CN105130774A - Hexaphenylbenzene structure-containing difluo monomer, preparation method and application of difluo monomer in preparation of polyarylether - Google Patents
Hexaphenylbenzene structure-containing difluo monomer, preparation method and application of difluo monomer in preparation of polyarylether Download PDFInfo
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Abstract
The invention provides a hexaphenylbenzene structure-containing novel difluo monomer, preparation method and application of the novel difluo monomer in preparation of polyarylether, and belongs to the technical field of high polymer materials and preparation of the high polymer materials. The name of the difluo monomer is (2,6-difluorobenzoyl) (4-(3-(4-(1,2,3,4,5-phenoxypentaphene))propyl)phenyl)ketone. The hexaphenylbenzene side chain structure-containing polyarylether prepared by the invention can be used for preparing a proton exchange membrane, assembling a membrane electrode of a proton exchange membrane fuel cell or a methanol fuel cell system, preparing a photoelectric material and the like. The polyarylether prepared by the invention not only has outstanding heat resistance, but also has excellent properties of the photoelectric functional material, moreover the polyarylether further has a multi-sulfonation cyclo-hexaphenyl structure, thus having wide application prospect in many fields such as photoelectric materials and proton exchange membranes.
Description
Technical field
The invention belongs to macromolecular material and preparing technical field thereof, be specifically related to a kind of novel two fluorine monomers, preparation method containing hexaphenyl benzene structure and preparing the application in polyarylether polymer.
Background technology
As everyone knows, fragrant polymkeric substance is the one of special engineering plastics, compare with other polymer phases, it has lot of superiority, and such as lower price, more easily prepares, outstanding thermal characteristics and mechanical property, and be widely used in aerospace, automobile making, the numerous areas such as mechanical means.And the polyarylether polymer that existing commercialization degree is higher, due to the unicity of its structure, not too adapt at present for its various ceaselessly demands.Therefore, the functionalization for polyarylether polymer becomes current important research topic.Wherein important means are exactly by a molecular designing, functionalization functional group are incorporated in the middle of polymer molecular structure, thus realize the lifting of polyalcohol integral performance.
The group of intensive benzene ring structure, due to its larger conjugate area, larger volume, makes the polymkeric substance containing this group have many potential application at materials such as photoelectric material, parting material, proton exchange membrane.The side chain containing intensive benzene ring structure is introduced in polyarylether polymer structure, realize the functional modification to polymkeric substance, make the polyarylether polymer of thermostability, chemical stability, good mechanical properties have potential using value in photoelectric material, proton exchange membrane field.
Summary of the invention
The object of this invention is to provide a kind of novel two fluorine monomers, preparation method containing hexaphenyl benzene structure and preparing the application in polyarylether polymer.A kind of two fluorine monomers containing hexaphenyl benzene structure of the present invention; its name is called (2; 6-difluoro benzoyl) (4-(3-(4-(1; 2; 3; 4,5-pentapheneyl phenoxy group)) propyl) phenyl) ketone, its structural formula is as follows:
The preparation method of a kind of two fluorine monomers containing hexaphenyl benzene structure of the present invention, its step is as follows:
The first step is reacted: under atmosphere of inert gases, with 2,6-difluoro-benzoic acid for raw material, thionyl chloride is not only solvent but also be reactant, and DMF is catalyzer, mixing is warming up to 70 ~ 80 DEG C to thionyl chloride backflow under magnetic stirring, reacts 6 ~ 8 hours; After air distillation steams thionyl chloride, being decompressed to vacuum tightness is that after-0.09 ~-0.1MPa, distillation obtains colourless transparent liquid A, i.e. 2,6-difluoro benzoyl chlorides; Wherein the usage ratio of 2,6-difluoro-benzoic acids, thionyl chloride and DMF is 100g:300 ~ 400mL:2 ~ 3mL;
