80mL dehydrated alcohol, 50mL (0.6mol) concentrated hydrochloric acid and 0.2mol (45.13g) two hydrated stannous chloride be at machinery Stirring and nitrogen are heated to back flow reaction 10 hours under protecting, and are down to room temperature, and discharging, in deionized water, uses 1mol/L hydroxide Sodium solution adjusts pH to 11～12, then is extracted with ethyl acetate three times, each 200mL, and merging organic facies is saturated the most molten with sodium chloride Liquid washs three times, and organic facies rotation boils off except solvent, obtains pure 4,4 '-two [3,5-bis-(2-trifluoromethyl-4-amido phenoxy groups) Phenoxy group] benzophenone monomer
Fig. 1 gives the hydrogen spectrum of the 300MHz test of 4,4 '-two [(3,5-dimethoxy) phenoxy group] benzophenone, figure acceptance of the bid Hydrogen on the chemical shift of 1, the 2,3,4,5 of note respectively corresponding phenyl ring and methyl, its area ratio is 2:2:2:1:6, meet 4,4 '- Two [(3,5-dimethoxy) phenoxy group] benzophenone structure, may certify that and synthesized 4,4 '-two [(3,5-dimethoxy) benzene oxygen Base] benzophenone.
Fig. 2 gives the hydrogen spectrum of the 300MHz test of 4,4 '-two [(3,5-dihydroxy) phenoxy group] benzophenone, marks in figure 1,2,3,4,5 chemical shift respectively corresponding phenyl ring and phenolic hydroxyl group on hydrogen, its area ratio is 2:2:2:1:2, meet 4,4 '- Two [(3,5-dihydroxy) phenoxy group] benzophenone structure, may certify that and synthesized 4,4 '-two [(3,5-dihydroxy) phenoxy groups] two Benzophenone.
Fig. 3 gives the 300MHz of 4,4 '-two [3,5-bis-(2-trifluoromethyl-4-nitrophenoxy) phenoxy group] benzophenone The hydrogen spectrum of test, the hydrogen of different chemical environment, its area on the chemical shift correspondence phenyl ring of 1,2,3,4,5,6,7 marked in figure Ratio is 2:2:2:1:2:2:2, meets 4,4 '-two [3,5-bis-(2-trifluoromethyl-4-nitrophenoxy) phenoxy group] benzophenone knot Structure, may certify that and synthesized 4,4 '-two [3,5-bis-(2-trifluoromethyl-4-nitrophenoxy) phenoxy group] benzophenone.
Fig. 4 gives the 300MHz of 4,4 '-two [3,5-bis-(2-trifluoromethyl-4-amido phenoxy group) phenoxy group] benzophenone The hydrogen spectrum of test, different chemical ring on the most corresponding phenyl ring of the chemical shift of 1,2,3,4,5,6,7,8 marked in figure and amido The hydrogen in border, its area ratio is 2:2:2:1:2:2:4:2, meets 4,4 '-two [3,5-bis-(2-trifluoromethyl-4-amido phenoxy groups) Phenoxy group] benzophenone structure, may certify that and synthesized 4,4 '-two [3,5-bis-(2-trifluoromethyl-4-amido phenoxy group) benzene oxygen Base] benzophenone.
Embodiment 2
The present embodiment first step is with the difference of embodiment 1 first step: by 4,4-difluoro benzophenone in embodiment 1 Consumption change 0.035mol (10.05g) into, the consumption of potassium carbonate changes 0.0525mol (7.25g), DMAC N,N' dimethyl acetamide into Consumption change 1.12mol (104mL) into, the consumption of toluene changes 0.42mol (44mL) into, be heated to reflux the band water time, and to change 3 into little Time, continue the response time change into 24 hours, the mol ratio of recrystallization mixed solvent water and acetone changes 1:5 into；
The present embodiment second step is with the difference of embodiment 1 second step: changed into by the consumption of dichloromethane 5.7mol (365mL), the consumption of Boron tribromide change 0.3mol (75.17g) into, the consumption of methanol changes 0.9mol (36mL), liquid into Nitrogen-acetone system controls that reaction temperature changes-30 DEG C into, the time for adding of dichloromethane solution changes 4 hours into, continues the response time Change into 5 hours, the methanol quencher time change into 2 hours, the mol ratio of recrystallization mixed solvent second alcohol and water changes 1:0.2 into；
The present embodiment the 3rd step is with the difference of embodiment 1 the 3rd step: by the consumption of DMAC N,N' dimethyl acetamide Change 1.35mol (125mL) into, the consumption of potassium carbonate changes 0.045mol (6.21g) into, the consumption of toluene changes 0.45mol into (48mL), the consumption of 2-chloro-5-nitro-benzotrifluoride changes 0.063mol (14.21g) into, being heated to reflux the band water time, to change 3 into little Time, continue the response time change 24 hours into；
The present embodiment the 4th step is with the difference of embodiment 1 the 4th step: changed into by the consumption of dehydrated alcohol 120mL, the consumption of concentrated hydrochloric acid change 55.6mL (0.67mol) into, the consumption of two hydrated stannous chlorides changes 0.22mol into (50.14g), reflux time changes 8 hours into.
