CN104003861A - Hexaphenyl terminated monomer and preparation method and application thereof in preparation of hexa-benzene ring terminated polyether ketone - Google Patents

Hexaphenyl terminated monomer and preparation method and application thereof in preparation of hexa-benzene ring terminated polyether ketone Download PDF

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CN104003861A
CN104003861A CN201410250680.2A CN201410250680A CN104003861A CN 104003861 A CN104003861 A CN 104003861A CN 201410250680 A CN201410250680 A CN 201410250680A CN 104003861 A CN104003861 A CN 104003861A
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hexaphenyl
benzophenone
polyether ketone
monomer
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CN104003861B (en
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庞金辉
姜振华
张海博
岳喜贵
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Jilin University
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    • C—CHEMISTRY; METALLURGY
    • 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
    • C07C45/67—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 isomerisation; by change of size of the carbon skeleton
    • C07C45/68—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 isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/72—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 isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
    • C—CHEMISTRY; METALLURGY
    • 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
    • C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
    • C07C45/46—Friedel-Crafts reactions
    • C—CHEMISTRY; METALLURGY
    • 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
    • C07C45/67—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 isomerisation; by change of size of the carbon skeleton
    • C07C45/68—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 isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
    • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
    • C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
    • 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
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterized by the type of post-polymerisation functionalisation
    • C08G2650/04—End-capping
    • 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
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
    • C08G2650/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group
    • C08G2650/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group containing ketone groups, e.g. polyarylethylketones, PEEK or PEK

Abstract

The invention discloses a hexaphenyl terminated monomer and a preparation method and application thereof in preparation of hexa-benzene ring terminated polyether ketone and belongs to the technical field of high polymer material. Since the polyether ketone material is prepared from aromatic biphenol and binary fluorine through the nucleophilic condensation polymerization; since the polymer has an active terminal group (OH or F), the melt viscosity of the polymer in high-temperature processing is increased and the processing stability is bad. For improving the processability of polyether ketone material, the termination is a good method for improving the processing property of a material. The hexaphenyl benzene structure terminated monomer with nucleophilic reaction activity is designed and synthesized, the polyether ketone polymer with a hexaphenyl structure is prepared through two termination ways including one-step feeding method and addition of a termination agent in the last phase of polymer reaction. The existence of the termination monomer with large-volume free radical is in favor of improvement of the terminal group stability of the polyether ketone material and increase of the processing stability of the material.