Second step reacts: the bromo-3-phenyl-propane of 2,6-difluoro benzoyl chloride, aluminum chloride, methylene dichloride, 1-mixes under ice-water bath, protection of inert gas magnetic agitation; React that to pour concentration into after 2 ~ 4 hours be that in the ice dilute hydrochloric acid solution of 1 ~ 2mol/L, separatory obtains organic phase; Organic phase is washed 2 ~ 3 times, after distillation washing 3 ~ 5 times with massfraction 10 ~ 20% sodium hydroxide solution respectively, use anhydrous magnesium sulfate drying organic phase again, and to be decompressed to vacuum tightness be steam methylene dichloride after-0.09 ~-0.1MPa, light yellow crystal B is obtained after leaving standstill, i.e. (4-(3-N-PROPYLE BROMIDE base) phenyl) (2,6-difluoro benzoyl) ketone; Wherein, the mol ratio of 2,6-difluoro benzoyl chloride, aluminum chloride, the bromo-3-phenyl-propane of 1-is 1:1 ~ 1.1:1; The ratio of 2,6-difluoro benzoyl chloride, aluminum chloride, 1-bromo-3-phenyl-propane total mass and methylene chloride volume is 1 ~ 1.1g:10mL;
Three-step reaction: under atmosphere of inert gases, adds the ammoniacal liquor of massfraction 24 ~ 28% in anhydrous cupric sulfate, mechanical stirring under ice-water bath, adds distilled water diluting 3 ~ 5 times after 3 ~ 5 minutes, stirs 3 ~ 5 minutes; Add oxammonium hydrochloride subsequently to the speed with 5 ~ 10mL/min in solution, solution is shoaled gradually by faint blue; Add the ethanolic soln (wherein the amount ratio of phenylacetylene and ethanol is 0.05mol:1 ~ 1.2L) of phenylacetylene in the backward system of 3 ~ 5 minutes, obtain pale yellow precipitate, filter after thin up, and respectively wash 3 ~ 5 times with water, ethanol, ether respectively; Final product vacuum-drying 2 ~ 4 hours at 50 ~ 65 DEG C, obtains light yellow crystal C, i.e. phenylacetylene copper; Wherein the mol ratio of anhydrous cupric sulfate, oxammonium hydrochloride, phenylacetylene is 1 ~ 1.1:2 ~ 2.2:1 ~ 1.1, and the usage ratio of anhydrous cupric sulfate and ammoniacal liquor is 1g:5 ~ 10mL;
Four-step reaction: light yellow crystal C, paraiodoanisole, pyridine mix under protection of inert gas magnetic agitation, be warming up to 114 ~ 116 DEG C, back flow reaction 6 ~ 8 hours, is poured into water reaction soln, filtration obtains white solid D, namely to phenylacetylene base methyl-phenoxide; The mol ratio of light yellow crystal C and paraiodoanisole is 1:1.1 ~ 1.5, and pyridine is 10 ~ 15mL:1 ~ 1.2g with the ratio of reactant (the light yellow crystal C+ paraiodoanisole) total amount added;
5th step reaction: white solid D, tetraphenylcyclopentadienone, tetramethylene sulfone mix under nitrogen protection mechanical stirring, be warming up to 260 ~ 280 DEG C of reactions 6 ~ 8 hours, be cooled to room temperature and obtain yellow solid, by washing with alcohol, re crystallization from toluene obtains white solid E, i.e. 1-(4-p-methoxy-phenyl)-2,3,4,5,6-pentapheneyl benzene; The mol ratio of white solid D, tetraphenylcyclopentadienone is 1:1 ~ 1.1; Tetramethylene sulfone is 10 ~ 15mL:1 ~ 1.2g with the ratio of reactant (the white solid D+ tetraphenylcyclopentadienone) total amount added;
Six-step process: white solid E is dissolved in the dichloromethane solution (ratio of white solid E and methylene dichloride is 1g:20 ~ 30mL) that methylene dichloride obtains E, boron tribromide is dissolved in (ratio of boron tribromide and methylene dichloride is 1g:20 ~ 30mL) in methylene dichloride simultaneously; Lentamente the dichloromethane solution of boron tribromide is dripped in the dichloromethane solution of E, and under ice-water bath, argon shield magnetic agitation, react 6 ~ 8 hours; Product is poured in frozen water and obtain white solid F, be i.e. 1-(4-hydroxyphenyl)-2,3,4,5,6-pentapheneyl benzene; The mol ratio of white solid E, boron tribromide is 1:3 ~ 4;
7th step reaction: light yellow crystal B, white solid F, salt of wormwood and DMF mix under argon atmosphere magnetic agitation, are heated to 80 ~ 90 DEG C; React N after 8 ~ 10 hours, dinethylformamide decompression steams, with after washing 2 ~ 3 times, with ethanol and trichloromethane recrystallization, obtain beige crystals G, namely (2,6-difluoro benzoyl) (4-(3-(4-(1,2,3,4,5-pentapheneyl phenoxy group)) propyl) phenyl) ketone; The mol ratio of light yellow crystal B, white solid F, salt of wormwood is 1: 1.1 ~ 1.2: 1.21 ~ 1.24; DMF is 10 ~ 15mL:1 ~ 1.2g with the ratio of reactant (the light yellow crystal B+ white solid F+ salt of wormwood) total amount added.
