CN108794406A - One kind has the active double fluorine monomers of necleophilic reaction, preparation method and its application in preparing polyarylether - Google Patents
One kind has the active double fluorine monomers of necleophilic reaction, preparation method and its application in preparing polyarylether Download PDFInfo
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- CN108794406A CN108794406A CN201810009244.4A CN201810009244A CN108794406A CN 108794406 A CN108794406 A CN 108794406A CN 201810009244 A CN201810009244 A CN 201810009244A CN 108794406 A CN108794406 A CN 108794406A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/26—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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- 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
- C08G65/4006—(I) or (II) containing elements other than carbon, oxygen, hydrogen or halogen as leaving group (X)
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- 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
- C08G65/4056—(I) or (II) containing sulfur
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Abstract
One kind has the active double fluorine monomers of necleophilic reaction, preparation method and its application in preparing polyarylether, belongs to high molecular material and its preparing technical field.Entitled 4,4'- bis--(4- fluorophenyls) -6,6'- bis--(4-R bases phenyl) -2,2'- of double fluorine monomers joins pyrimidine, and structural formula is as follows.The polyarylether that main chain prepared by the present invention contains connection pyrimidine structure can be used for preparing gas separation membrane, the preparation etc. of the bulking agent and photoelectric material of the composite material of polymer and metal organic framework.The polyarylether polymer that the present invention is prepared not only has excellent heat resistance, the excellent performance of photoelectric functional material is also had both simultaneously, also possess nitrogenous heterocyclic structure in structure, therefore has a wide range of applications in numerous areas such as photoelectric material, Coordinative Chemistry and gas separation.
Description
Technical field
The invention belongs to technical field of polymer materials, and in particular to a kind of novel have the active double fluorine of necleophilic reaction
Monomer, preparation method and its application in preparing polyarylether.
Background technology
It is well known that polyarylether is a kind of important functional material, have temperature classification height, good mechanical property, size steady
The excellent properties such as qualitative good, excellent electrical property, fire-retardant and easily molded processing, are widely used in delicate electronic device, aviation boat
It, national defence, the fields such as industry.But commercialized polyarylether type is less at present.In order to extend type and the imparting of polyarylether
Its new function, it is highly important to be modified to polyarylether.It commonly uses and imitates currently, physical modification and chemical modification are polyarylethers
The most significant method of modifying of fruit.Physical modification is mainly blending and modifying, for example is blended with carbon fiber, elevating mechanism performance and resistance to thermal energy
Power.Chemical modification method mainly has：Introduce big side group, modification by copolymerization, introduce distortion non-co-planar structure, main chain introduce it is miscellaneous
Atom etc..
The non-co-planar structural compounds that connection pyrimidine is distorted as a kind of nitrogen heterocyclic ring are led in photoelectric field and Coordinative Chemistry
Domain is extensively studied.In addition, the thermal stability of pyrimidine ring is better than phenyl ring.Therefore, connection pyrimidine structure is introduced into polyarylether, no
But the functionalization of polyarylether may be implemented, and the hot property of polyarylether can be improved.
Invention content
The object of the present invention is to provide it is a kind of it is novel have the active double fluorine monomers of necleophilic reaction, preparation method and its
Prepare the application in polyarylether.
It is of the present invention a kind of with the active double fluorine monomers of necleophilic reaction, entitled 4,4'- bis--(4- fluorobenzene
Base) -6,6'- bis--(4-R bases phenyl) -2,2'- joins pyrimidine, and structural formula is as follows：
Wherein, R H, CH3、OCH3、NO2、C6H5One kind in (phenyl).