Embodiment 3
The present embodiment first step is with the difference of embodiment 1 and embodiment 2 first step: by 4,4-in embodiment 1 The consumption of difluoro benzophenone changes 0.050mol (10.9g) into, the consumption of potassium carbonate changes 0.075mol (10.35g) into, N, N-diformazan The consumption of yl acetamide changes 1.6mol (149mL) into, the consumption of toluene changes 0.6mol (63mL) into, band water return time changes 3 into Hour, 150 DEG C continue the response time change into 18 hours, the mol ratio of recrystallization mixed solvent water and acetone changes 1:6 into；
The present embodiment second step is with the difference of embodiment 1 and embodiment 2 second step: recrystallization mixed solvent second The mol ratio of alcohol and water changes 1:0.1 into；
The present embodiment the 3rd step is with the difference of embodiment 1 and embodiment 2 the 3rd step: the temperature continuing reaction changes Being 130 DEG C, the response time is 18 hours；
The present embodiment the 4th step is with the difference of embodiment 1 and embodiment 2 the 4th step: by the consumption of dehydrated alcohol Change 100mL into, the consumption of concentrated hydrochloric acid changes 53.9mL (0.65mol) into, the consumption of two hydrated stannous chlorides changes 0.213mol into (48.54g), reflux time changes 9 hours into.
Proving through characterizing test, embodiment 2 and embodiment 3 have identical technique effect with embodiment 1.
Embodiment 4
1.5mmol (0.6664g) hexafluorodianhydride (6FDA) (6FDA) is dissolved in 0.1mol (10mL) DMAC N,N' dimethyl acetamide Formation hexafluorodianhydride (6FDA) solution, 4,4 ' at room temperature 0.5mmol (0.533g) embodiment 1, embodiment 2 or embodiment 3 prepared- Two [3,5-bis-(2-trifluoromethyl-4-amido phenoxy group) phenoxy group] benzophenone is dissolved in 0.08mol (8mL) N, N-dimethylacetamide The solution that amine is formed was added dropwise in described hexafluorodianhydride (6FDA) solution in 1 hour, and solution viscosity gradually increases in the course of the polymerization process Greatly, continue reaction 24 hours, add 0.025mol (2mL) pyridine and 0.064mol (6mL) acetic anhydride, react after being heated to 70 DEG C 12 hours, obtaining polymer solution, discharging is in 500mL dehydrated alcohol, with absolute ethanol washing 3 times, true in 80 DEG C after filtration Empty dry 12 hours, obtain the super-branched polyimide of A2+B4 type anhydride end-blocking, be designated as B4-6FDA-PI-AN.
Fig. 5 gives the embodiment 3 recorded with Germany's BRUKER company Vector22 type fourier transform infrared spectroscopy instrument Infrared spectrogram.1778 and 1728cm-1The carbonyl of the most corresponding imide group in place is asymmetric and symmetrical stretching vibration absorbs Peak, 1377cm-1The stretching vibration absworption peak of the corresponding C-N key in place, 720cm-1The deformation vibration of the corresponding imide ring in place, and 1660cm-1Place does not observe absworption peak and the 3265cm of carbonyl in amido link-1Place does not observe the N-H in amido link Key characteristic absorption peak, illustrates that imidization is complete, 3400～3100cm-1Place's substantially flat, shows do not have amido, i.e. acid Acid anhydride blocks, and is absorbed as the stretching vibration of C-H on phenyl ring at 3050.
Fig. 6 gives with Switzerland Mettler-Toledo DSC821eThe spectrum of the embodiment 3 that differential scanning calorimeter records Figure.From fig. 6, it can be seen that the glass transition temperature of this polymer is 270 DEG C, show that resulting polymers has good calorifics Performance.