The application of two fluorine monomers containing hexaphenyl benzene structure in synthesis polyarylether polymer: by (2,6-difluoro benzoyl) (4-(3-(4-(1,2,3,4,5-pentapheneyl phenoxy group)) propyl) phenyl) ketone, two halogen monomer and biphenol monomer add in container as reactant, wherein (2,6-difluoro benzoyl) (4-(3-(4-(1,2,3,4,5-pentapheneyl phenoxy group)) propyl) phenyl) the consumption mol ratio of ketone, two halogen monomer and biphenol monomer is m:(1-m): 1, wherein m=0.1 ~ 0.2; Under the condition of biphenol monomer 1.1 ~ 1.2 times of molar weight catalyzer, add tetramethylene sulfone, make reaction system solid content (comprising catalyzer) be 20 ~ 40%, then add the azeotropy dehydrant of tetramethylene sulfone volume 20% ~ 30%; Under nitrogen protection mechanical stirring, be warming up to azeotropy dehydrant backflow, react 2 ~ 3 hours, get rid of azeotropy dehydrant, be warming up to 210 ~ 220 DEG C and continue reaction 8 ~ 12 hours; Being separated out in distilled water by the solution obtained, obtain brown solid, by distilled water and washing with alcohol, obtain pale yellowish brown solid, obtain preliminary polymerization thing in oven for drying, is namely the polyarylether polymer with hexaphenyl benzene side-chain structure.
Wherein, azeotropy dehydrant is toluene or dimethylbenzene.
Further, two halogen monomer can be 4,4 '-dihalo-benzophenone, 4,4 '-dihalo-sulfobenzide, and halogen is arbitrary halogen, particularly fluorine, chlorine, bromine; Biphenol monomer can be Resorcinol, 4,4 '-'-biphenyl diphenol, 4,4 '-dihydroxy diphenylsulphone, 4,4'-Dihydroxybenzophenone, dihydroxyphenyl propane, bisphenol AF.
Further, catalyzer is selected from one or more of salt of wormwood, sodium carbonate, calcium carbonate, potassium hydroxide, sodium hydroxide and hydrolith.
The polyarylether polymer of hexaphenyl benzene lateral group structure that prepared by the present invention have, its structural formula is as follows:
Wherein, m=0.1 ~ 0.2;
X is
Y is
The building-up process with the polyaryletherketone of hexaphenyl benzene structure side chain of the present invention, can represent with following reaction formula:
Wherein, m=0.1 ~ 0.2; N is positive integer, represents the quantity of repeating unit;
X is
Y is
R is F, Cl, Br
The purposes of the polyarylether material containing hexaphenyl benzene side-chain structure of the present invention can be used for preparing proton exchange membrane, and the membrane electrode for pem cell or methanol fuel-cell system is assembled, and the preparation etc. of photoelectric material.The polyarylether polymer that the present invention prepares not only has excellent resistance toheat, also have the premium properties of photoelectric functional material concurrently simultaneously, structurally also having can six benzene ring structure of polynary sulfonation, therefore has a wide range of applications at the numerous areas such as photoelectric material, proton exchange membrane.
Accompanying drawing illustrates:
Fig. 1: the nucleus magnetic hydrogen spectrum figure of the two fluorine monomers containing hexaphenyl benzene structure prepared by the embodiment of the present invention 1;
As can be seen from the figure, chemical shift is the peak corresponding H respectively of 1.93 ~ 2.03ppm, 2.76 ~ 2.81ppm, 3.74 ~ 3.78ppm respectively
f, H
e, H
ghydrogen on three methylene radical; The peak of chemical shift between 6.7 ~ 6.9ppm then on corresponding six phenyl ring except H
hh in addition
i, H
h ', H
i ', H
jhydrogen; H
hconjugative effect due to ortho position ehter bond makes shielding effect larger, and therefore its chemical shift is at 6.4ppm; H
a, H
b, H
c, H
drespectively at 7.39 ~ 7.49ppm, 6.98 ~ 7.03ppm, 7.75 ~ 7.78ppm, 7.22 ~ 7.25ppm find corresponding peak.To sum up can find out the two fluorine monomers successfully synthesized containing hexaphenyl benzene structure.