Description

Hexaphenyl end-blocking monomer, preparation method and the application in preparation six phenyl ring end capped polyether ketone
Technical field
The invention belongs to technical field of polymer materials, be specifically related to a class hexaphenyl benzene end-blocking monomer, preparation method and the application in preparation six phenyl ring end capped polyether ketone thereof.
Background technology
The special engineering plastics of the multiple excellent properties such as that polyetherketone base polymer belongs to is high temperature resistant, high strength, radiation hardness, belongs to s-generation polyether-ether-ketone product.By Britain ICI company, first released after polyetherketone (PEEK-HT) commodity, nearly ten years always with speed development faster.Polyetherketone material has higher resistance toheat and life-time service temperature than polyether-ether-ketone, but the processing temperature of polyetherketone material is also higher.Because polyetherketone material is made by nucleophilic condensation polymerization by aromatic dicarboxylic phenol and binary fluorine, so there is active end group (OH or F) in polymkeric substance, thereby cause polymkeric substance melt viscosity in high temperature process process to increase, and processing stability is poor.In order to improve the processibility of polyetherketone material, end-blocking is acknowledged as a kind of good approach.Research and develop the applicable end-blocking monomer of a class, develop thus end-sealed type polyetherketone material and be very important.
Summary of the invention
The present invention, from the design of molecular structure, has prepared the hexaphenyl end-blocking monomer with larger molecular weight.Develop the syntheti c route of monomer, and purge process, characterized the structure of monomer.
The preparation technology that the present invention adopts a step to feed intake and feeding method has been researched and developed six phenyl ring end capped polyether ketone materials step by step.Structure, crystallization behavior and the thermal characteristics of products obtained therefrom have been tested.
The structural formula of six phenyl ring end capped polyether ketone materials prepared by the present invention is as follows:
(1) preparation of hexaphenyl end-blocking monomer
Being prepared as follows shown in formula of monomer, its concrete preparation process comprises following three steps:
1) bromobenzene, aluminum trichloride (anhydrous) are joined in reaction vessel, mechanical stirring under ice-water bath, by 4 fluorobenzoyl chloride slowly splash in this reaction system, treat that raw material all drips off, and removes ice-water bath; Be warming up to bromobenzene and reflux, react 4～6 hours; Then reaction system is down in the aqueous hydrochloric acid that discharging is 15～20% in mass concentration after room temperature, uses chloroform extraction organic phase, with sodium hydroxide solution and the distilled water of mass concentration 5～8%, wash respectively organic phase; Collect extraction liquid and carry out underpressure distillation and remove bromobenzene, product with sherwood oil recrystallization obtain 4 Xiu 4 ’ fluorine benzophenone white crystal; Wherein bromobenzene is excessive, is reactant and reaction solvent, the mole dosage of aluminum trichloride (anhydrous) be 4 1.2～3 times of fluorobenzoyl chloride.
2) by 4 Xiu 4 ’ cuprous iodide, triphenylphosphine and two (triphenylphosphine) palladium chloride (II), the triethylamine of fluorine benzophenone, catalytic amount put in reaction vessel, mechanical stirring under nitrogen protection; When reaction system is warming up to 30～70 ℃, more slowly drip the triethylamine solution of phenylacetylene, after dripping off, be warming up to 80～90 ℃ of reactions 4～6 hours; Reaction system is filtered after being down to room temperature, by distilled water wash filtration product, obtains white solid, with after ethyl alcohol recrystallization, obtain 4 (phenylacetylene base) 4 ’ the yellow needle-like crystal of fluorine benzophenone; Wherein, 4 Xiu 4 ’ the mole dosage ratio of fluorine benzophenone and phenylacetylene be 0.2～5:1, when 4 Xiu 4 ’ the mole dosage of fluorine benzophenone and phenylacetylene when identical, productive rate is the highest;
3) by 4 (phenylacetylene base) 4 ’ fluorine benzophenone, tetraphenylcyclopentadienone, tetramethylene sulfone or phenyl ether join in reaction vessel, mechanical stirring under nitrogen protection, 260～280 ℃ are reacted 6～8 hours, are cooled to room temperature and obtain yellow solid, by washing with alcohol, toluene recrystallization obtains white solid, be hexaphenyl end-blocking monomer 4 Fu 4 ’ (2,3,4,5,6 pentapheneyl) benzophenone; Wherein, 4 (phenylacetylene base) 4 ’ the mole dosage ratio of fluorine benzophenone and tetraphenylcyclopentadienone be 0.2～5:1, when 4 (phenylacetylene base) 4 ’ fluorine benzophenone when identical with tetraphenylcyclopentadienone mole dosage, productive rate is the highest.
(2) six phenyl ring end capped polyether ketone materials.With the end group with large free volume, polyetherketone active end group is reacted away, can improve polyetherketone material in solution and the stability of molten state.