Fig. 7 gives the embodiment 3 that records with the Pyrisl type thermal gravimetric analyzer of Perkin-Elmer company of the U.S. Spectrogram.From figure 7 it can be seen that 5% thermal weight loss temperature of this polymer is 578 DEG C, show that synthesized polymer has high Heat stability.
Embodiment 5
The present embodiment is with the difference of embodiment 4: replace with 1.5mmol (0.4833g) ketone acid anhydride (BTDA) 1.5mmol (0.6664g) hexafluorodianhydride (6FDA), obtains the super-branched polyimide of anhydride end-blocking, is designated as B4-BTDA-PI-AN.
Embodiment 6
The present embodiment is with the difference of embodiment 4 and embodiment 5: with 1.5mmol (0.4653g) monoether dianhydride (ODPA) replace 1.5mmol (0.6664g) hexafluorodianhydride (6FDA), obtain the A2+B4 type super-branched polyimide of anhydride end-blocking, be designated as: B4-ODPA-PI-AN。
Embodiment 7
The present embodiment is with the difference of embodiment 4～6: with 1.5mmol (0.4413g) biphenyl dianhydride (BPDA) generation For 1.5mmol (0.6664g) hexafluorodianhydride (6FDA), obtain the A2+B4 type super-branched polyimide of anhydride end-blocking, be designated as: B4-BPDA- PI-AN。
Embodiment 8
The present embodiment is with the difference of embodiment 4～7: with 1.5mmol (0.7415g) four benzene three ether dianhydride (QBTE) replace 1.5mmol (0.6664g) hexafluorodianhydride (6FDA), to the A2+B4 type super-branched polyimide of anhydride end-blocking, be designated as: B4- QBTE-PI-AN。
Embodiment 9
4,4 '-two [3,5-bis-(the 2-fluoroforms that 1mmol (1.066g) embodiment 1, embodiment 2 or embodiment 3 are prepared Base-4-amido phenoxy group) phenoxy group] benzophenone be dissolved in 0.08mol (8mL) N,N-dimethylacetamide prepare four amine aqueous solutions, 1mmol (0.444g) hexafluorodianhydride (6FDA) (6FDA) is dissolved in 0.1mol (10mL) DMAC N,N' dimethyl acetamide formation hexafluorodianhydride (6FDA) Solution, at ambient temperature, was added drop-wise to described hexafluorodianhydride (6FDA) solution in four amine aqueous solutions, the most instead in 2 hours The viscosity answering system is gradually increased, and adds 0.2mol (21mL) dimethylbenzene, after being heated to 170 DEG C after continuing reaction 20～24 hours Backflow band water 6 hours, steams described dimethylbenzene, obtains polymer solution, and discharging is in 500mL dehydrated alcohol, by washing with alcohol 3 Secondary, it is vacuum dried 12 hours in 80 DEG C after filtration, obtains the super-branched polyimide of amido end-blocking, be designated as: B4-6FDA-PI- AM。
Embodiment 10
The present embodiment is with the difference of embodiment 9: replace with 1mmol (0.294g) biphenyl dianhydride (BPDA) 1mmol (0.444g) hexafluorodianhydride (6FDA), obtains the A2+B4 type super-branched polyimide of amido end-blocking, is designated as: B4-BPDA-PI-AM.
Embodiment 11
The present embodiment is with the difference of embodiment 9 and embodiment 10: with 1mmol (0.322g) ketone acid anhydride (BTDA) generation For 1mmol (0.444g) hexafluorodianhydride (6FDA), obtain the A2+B4 type super-branched polyimide of amido end-blocking, be designated as: B4-BTDA-PI- AM。
Embodiment 12
The present embodiment is with the difference of embodiment 9～11: replace with 1mmol (0.310g) monoether dianhydride (ODPA) 1mmol (0.444g) hexafluorodianhydride (6FDA), obtains the A2+B4 type super-branched polyimide of amido end-blocking, is designated as: B4-ODPA-PI-AM.