Fig. 2: the nucleus magnetic hydrogen spectrum figure of the polyaryletherketone containing hexaphenyl benzene side-chain structure prepared by the embodiment of the present invention 2;
As can be seen from the figure, chemical shift is the peak corresponding H respectively of 1.93 ~ 2.03ppm, 2.76 ~ 2.81ppm, 3.74 ~ 3.78ppm respectively
f, H
e, H
ghydrogen on three methylene radical; Due to H
bbecome cause its chemical shift to diminish to the ortho position ehter bond of electronics becoming 6.7ppm from being polymerized front electrophilic ortho position F; H
c, H
nbecause ortho position carbonyl causes deshielding effect remarkable, therefore chemical shift is maximum, at 7.78 ~ 7.85ppm; Six benzene ring hydrogens then appear at about 6.8ppm.In summary it can be seen that subject polymer successfully synthesizes.
Fig. 3: the infrared spectrum of the polyaryletherketone containing hexaphenyl benzene side-chain structure prepared by the embodiment of the present invention 2
As can be seen from the figure, wavelength is at 1658cm
-1there is the absorption peak of carbonyl at place, proves the successful polymerization of polymkeric substance;
Fig. 4: the TGA curve of the polyaryletherketone containing hexaphenyl benzene side-chain structure prepared by the embodiment of the present invention 2
As can be seen from the figure, 5% thermal weight loss of polymkeric substance is greatly about about 500 DEG C, and the thermostability of visible polymkeric substance is very good.
Concrete implementing method:
Embodiment 1: synthesis (2,6-difluorobenzoyl) (4-(3-(4-(1,2,3,4,5-pentapheneyl phenoxy group)) propyl) phenyl) ketone monomer
The first step is reacted: add 100g (0.63mol) 2 being equipped with in churned mechanically 1000mL there-necked flask, 6-difluoro-benzoic acid, 400mL thionyl chloride, instill 2 N under nitrogen atmosphere, dinethylformamide, stir after adding, be heated to thionyl chloride backflow, react 8 hours, air distillation removing thionyl chloride after completion of the reaction, underpressure distillation obtains colourless transparent liquid.Product colourless transparent liquid is 2,6-difluoro benzoyl chloride.
Second step reacts: being equipped with mechanical stirring, the 1000mL there-necked flask of drying tube adds 31.72g (0.24mol) aluminum trichloride (anhydrous), 500mL (8.1mol) methylene dichloride, 22g (0.12mol) 2 is slowly instilled under ice-water bath argon gas atmosphere, 6-difluoro benzoyl chloride, the bromo-3-phenyl-propane of 21.89g (0.11mol) 1-is dissolved with 100mL methylene dichloride (1.6mol), slow instillation reaction system, drip off rear stirring 15 minutes, then ice-water bath is removed, normal-temperature reaction 6 hours, discharging is in 10% aqueous hydrochloric acid after completion of the reaction.Use dichloromethane extraction organic phase, use sodium hydroxide solution and deionized water wash respectively, revolve steaming extraction liquid and obtain white solid.White crystal is obtained with 1,2-ethylene dichloride recrystallization.Product light yellow crystal is (4-(3-N-PROPYLE BROMIDE base) phenyl) (2,6-difluoro benzoyl) ketone.
Three-step reaction: add 25.0g (0.1mol) cupric sulfate pentahydrate in the 3000mL there-necked flask that mechanical stirring, argon gas port, drying tube are housed, 100mL (28%) ammoniacal liquor, stirs 5 minutes under argon shield; Add 400mL distilled water and stir 5 minutes, slowly add 13.9g (0.2mol) oxammonium hydrochloride, now faint blue solution shoals, and stirs 10 minutes; Add 10.2g (0.1mol) phenylacetylene and 500mL ethanol obtains pale yellow precipitate, filter after adding 500mL water, respectively wash 5 times respectively with 100mL water, ethanol, ether, vacuum-drying 4h at 65 DEG C, obtaining faint yellow solid is phenylacetylene copper.