As above formula, from Molecular Structure Design angle, the present invention has designed two kinds of routes of preparing the polyetherketone material (E PEK) of six phenyl ring end-blockings.
The first syntheti c route is the mode of taking a step to feed intake, as shown in above formula.First according to the molecular weight of setting end-sealed type polyetherketone, calculate the repeating unit of polymkeric substance and the number of end-blocking monomer.Theoretical according to the polycondensation of Tang Aoqing polymer: r=(1+n)/(1 n), the group that wherein r is monomer is counted ratio, the number of repeat unit that n is polymkeric substance.R=N a/ (N b+ 2N b'), N wherein a, N b, N b 'represent respectively the reactive group number of two fluorine monomers, biphenol monomer and end-blocking monomer.The end-sealed type polyetherketone that the molecular weight of take is 10000 describes as example: end group molecular weight 638 * 2=1276, polyetherketone repeating unit molecular weight M=392, calculates n=(10000 1276)/392=22.3.By n, calculate r=0.914.Set N a=N b, release end group N b '=0.047N a.Therefore, the six phenyl ring list fluorine according to end-blocking are 0.047mol, 4,4 ’ difluoro benzophenone 1.0mol, 4,4 ’ dihydroxy benaophenonel 1.0mol, (charging capacity is 4 to carbonate, 4 ’ 1.1～2 times of equivalents of dihydroxy benaophenonel), one step feeding mode of sulfobenzide (theoretical polyetherketone quality product 2～4 times), gradient increased temperature (210 degrees Celsius of reactions 1 hour, 250 degrees Celsius of reactions 1 hour, 280 degrees Celsius of reactions 1 hour, 320 degrees Celsius of reactions 1 hour) can prepare six phenyl ring end-sealed type polyetherketone polymkeric substance (E-PEK-10000) of molecular weight 10000.
The second syntheti c route is the mode of taking two steps to feed intake.As shown in above formula, first prepare hydroxy-end capped polyetherketone material, then at last stage reaction, add six phenyl ring end-blocking monomers to carry out end-blocking.Concrete reactant feed ratio can be theoretical according to Tang Aoqing polymer polycondensation meter: polymerization degree r=(1+n)/(1 n), the group that wherein r is monomer is counted ratio, the number of repeat unit that n is polymkeric substance.The six phenyl ring end-sealed type polyetherketones that to prepare molecular weight be 50000 of take describe as example.End group molecular weight 638 * 2=1276, polyetherketone repeating unit molecular weight M=2n=392, calculates n=(50000 1276)/392=124.3.R=0.984 by above formula.By number of repeat unit, calculate and obtain charging capacity: Resorcinol 1mol, 4,4 ’ difluoro benzophenone 1mol, (charging capacity is 4 to carbonate, 4 ’ 1.1～2 times of equivalents of dihydroxy benaophenonel), sulfobenzide (theoretical polyetherketone quality product 2～4 times), (210 degrees Celsius are reacted 1 hour gradient increased temperature, 250 degrees Celsius are reacted 1 hour, 280 degrees Celsius are reacted 1 hour, 320 degrees Celsius of reactions 1 hour) last stage reaction adds six excessive phenyl ring end-blocking monomers (2～100 times of equivalents of endgroup content) to carry out end-blocking, makes E-PEK-50000.
Prepared first the polyetherketone polymkeric substance that just has hexaphenyl structure herein.The having of end-blocking monomer with large volume free radical is beneficial to the end group stabilization of improving polyetherketone material, improves the processing stability of material.
Accompanying drawing explanation
The hexaphenyl end-blocking monomer of Fig. 1: embodiment 1 preparation 1hNMR spectrogram;
Fig. 2: wide-angle x-ray diffraction (WAXD) figure of six phenyl ring end capped polyether ketone (E-PEK-50000) polymkeric substance;
Fig. 3: the infrared spectrogram of six phenyl ring end capped polyether ketone (E-PEK-50000) polymkeric substance;
Fig. 4: the thermogravimetric curve of six phenyl ring end capped polyether ketone (E-PEK-50000) polymkeric substance.
The present invention utilizes 1h NMR has carried out structural characterization to the prepared end-blocking monomer containing six phenyl ring.As shown in Figure 1, the nuclear-magnetism response signal of monomer and its structure have good corresponding relation.Prove that we successfully develop the syntheti c route of end-blocking monomer, made pure end-blocking monomer.
Prepared E-PEK polymkeric substance has been carried out to the test of solubility property, find that prepared polymkeric substance is all insoluble to conventional organic solvent, as N-Methyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO) (DMSO), N, N-N,N-DIMETHYLACETAMIDE (DMAc), chloroform, tetrahydrofuran (THF)s etc., can be dissolved in the vitriol oil.The superpower solvent resistance of polymkeric substance is because polymkeric substance inside exists physics cross-linking type crystalline network structure.
The crystal habit (accompanying drawing 2) of having observed E-PEK polymkeric substance by WAXD, there is the feature peak crystallization of polyetherketone material in E-PEK polymkeric substance.
Utilize infrared spectra to observe the molecular structure of E-PEK polymkeric substance, as shown in Figure 3, at 1652cm -1all there is the charateristic avsorption band of carbonyl in wave number place; At 1235cm -1there is ehter bond charateristic avsorption band in wave number place.