Embodiment 13
The present embodiment is with the difference of embodiment 9～12: with 1mmol (0.494g) four benzene three ether dianhydride (QBTE) Replace 1mmol (0.444g) hexafluorodianhydride (6FDA), obtain the A2+B4 type super-branched polyimide of amido end-blocking, be designated as: B4-QBTE- PI-AM。
Embodiment 14
1.5mmol (0.6664g) hexafluorodianhydride (6FDA) (6FDA) is dissolved in 0.1mol (10mL) N,N-dimethylacetamide, To two anhydride solutions；4,4 '-two [3,5-bis-(2-tri-that 0.5mmol (0.533g) embodiment 1, embodiment 2 or embodiment 3 are prepared Methyl fluoride-4-amido phenoxy group) phenoxy group] benzophenone is dissolved in 0.08mol (8mL) N,N-dimethylacetamide, obtains tetramine Solution；Under room temperature, described four amine aqueous solutions were dropwise instilled in described dianhydride in 4 hours；Solution viscosity is gradually in the course of the polymerization process Increase, continue reaction 20～24 hours, add (4-amino) diphenylphosphino ferrocene 1mmol, room temperature reaction 12 hours, 0.025mol (2mL) pyridine and 0.064mol (6mL) acetic anhydride, be increased to 70 DEG C of imidizations 24 hours by temperature, discharging in 500mL without In water-ethanol, with absolute ethanol washing 3 times, in 80 DEG C of dry vacuum 4～8 hours after filtration, little extracting 48 with dehydrated alcohol Time 80 DEG C of drying of final vacuum obtain (4-amino) diphenylphosphino ferrocene end-blocking super-branched polyimide (B4-6FDA-ph-Fc).
Fig. 8 gives B4-6FDA-ph-Fc and end-capping reagent NH2The hydrogen spectrogram of the 300MHz test of-ph-Fc, can from figure To find out, the spectrogram of polymer B 4-6FDA-ph-Fc occurs in that NH at 4.66ppm, 4.36ppm and 4.09ppm2-ph-Fc's Characteristic peak, and there is no NH at 3.5ppm2Amino peak in-ph-Fc, illustrates that polymer is by NH2-ph-Fc blocks.
Fig. 9 gives with Switzerland Mettler-Toledo DSC821eThe B4-6FDA-ph-that differential scanning calorimeter records The spectrogram of Fc.From fig. 9, it can be seen that the glass transition temperature of polymer B 4-6FDA-ph-Fc is 270 DEG C, show polymer There is good thermal property.
Figure 10 gives the B4-6FDA-recorded with the Pyrisl type thermal gravimetric analyzer of Perkin-Elmer company of the U.S. The spectrogram of ph-Fc.From fig. 10 it can be seen that 5% thermal weight loss temperature of this polymer is 492 DEG C, show that synthesized polymer has There is preferable heat stability.
Embodiment 15
The present embodiment is with the difference of embodiment 14: replace with 1.5mmol (0.4833g) ketone acid anhydride (BTDA) 1.5mmol (0.6664g) hexafluorodianhydride (6FDA), obtains the super-branched polyimide of Ferrocene-blocked, is designated as B4-BTDA-ph-Fc.Warp Characterizing, the glass transition temperature of B4-BTDA-ph-Fc is 277 DEG C, and 5% weightless temperature is 488 DEG C.
Embodiment 16
The present embodiment is with the difference of embodiment 14 and 15: with 1.5mmol (0.4653g) monoether dianhydride (ODPA) Replace 1.5mmol (0.6664g) hexafluorodianhydride (6FDA), obtain the super-branched polyimide of Ferrocene-blocked, be designated as B4-ODPA-ph- Fc.Through characterizing, the glass transition temperature of B4-ODPA-ph-Fc is 224 DEG C, and 5% weightless temperature is 502 DEG C.
Embodiment 17
The present embodiment is with the difference of embodiment 14～16: with 0.5mmol (0.4413g) biphenyl dianhydride (BPDA) Replace 1.5mmol (0.6664g) hexafluorodianhydride (6FDA), obtain the super-branched polyimide of Ferrocene-blocked, be designated as B4-BPDA-ph- Fc.Through characterizing, the glass transition temperature of B4-BPDA-ph-Fc is 262 DEG C, and 5% weightless temperature is 465 DEG C.
Embodiment 18
The present embodiment is with the difference of embodiment 14～17: with 1.5mmol (0.7415g) four benzene three ether dianhydride (QBTE) replace 1.5mmol (0.6664g) hexafluorodianhydride (6FDA), obtain the super-branched polyimide of Ferrocene-blocked, be designated as B4- QBTE-ph-Fc.Through characterizing, the glass transition temperature of B4-QBTE-ph-Fc is 200 DEG C, and 5% weightless temperature is 558 DEG C.