Four-step reaction: add 10g (0.06mol) phenylacetylene copper, 14.21g (0.06mol) paraiodoanisole and 180mL pyridine in the 500mL there-necked flask that magnetic agitation, argon gas port, reflux condensing tube are housed; stirring and refluxing 8 hours under argon shield; reaction soln is poured in 600mL water; filtration obtains white solid, namely to phenylacetylene base methyl-phenoxide.
5th step reaction: add in the 50mL there-necked flask that magnetic agitation, argon gas port, reflux condensing tube are housed phenylacetylene base methyl-phenoxide 4g (0.01mol); tetraphenylcyclopentadienone 4.55g (0.01mol), solvent sulfolane 25mL, under argon shield, 280 DEG C are reacted 8 hours; obtain yellow solid; wash 5 times with ethanol, re crystallization from toluene obtains white powder, i.e. 1-(4-p-methoxy-phenyl)-2; 3; 4,5,6-pentapheneyl benzene.
Six-step process: add 6.7g (0.012mol) 1-(4-p-methoxy-phenyl)-2 in the 250mL there-necked flask that magnetic agitation, argon gas port, the low liquid funnel of constant voltage are housed, 3,4,5,6-pentapheneyl benzene, dissolves with the methylene dichloride of 20mL, in ice-water bath, cool 20 minutes, (wherein boron tribromide is 9.02g, 0.036mol slowly to drip the dichloromethane solution of boron tribromide wherein; Methylene dichloride is 20mL), add 80mL methylene dichloride subsequently, stir 8 hours, product is poured in frozen water and obtains white precipitate, filter, oven dry obtains white powder, is 1-(4-hydroxyphenyl)-2,3,4,5,6-pentapheneyl benzene.
7th step reaction: add 4g (7.3mmol) 1-(4-hydroxyphenyl)-2 in the 250mL there-necked flask that magnetic agitation, argon gas port, reflux condensing tube are housed, 3,4,5,6-pentapheneyl benzene, 2.97g (8.76mmol) are to phenylacetylene base methyl-phenoxide, 1.21g (8.76mmol) salt of wormwood and 100mLN, dinethylformamide, is heated to 85 DEG C, reacts 10 hours; By N; dinethylformamide decompression steams; solid washed with water 3 times; obtaining beige crystals with ethanol and trichloromethane recrystallization, is (2,6-difluoro benzoyl) (4-(3-(4-(1; 2; 3,4,5-pentapheneyl phenoxy group)) propyl) phenyl) ketone.The nucleus magnetic hydrogen spectrum figure of (2,6-difluoro benzoyl) (4-(3-(4-(1,2,3,4,5-pentapheneyl phenoxy group)) propyl) phenyl) ketone is shown in Fig. 1.As can be seen from Figure 1; there is rational ownership the position at each peak; thus prove (2; 6-difluoro benzoyl) (4-(3-(4-(1; 2,3,4; 5-pentapheneyl phenoxy group)) propyl) phenyl) the successful synthesis of ketone, purity is 99%.
Embodiment 2: the polyaryletherketone HP-PAEK-10 of the two fluorine monomer content 10% of synthesis containing hexaphenyl benzene structure
Input (2 in churned mechanically 25mL there-necked flask is being housed; 6-difluoro benzoyl) (4-(3-(4-(1; 2; 3; 4; 5-pentapheneyl phenoxy group)) propyl) phenyl) ketone 0.3236g (0.0004mol), 4; 4 '-difluoro benzophenone 0.7855g (0.0036mol), bisphenol AF 1.3449g (0.004mol), salt of wormwood 0.6081g (0.0044mol); feed ratio is: 1:9:10:11; solvent sulfolane 6mL, dimethylbenzene 5mL are azeotropy dehydrant.React under argon shield; 175 DEG C of band water steam except dimethylbenzene after 3 hours; be warming up to 210 DEG C of reactions 6 hours; discharging is in deionized water; obtain brown solid; obtaining pale yellowish brown solid by distilled water and washing with alcohol, is namely the polyaryletherketone HP-PAEK-10 of the two fluorine monomer content 10% containing hexaphenyl benzene structure.