Accompanying drawing 4, has provided the resistance toheat of E-PEK polymkeric substance under nitrogen environment.From experimental data, can find out, E-PEK has very excellent thermostability, and initial heat decomposition temperature is more than 500oC.
Embodiment
Embodiment 1: synthetic hexaphenyl end-blocking monomer
The first step adds 0.12mol aluminum trichloride (anhydrous) 0.5mol bromobenzene in the 250mL there-necked flask of mechanical stirring, drying tube is housed, under ice-water bath nitrogen atmosphere, slowly splash into 0.1mol4 fluorobenzoyl chloride, drip off rear stirring 15 minutes.Then remove ice-water bath, be heated to bromobenzene and reflux, react 4 hours, after question response system is down to room temperature, discharging is in massfraction 15% aqueous hydrochloric acid.Use chloroform extraction organic phase, with massfraction 5% sodium hydroxide solution and distilled water, wash respectively organic phase, underpressure distillation extraction liquid obtains white solid.With sherwood oil recrystallization, obtain 25 grams of white crystals.
Second step, in the 250mL there-necked flask of mechanical stirring, thermometer is housed, add 4 Xiu 4 fluorine benzophenone 0.05mol, triphenylphosphine 0.1g, cuprous iodide 0.05g, two (triphenylphosphine) palladium chloride (II) 0.05g is as catalyzer, 150mL triethylamine.Under nitrogen protection, constantly stir and be warming up to 60 ℃, solution becomes after clarification, slowly splashes into the triethylamine solution (0.001mol/mL) of 50mL phenylacetylene.After all dripping, rise to 80 ℃ and continue reaction 6 hours.Be cooled to after room temperature, filter and obtain white filter cake, with distilled water, wash away inorganic salt, ethyl alcohol recrystallization obtains 13 grams of light yellow crystal.
The 3rd step; in churned mechanically 50mL there-necked flask is housed, drop into 4 (phenylacetylene base) 4 difluoro benzophenone 0.01mol; tetraphenylcyclopentadienone 0.01mol; solvent sulfolane 25mL; under nitrogen protection, 260 ℃ are reacted 6 hours, obtain yellow solid, with ethanol, wash 5 times; it is target product that toluene recrystallization obtains 6 grams of white powders, productive rate >95%.Through 1HNMR, proved the structure (accompanying drawing 1) of monomer.
Embodiment 2: synthetic hexaphenyl end-blocking monomer
Method is with embodiment 1, by the first step in embodiment 1 drip off 4 after difluoro benzoyl chloride churning time become 30 minutes, bromobenzene return time is 6 hours; 80 ℃ of reaction times of second step are 4 hours, are then cooled to room temperature, stir 12 hours; The 3rd step solvent changes phenyl ether into, can obtain equally hexaphenyl benzene end-blocking monomer.
3: one step feeding methods of embodiment are prepared six phenyl ring end capped polyether ketone (E-PEK-10000) of molecular weight 10000
Six phenyl ring end-blocking monomer I (0.047mol), 4,4 '-difluoro benzophenone (1mol), 4,4 '-dihydroxy benzophenone (1mol), anhydrous sodium carbonate (1.3mol), sulfobenzide enter to be equipped with in the there-necked flask of water-taker.Nitrogen atmosphere Gradient intensification (210 degrees Celsius are reacted 1 hour, and 250 degrees Celsius are reacted 1 hour, and 280 degrees Celsius are reacted 1 hour, and 320 degrees Celsius are reacted 1 hour).Polymkeric substance is separated out in water, through pulverizing, hot ethanol, extract sulfobenzide solvent 5 times, after deionized water extrct desalts, filtration drying is to polymkeric substance.
4: two step feeding methods of embodiment are prepared six phenyl ring end capped polyether ketone (E-PEK-50000) of molecular weight 50000
4,4 '-difluoro benzophenone (0.984mol), 4,4 '-dihydroxy benzophenone (1.0mol), anhydrous sodium carbonate (1.3mol), sulfobenzide drop in there-necked flask.Nitrogen atmosphere Gradient heats up (210 degrees Celsius are reacted 1 hour, and 250 degrees Celsius are reacted 1 hour, and 280 degrees Celsius are reacted 1 hour, and 320 degrees Celsius are reacted 1 hour), at last stage reaction, adds six phenyl ring end-blocking monomers of 50 times of end group amounts to continue to react 30min.Polymkeric substance is separated out in water, through pulverizing, hot ethanol, extract sulfobenzide solvent 5 times, after deionized water extrct desalts, filtration drying is to polymkeric substance.
Embodiment 5: the preparation of six phenyl ring end capped polyether ketone materials of different molecular weight content
By the calculating feed ratio of number of repeat unit, according to the reaction conditions of embodiment 3 and embodiment 4, the proportioning of biphenol monomer, two fluorine monomer and the end-blocking monomer only changing (the two fluorine monomer/biphenol monomer <1.1 of 0.9<), other conditions are constant, all can successfully prepare different molecular weight E PEK polymkeric substance
Embodiment 6: different types of manufacture of carbonates E PEK
By the sodium carbonate in embodiment 1 and embodiment 2, replace with salt of wormwood or cesium carbonate or their mixing salt, all successfully make E PEK polymkeric substance.