Figure 11 gives the embodiment 4 with the test of Shimadzu UV-2501 type ultraviolet-visible spectrometer and embodiment 14 ～18 ultraviolet-visible spectrums of gained terminated polymer.Terminated polymer has from NH at 450nm as can be seen from Figure 112- The obvious absorption of ph-Fc, and uncapped polymer the most substantially absorbs, and shows that polymer is by NH2-ph-Fc blocks.
Figure 12 and Figure 13 gives embodiment 4 and the embodiment 14 of Shanghai occasion China CHI604E type electrochemical workstation test ～the cyclic voltammetry curve of 18.It can be seen that the oxidation peak of uncapped polymer is inconspicuous, and oxidizing potential is relatively Greatly；The oxidation peak of the post-consumer polymer of end-blocking is obvious, and with ferrocene very close to, oxidation point position is low, shows that terminated polymer holds Easily receiving and losing electrons, thus it is likely to be of the electric property of excellence.

Claims (8)

1. a tetramine monomers, it is characterised in that entitled 4,4 '-two [3,5-bis-(2-trifluoromethyl-4-amido phenoxy group) benzene Epoxide] benzophenone, structural formula such as formula I；
The preparation method of tetramine monomers the most according to claim 1 is as follows:
The first step: 3,5-syringol, 4,4 '-difluoro benzophenone, potassium carbonate, DMAC N,N' dimethyl acetamide, toluene are put Enter in reaction vessel, band water back flow reaction 2～3 hours, toluene is then distilled off；Under the conditions of 130～150 DEG C react 18～ Within 24 hours, preparing 4,4 '-two [(3,5-dimethoxy) phenoxy group] benzophenone, in deionized water, washing to filtrate is nothing in discharging Color, the mixed solvent recrystallization of dried water and acetone purifies；Wherein, 3,5-syringol, 4,4-difluoro benzophenone, The mol ratio of potassium carbonate, DMAC N,N' dimethyl acetamide and toluene is 1:(0.35～0.5): (0.525～0.75): (11.2～ 16): (4～6)；The mol ratio of water and acetone is 1:(4～6)；
Second step: be dissolved in dichloromethane and obtain reaction solution by 4,4 '-two [(3,5-dimethoxy) phenoxy group] benzophenone, utilizes Liquid nitrogen-acetone/ethanol system controls reaction temperature between-40～-20 DEG C；Separately Boron tribromide is dissolved in dichloromethane to obtain The solution of 1mol/L, was added dropwise to this solution in reaction solution in 2～4 hours, was transferred to ice bath bar after dropping After continuing reaction under part 3～5 hours, it is stirred at room temperature more than 12 hours, in 1～2 hour, is then added dropwise over methanol quencher, To 4,4 '-two (3,5-dihydroxy benzenes epoxide) benzophenone, discharging, in substantial amounts of frozen water, is filtered and washs to filtrate colourless, dry Purify with the mixed solvent recrystallization of ethanol and distilled water again after dry；Described 4,4 '-two (3,5-dimethoxy phenoxy group) hexichol The mol ratio of ketone, dichloromethane, Boron tribromide and methanol is 1:(110～190): (6～10): (18～30)；Second alcohol and water Mol ratio is 1:(0.5～0.1)；
3rd step: by 4,4 '-two (3,5-dihydroxy benzenes epoxide) benzophenone, 2-chloro-5-nitro-trifluoromethyl toluene, potassium carbonate, N, N- Dimethyl acetylamide and toluene add in reaction vessel, backflow band water 2～toluene is distilled off after 3 hours, then 130～ Continue reaction 18～24 hours under the conditions of 150 DEG C, prepare 4,4 '-two [3,5-bis-(2-trifluoromethyl-4-nitrophenoxies) Phenoxy group] benzophenone, after cooling, discharging is in ethanol, is colourless by washing with alcohol to filtrate, separates by chromatography after drying and carries Pure；Described 4,4 '-two (3,5-dihydroxy benzenes epoxide) benzophenone, 2-chloro-5-nitro-trifluoromethyl toluene, potassium carbonate, N, N-dimethyl The mol ratio of acetamide and toluene is 1:(4～4.2): (2.4～3): (60～90): (20～30)；
4th step: with 4,4 '-two [3,5-bis-(2-trifluoromethyl-4-nitrophenoxy) phenoxy group] benzophenone, concentrated hydrochloric acid and two Hydrated stannous chloride 1:(60 in molar ratio～67): (20～22) are raw material, and dehydrated alcohol makees solvent, and back flow reaction 8～10 is little Time, prepare 4,4 '-two [3,5-bis-(2-trifluoromethyl-4-amido phenoxy group) phenoxy group] benzophenone.