Embodiment 3: the polyaryletherketone HP-PAEK-15 of the two fluorine monomer content 15% of synthesis containing hexaphenyl benzene structure
By (2 in embodiment 2; 6-difluoro benzoyl) (4-(3-(4-(1; 2,3,4; 5-pentapheneyl phenoxy group)) propyl) phenyl) ketone, 4; the ratio of 4 '-difluoro benzophenone, bisphenol AF and salt of wormwood changes 3:17:20:22 into, and the molar ratio that namely the novel pair of fluorine monomer accounts for all pairs of fluorine monomers becomes 0.15, and other conditions are constant; repeat embodiment 2, obtain another kind of polymkeric substance HP-PAEK-15
Embodiment 4: the polyaryletherketone HP-PAEK-20 of the two fluorine monomer content 20% of synthesis containing hexaphenyl benzene structure
By (2 in embodiment 2; 6-difluoro benzoyl) (4-(3-(4-(1; 2; 3; 4; 5-pentapheneyl phenoxy group)) propyl) phenyl) ketone, 4; the ratio of 4 '-difluoro benzophenone, bisphenol AF and salt of wormwood changes 1:4:5:5.5 into; namely the molar ratio that the novel pair of fluorine monomer accounts for all pairs of fluorine monomers becomes 0.2; other conditions are constant; repeat embodiment 2, obtain the polyaryletherketone HP-PAEK-20 of the two fluorine monomer content 20% containing hexaphenyl benzene structure.
Embodiment 5: the preparation of other polymkeric substance
In embodiment 2,3,4, replace 4 with 4,4 '-difluorodiphenyl sulfone, 4 '-difluoro benzophenone; With Resorcinol, 4,4 '-'-biphenyl diphenol, 4,4 '-dihydroxy diphenylsulphone, 4,4'-Dihydroxybenzophenone, dihydroxyphenyl propane replace bisphenol AF.The polyaryletherketone base polymer containing hexaphenyl benzene side-chain structure of counter structure can be obtained equally.
Claims (3)
1. the two fluorine monomers containing hexaphenyl benzene structure, i.e. (2,6-difluoro benzoyl) (4-(3-(4-(1; 2,3,4; 5-pentapheneyl phenoxy group)) propyl) phenyl) ketone, its structural formula is as follows:
2. the preparation method of a kind of two fluorine monomers containing hexaphenyl benzene structure according to claim 1, its step is as follows:
The first step is reacted: under atmosphere of inert gases, with 2,6-difluoro-benzoic acid for raw material, thionyl chloride is not only solvent but also be reactant, and DMF is catalyzer, mixing is warming up to 70 ~ 80 DEG C to thionyl chloride backflow under magnetic stirring, reacts 6 ~ 8 hours; After air distillation steams thionyl chloride, being decompressed to vacuum tightness is that after-0.09 ~-0.1MPa, distillation obtains colourless transparent liquid A, i.e. 2,6-difluoro benzoyl chlorides; Wherein the usage ratio of 2,6-difluoro-benzoic acids, thionyl chloride and DMF is 100g:300 ~ 400mL:2 ~ 3mL;
Second step reacts: the bromo-3-phenyl-propane of 2,6-difluoro benzoyl chloride, aluminum chloride, methylene dichloride, 1-mixes under ice-water bath, protection of inert gas magnetic agitation; React that to pour concentration into after 2 ~ 4 hours be that in the ice dilute hydrochloric acid solution of 1 ~ 2mol/L, separatory obtains organic phase; Organic phase is washed 2 ~ 3 times, after distillation washing 3 ~ 5 times with massfraction 10 ~ 20% sodium hydroxide solution respectively, use anhydrous magnesium sulfate drying organic phase again, and to be decompressed to vacuum tightness be steam methylene dichloride after-0.09 ~-0.1MPa, light yellow crystal B is obtained after leaving standstill, i.e. (4-(3-N-PROPYLE BROMIDE base) phenyl) (2,6-difluoro benzoyl) ketone; Wherein, the mol ratio of 2,6-difluoro benzoyl chloride, aluminum chloride, the bromo-3-phenyl-propane of 1-is 1:1 ~ 1.1:1; The ratio of 2,6-difluoro benzoyl chloride, aluminum chloride, 1-bromo-3-phenyl-propane total mass and methylene chloride volume is 1 ~ 1.1g:10mL;