Claims (4)

1. fluoro-4 '-(2,3,4,5, the 6-pentapheneyl) benzophenone of hexaphenyl end-blocking monomer 4-, its structural formula is as follows:
2. the preparation method of fluoro-4 '-(2,3,4,5, the 6-pentapheneyl) benzophenone of hexaphenyl end-blocking monomer 4-claimed in claim 1, its step is as follows:
1) bromobenzene, aluminum trichloride (anhydrous) are joined in reaction vessel, mechanical stirring under ice-water bath, slowly splashes into 4-fluorobenzoyl chloride in this reaction system, treats that raw material all drips off, and removes ice-water bath; Be warming up to bromobenzene and reflux, react 4～6 hours; Then reaction system is down in the aqueous hydrochloric acid that discharging is 15～20% in mass concentration after room temperature, uses chloroform extraction organic phase, with sodium hydroxide solution and the distilled water of mass concentration 5～8%, wash respectively organic phase; Collection extraction liquid carries out underpressure distillation and removes bromobenzene, and product obtains the bromo-4 '-fluorine benzophenone of 4-white crystal with sherwood oil recrystallization; Wherein bromobenzene is excessive, is reactant and reaction solvent, and the mole dosage of aluminum trichloride (anhydrous) is 1.2～3 times of 4-fluorobenzoyl chloride;
2) cuprous iodide of the bromo-4 '-fluorine benzophenone of 4-, catalytic amount, triphenylphosphine and two (triphenylphosphine) palladium chloride (II), triethylamine are put in reaction vessel to mechanical stirring under nitrogen protection; When reaction system is warming up to 30～70 ℃, more slowly drip the triethylamine solution of phenylacetylene, after dripping off, be warming up to 80～90 ℃ of reactions 4～6 hours; Reaction system is filtered after being down to room temperature, by distilled water wash filtration product, obtains white solid, with obtaining the yellow needle-like crystal of 4-(phenylacetylene base)-4 '-fluorine benzophenone after ethyl alcohol recrystallization; Wherein, the mole dosage ratio of the bromo-4 '-fluorine benzophenone of 4-and phenylacetylene is 0.2～5:1;
3) 4-(phenylacetylene base)-4 '-fluorine benzophenone, tetraphenylcyclopentadienone, tetramethylene sulfone or phenyl ether are joined in reaction vessel, mechanical stirring under nitrogen protection, 260～280 ℃ are reacted 6～8 hours, are cooled to room temperature and obtain yellow solid, by washing with alcohol, toluene recrystallization obtains white solid, be hexaphenyl end-blocking monomer 4-fluoro-4 '-(2,3,4,5,6-pentapheneyl) benzophenone; Wherein, the mole dosage ratio of 4-(phenylacetylene base)-4 '-fluorine benzophenone and tetraphenylcyclopentadienone is 0.2～5:1.
3. the application of fluoro-4 '-(2,3,4,5, the 6-pentapheneyl) benzophenone of hexaphenyl end-blocking monomer 4-claimed in claim 1 aspect preparation six phenyl ring end capped polyether ketone materials.
4. hexaphenyl end-blocking monomer 4-fluoro-4 '-(2,3,4 as claimed in claim 3,5,6-pentapheneyl) application of benzophenone aspect preparation six phenyl ring end capped polyether ketone materials, is characterized in that: the structural formula of six prepared phenyl ring end capped polyether ketone materials is as follows
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CN105130774A (en) * 2015-09-09 2015-12-09 吉林大学 Hexaphenylbenzene structure-containing difluo monomer, preparation method and application of difluo monomer in preparation of polyarylether
CN105646174A (en) * 2016-01-27 2016-06-08 吉林大学 Bis(tetraphenylmethane)-substituted terminated monomer, preparation method and application in preparation of terminated-type polyether sulfone material and post-sulfonation treatment
CN106045828A (en) * 2016-07-01 2016-10-26 大连鼎燕医药化工有限公司 Preparation method of 4,4'-difluorobenzophenone
CN106045828B (en) * 2016-07-01 2018-09-25 大连鼎燕医药化工有限公司 A kind of preparation method of 4,4 '-difluoro benzophenones

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