The preparation method of tetramine monomers the most according to claim 1, it is characterised in that four-step reaction complete after question response body System is cooled to room temperature, and discharging, in deionized water, regulates pH to 11～12, then is extracted with ethyl acetate and uses sodium chloride saturated molten Liquid washs, and removes solvent, purifies 4,4 '-two [3,5-bis-(2-trifluoromethyl-4-amido phenoxy group) phenoxy group] hexichol further Ketone.
4. tetramine monomers described in a claim 1 is used for preparing super-branched polyimide.
5. the application of tetramine monomers described in a claim 4, it is characterised in that described super-branched polyimide is anhydride end-blocking A2+B4 type super-branched polyimide, amido end-blocking A2+B4 type super-branched polyimide or (4-amino) diphenylphosphino ferrocene envelope The branched polyimide of end；
Wherein, the A2+B4 type super-branched polyimide of anhydride end-blocking, structural formula is as shown in formula II；
The A2+B4 type super-branched polyimide of amido end-blocking, structural formula is as shown in formula III；
The branched polyimide of (4-amino) diphenylphosphino ferrocene end-blocking, structural formula is as shown in formula IV；
In formula I, (II), (III) and (IV), n is chain hop count (2 < n < 200)；
For
For In any one.
6. the application of tetramine monomers described in a claim 5, it is characterised in that tetramine monomers is for preparing the A2 of anhydride end-blocking The method of+B4 type super-branched polyimide, specifically comprises the following steps that
Dianhydride is dissolved in N,N-dimethylacetamide and forms two anhydride solutions, at room temperature by 4,4 '-two [3,5-bis-(2-tri- Methyl fluoride-4-amido phenoxy group) phenoxy group] benzophenone be dissolved in DMAC N,N' dimethyl acetamide formed solution in 1～2 hour by It is added dropwise in above-mentioned two anhydride solutions, adds pyridine and acetic anhydride after reacting 20～24 hours, react after being heated to 60～80 DEG C 10～12 hours, discharging was in dehydrated alcohol, then with absolute ethanol washing, through filtering and dried, obtained anhydride end-blocking A2+B4 type super-branched polyimide；
Wherein, 4,4 '-two [3,5-bis-(2-trifluoromethyl-4-amido phenoxy group) phenoxy group] benzophenone, dianhydride, N, N-dimethyl The mol ratio of acetamide, pyridine and acetic anhydride is 1:3:(360～440): 50:128；Described dianhydride monomer be biphenyl dianhydride, six Any one in fluorine dianhydride, monoether dianhydride, ketone acid anhydride and four benzene three ether dianhydrides.
7. the application of tetramine monomers described in a claim 5, it is characterised in that tetramine monomers is for preparing the A2 of amido end-blocking The method of+B4 type super-branched polyimide, specifically comprises the following steps that
4,4 '-two [3,5-bis-(2-trifluoromethyl-4-amido phenoxy group) phenoxy group] benzophenone is dissolved in N, N-dimethylacetamide Amine prepares four amine aqueous solutions, dianhydride monomer is dissolved in N,N-dimethylacetamide and forms two anhydride solutions；At ambient temperature, In 1～2 hour, described two anhydride solutions are added drop-wise in four amine aqueous solutions, add dimethylbenzene after reacting 20～24 hours, be heated to Refluxing after 170 DEG C band water 6～7 hours, dimethylbenzene is removed in distillation, and discharging is in dehydrated alcohol, with absolute ethanol washing, through filtering After drying, the A2+B4 type super-branched polyimide of amido end-blocking is obtained；
Wherein, 4,4 '-two [3,5-bis-(2-trifluoromethyl-4-amido phenoxy group) phenoxy group] benzophenone, dianhydride, N, N-dimethyl Acetamide, the mol ratio of dimethylbenzene are 1:1:(180～220): (200～300)；Described dianhydride monomer is biphenyl dianhydride, hexafluoro Any one in dianhydride, monoether dianhydride, ketone acid anhydride and four benzene three ether dianhydrides.