Three-step reaction: under atmosphere of inert gases, adds the ammoniacal liquor of massfraction 24 ~ 28% in anhydrous cupric sulfate, mechanical stirring under ice-water bath, adds distilled water diluting 3 ~ 5 times after 3 ~ 5 minutes, stirs 3 ~ 5 minutes; Add oxammonium hydrochloride subsequently to the speed with 5 ~ 10mL/min in solution, solution is shoaled gradually by faint blue; Add the ethanolic soln of phenylacetylene in the backward system of 3 ~ 5 minutes, wherein the amount ratio of phenylacetylene and ethanol is 0.05mol:1 ~ 1.2L, obtains pale yellow precipitate, filters after thin up, and respectively washes 3 ~ 5 times with water, ethanol, ether respectively; Final product vacuum-drying 2 ~ 4 hours at 50 ~ 65 DEG C, obtains light yellow crystal C, i.e. phenylacetylene copper; Wherein the mol ratio of anhydrous cupric sulfate, oxammonium hydrochloride, phenylacetylene is 1 ~ 1.1:2 ~ 2.2:1 ~ 1.1, and the usage ratio of anhydrous cupric sulfate and ammoniacal liquor is 1g:5 ~ 10mL;
Four-step reaction: light yellow crystal C, paraiodoanisole, pyridine mix under protection of inert gas magnetic agitation, be warming up to 114 ~ 116 DEG C, back flow reaction 6 ~ 8 hours, is poured into water reaction soln, filtration obtains white solid D, namely to phenylacetylene base methyl-phenoxide; The mol ratio of light yellow crystal C and paraiodoanisole is 1:1.1 ~ 1.5, and pyridine is 10 ~ 15mL:1 ~ 1.2g with the ratio of the reaction-ure mixture added;
5th step reaction: white solid D, tetraphenylcyclopentadienone, tetramethylene sulfone mix under nitrogen protection mechanical stirring, be warming up to 260 ~ 280 DEG C of reactions 6 ~ 8 hours, be cooled to room temperature and obtain yellow solid, by washing with alcohol, re crystallization from toluene obtains white solid E, i.e. 1-(4-p-methoxy-phenyl)-2,3,4,5,6-pentapheneyl benzene; The mol ratio of white solid D, tetraphenylcyclopentadienone is 1:1 ~ 1.1; Tetramethylene sulfone is 10 ~ 15mL:1 ~ 1.2g with the ratio of the reaction-ure mixture added;
Six-step process: white solid E is dissolved in the dichloromethane solution that methylene dichloride obtains E, the ratio of white solid E and methylene dichloride is 1g:20 ~ 30mL; Be dissolved in methylene dichloride by boron tribromide, the ratio of boron tribromide and methylene dichloride is 1g:20 ~ 30mL simultaneously; Lentamente the dichloromethane solution of boron tribromide is dripped in the dichloromethane solution of E, and under ice-water bath, argon shield magnetic agitation, react 6 ~ 8 hours; Product is poured in frozen water and obtain white solid F, be i.e. 1-(4-hydroxyphenyl)-2,3,4,5,6-pentapheneyl benzene; The mol ratio of white solid E, boron tribromide is 1:3 ~ 4;
7th step reaction: light yellow crystal B, white solid F, salt of wormwood and DMF mix under argon atmosphere magnetic agitation, are heated to 80 ~ 90 DEG C; React N after 8 ~ 10 hours, dinethylformamide decompression steams, with after washing 2 ~ 3 times, with ethanol and trichloromethane recrystallization, obtain beige crystals G, namely (2,6-difluoro benzoyl) (4-(3-(4-(1,2,3,4,5-pentapheneyl phenoxy group)) propyl) phenyl) ketone; The mol ratio of light yellow crystal B, white solid F, salt of wormwood is 1: 1.1 ~ 1.2: 1.21 ~ 1.24; DMF is 10 ~ 15mL:1 ~ 1.2g with the ratio of the reaction-ure mixture added.
3. a kind of two fluorine monomers containing hexaphenyl benzene structure according to claim 1 are preparing the application in structural formula polyarylether polymer as follows,
wherein, m=0.1 ~ 0.2; N is positive integer, represents the quantity of repeating unit;
X is
Y is
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