8. the application of tetramine monomers described in a claim 5, it is characterised in that tetramine monomers is used for preparing (4-amino) phenyl The method of the branched polyimide of Ferrocene-blocked, specifically comprises the following steps that
Dianhydride is dissolved in N,N-dimethylacetamide, obtains two anhydride solutions, by described 4,4 '-two [3,5-bis-(2-fluoroforms Base-4-amido phenoxy group) phenoxy group] benzophenone is dissolved in N,N-dimethylacetamide, obtains four amine aqueous solutions；By described under room temperature Four amine aqueous solutions dropwise instilled in described two anhydride solutions in 4～6 hours；Solution viscosity is gradually increased in the course of the polymerization process, continues React 24 hours, add (4-amino) diphenylphosphino ferrocene, room temperature reaction 10～12 hours, be subsequently adding triethylamine and acetic anhydride, Will heat up 60～80 DEG C and continue reaction 20～24 hours, discharging is in dehydrated alcohol, with absolute ethanol washing, through filtration drying After, extract more than 48 hours with dehydrated alcohol, dry the super-branched polyimide obtaining (4-amino) diphenylphosphino ferrocene end-blocking；
Wherein, 4,4 '-two [3,5-bis-(2-trifluoromethyl-4-amido phenoxy group) phenoxy group] benzophenone, dianhydride monomer, (4-ammonia Base) diphenylphosphino ferrocene, DMAC N,N' dimethyl acetamide, the mol ratio of pyridine and acetic anhydride be 1:3:2:(360～440): 128:50； Described dianhydride monomer is any one in biphenyl dianhydride, monoether dianhydride, hexafluorodianhydride (6FDA), ketone acid anhydride and four benzene three ether dianhydrides.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106398211A (en) * 2016-11-04 2017-02-15 东华大学 PMDA type BDATHQ branched polyimide resin film and production method thereof
CN106398210A (en) * 2016-11-04 2017-02-15 东华大学 BTDA type 13BDAPB branched polyimide resin film and preparation method thereof
CN106519671A (en) * 2016-11-04 2017-03-22 东华大学 BPADA-type fluorine-containing branched polyimide resin film and preparation method thereof
CN106519674A (en) * 2016-11-04 2017-03-22 东华大学 ODPA-type fluorine-containing branched polyimide resin film and preparation method thereof
CN106519227A (en) * 2016-11-04 2017-03-22 东华大学 ODPA type BDADTBHQ branched polyimide resin film and preparation method thereof
CN106519684A (en) * 2016-11-04 2017-03-22 东华大学 6FDA-type 13BDAPB branched polyimide resin film and preparation method thereof
CN106519679A (en) * 2016-11-04 2017-03-22 东华大学 HQDA type 13BDAPB branched polyimide resin film and preparation method thereof
CN106519676A (en) * 2016-11-04 2017-03-22 东华大学 PMDA (pyromellitic dianhydride) type 13BDAPB branched polyamide resin film and preparation method thereof
CN106519681A (en) * 2016-11-04 2017-03-22 东华大学 HQDA-type fluorine-containing branched polyimide resin film and preparation method thereof
CN106519672A (en) * 2016-11-04 2017-03-22 东华大学 6FDA-type fluorine-containing branched polyimide resin film and preparation method thereof
CN106633876A (en) * 2016-11-04 2017-05-10 东华大学 BPADA type 13BDAPB branched polyimide resin film and preparation method thereof
CN106633868A (en) * 2016-11-04 2017-05-10 东华大学 BPADA (bisphenol-A-bisether-4-phthalic dianhydride) type bisphenol-A tetramine branched resin film and preparation method thereof
CN106633870A (en) * 2016-11-04 2017-05-10 东华大学 BPDA type 13BDAPB branched polyimide resin film and preparation method thereof
CN106633866A (en) * 2016-11-04 2017-05-10 东华大学 BTDA type BDADTBHQ branched polyimide resin thin film and preparation method thereof
CN106633872A (en) * 2016-11-04 2017-05-10 东华大学 ODPA type 13BDAPB branched polyimide resin film and preparation method thereof
CN106675024A (en) * 2016-11-04 2017-05-17 东华大学 Pyromellitic dianhydride (PMDA) type 14 BDAPB branched polyimide resin film and preparation method thereof
CN110041276A (en) * 2019-04-24 2019-07-23 吉林大学 The polynary amine monomers and its polymer and preparation method and application of polyimides containing triazole structure

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101234989A (en) * 2008-03-05 2008-08-06 东华大学 Method for preparing 4,4'-di(2,4-dinitrophenoxy)benzophenone
CN102924534A (en) * 2012-11-14 2013-02-13 北京化工大学 4,4'-diamido-4''-ferrocenyl triphenylamine and preparation method thereof
CN104529839A (en) * 2014-12-17 2015-04-22 吉林大学 4, 4'-di[3, 5-di(2-trifluoromethyl-4-amino phenoxyl) phenoxy] diphenyl sulfone and preparation method and application thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101234989A (en) * 2008-03-05 2008-08-06 东华大学 Method for preparing 4,4'-di(2,4-dinitrophenoxy)benzophenone
CN102924534A (en) * 2012-11-14 2013-02-13 北京化工大学 4,4'-diamido-4''-ferrocenyl triphenylamine and preparation method thereof
CN104529839A (en) * 2014-12-17 2015-04-22 吉林大学 4, 4'-di[3, 5-di(2-trifluoromethyl-4-amino phenoxyl) phenoxy] diphenyl sulfone and preparation method and application thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
HAIWEI TAN,ET AL.: "Design and synthesis of ferrocene-terminated hyperbranched polyimide for memory devices", 《DYES AND PIGMENTS》 *
高鸿宾主编: "《有机化学》", 31 May 2005 *

Cited By (18)

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Publication number Priority date Publication date Assignee Title
CN106398211A (en) * 2016-11-04 2017-02-15 东华大学 PMDA type BDATHQ branched polyimide resin film and production method thereof
CN106398210A (en) * 2016-11-04 2017-02-15 东华大学 BTDA type 13BDAPB branched polyimide resin film and preparation method thereof
CN106519671A (en) * 2016-11-04 2017-03-22 东华大学 BPADA-type fluorine-containing branched polyimide resin film and preparation method thereof
CN106519674A (en) * 2016-11-04 2017-03-22 东华大学 ODPA-type fluorine-containing branched polyimide resin film and preparation method thereof
CN106519227A (en) * 2016-11-04 2017-03-22 东华大学 ODPA type BDADTBHQ branched polyimide resin film and preparation method thereof
CN106519684A (en) * 2016-11-04 2017-03-22 东华大学 6FDA-type 13BDAPB branched polyimide resin film and preparation method thereof
CN106519679A (en) * 2016-11-04 2017-03-22 东华大学 HQDA type 13BDAPB branched polyimide resin film and preparation method thereof
CN106519676A (en) * 2016-11-04 2017-03-22 东华大学 PMDA (pyromellitic dianhydride) type 13BDAPB branched polyamide resin film and preparation method thereof
CN106519681A (en) * 2016-11-04 2017-03-22 东华大学 HQDA-type fluorine-containing branched polyimide resin film and preparation method thereof
CN106519672A (en) * 2016-11-04 2017-03-22 东华大学 6FDA-type fluorine-containing branched polyimide resin film and preparation method thereof
CN106633876A (en) * 2016-11-04 2017-05-10 东华大学 BPADA type 13BDAPB branched polyimide resin film and preparation method thereof
CN106633868A (en) * 2016-11-04 2017-05-10 东华大学 BPADA (bisphenol-A-bisether-4-phthalic dianhydride) type bisphenol-A tetramine branched resin film and preparation method thereof
CN106633870A (en) * 2016-11-04 2017-05-10 东华大学 BPDA type 13BDAPB branched polyimide resin film and preparation method thereof
CN106633866A (en) * 2016-11-04 2017-05-10 东华大学 BTDA type BDADTBHQ branched polyimide resin thin film and preparation method thereof
CN106633872A (en) * 2016-11-04 2017-05-10 东华大学 ODPA type 13BDAPB branched polyimide resin film and preparation method thereof
CN106675024A (en) * 2016-11-04 2017-05-17 东华大学 Pyromellitic dianhydride (PMDA) type 14 BDAPB branched polyimide resin film and preparation method thereof
CN110041276A (en) * 2019-04-24 2019-07-23 吉林大学 The polynary amine monomers and its polymer and preparation method and application of polyimides containing triazole structure
CN110041276B (en) * 2019-04-24 2022-09-27 吉林大学 Polyamine monomer of polyimide containing triazole structure, polymer thereof, preparation method and application

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