The above-mentioned preparation method with the active double fluorine monomers of necleophilic reaction of the present invention, its step are as follows：
(1) under atmosphere of inert gases, using to fluoro acetophenone, to R benzaldehydes and urea as reactant, trimethylchloro-silicane
Alkane and copper chloride are catalyst, and acetonitrile is solvent, and mixing under stiring is warming up to reflux, reacts 6~12 hours；Then it discharges
It into deionized water, and is washed with deionized water 3~6 times, ethyl alcohol is washed 3~6 times, and 6- (4- phenyl) -4- (4-R bases are recrystallized to give
Phenyl) pyrimidine -2 (1 hydrogen) -one；Throwing wherein to fluoro acetophenone, to R benzaldehydes, urea, copper chloride and trim,ethylchlorosilane
Expect that molar ratio is 1：0.9~1.1：1.2~3：0.05~0.5：0.9~1.1；Every mole to fluoro acetophenone with acetonitrile 500~
3000mL；
(2) using 6- (4- phenyl) -4- (4-R bases phenyl) pyrimidine -2 (1 hydrogen) -one and phosphorus oxychloride as reactant, N, N'-
Dimethylaniline is catalyst, is mixed under inert gas shielding and magnetic agitation；90~170 DEG C are warming up to, reaction 3~9 is small
When after steam most of phosphorus oxychloride, be cooled to room temperature, be subsequently poured into ice water, be precipitated yellow solid, filter, solid spend from
Son washing 3~8 times；It is recrystallized to give the chloro- 4- of 2- (4- fluorophenyls) -6- (4-R bases phenyl) pyrimidine；Wherein, 6- (4- phenyl)-
4- (4-R bases phenyl) pyrimidine -2 (1 hydrogen) -one, phosphorus oxychloride and N,N' dimethyl aniline amount ratio are 1g：3~10mL：0.02
~0.2mL；
(3) under atmosphere of inert gases, Dehydrated nickel chloride, triphenylphosphine and zinc powder are added to anhydrous DMF (N, N- bis-
Methylformamide) in, after being stirred 20~120 minutes at 40~70 DEG C, 2- chloro- 4- (4- fluorophenyls) -6- (4-R base benzene is added dropwise
Base) pyrimidine DMF solution, be added dropwise completely after reaction 3~9 hours；It discharges into the mixed system of ammonium hydroxide and chloroform, point
Liquid, chloroform layer are washed with water 2~6 times, and revolving, solid vacuum drying, column chromatography for separation is spin-dried for, and obtains 4,4'- bis--(4- fluorine
Phenyl) -6,6'- two-(4-R bases phenyl) -2,2'- connection pyrimidines；Wherein Dehydrated nickel chloride, triphenylphosphine, zinc powder and the chloro- 4- of 2-
The molar ratio of (4- fluorophenyls) -6- (4-R bases phenyl) pyrimidine is 1：3~8：1~2：0.5~2.
A kind of main chain for having the active double fluorine monomers of necleophilic reaction as follows in preparation structure formula of the present invention
It can be applied in polyarylether containing connection pyrimidine structure.
Wherein, 0<M≤1, n are positive integer, repeateding unit number, 0<n<200；
For
Y isR is H, CH3、OCH3、NO2、C6H5One kind in (phenyl).
The preparation method that main chain of the present invention contains the polyarylether of connection pyrimidine structure is as follows：
4,4'- bis--(4- fluorophenyls) -6,6'- two-(4-R bases phenyl) -2,2'- is joined into pyrimidine, double halogen monomers and bis-phenol list
Body is added to the container as reactant, wherein 4,4'- bis--(4- fluorophenyls) -6,6'- bis--(4-R bases phenyl) -2,2'- connection are phonetic
The dosage molar ratio of pyridine, biphenol monomer and double halogen monomers is m：(1-m)：1, wherein 0<m≤1；Double halogen monomers 1.1~1.2 are added
Solvent is added in times mole catalyst, and it is 15~40% to make reaction system solid content (including catalyst), adds solvent volume
20%~90% azeotropy dehydrant；Under inert atmosphere protection, mechanical agitation is warming up to azeotropy dehydrant and flows back, and reaction 2~
6 hours, steam azeotropy dehydrant；Being warming up to 170~220 DEG C again, the reaction was continued 5~12 hours, and deionized water is arrived in then discharging
In, strip solid is obtained, is washed 3~6 times with deionized water and ethyl alcohol, vacuum drying, it is phonetic containing joining to obtain main chain of the present invention
The polyarylether of pyridine structure.
Wherein, azeotropy dehydrant is toluene or dimethylbenzene, and solvent is dimethyl sulfoxide (DMSO), sulfolane (TMS) or N- first
Base pyrrolidones (NMP).
Double halogen monomers can be 4,4 '-dihalo- benzophenone or 4, and 4 '-dihalo- diphenyl sulphone (DPS)s, halogen is fluorine or chlorine；Bis-phenol list
Body can be hydroquinone, 4,4 '-'-biphenyl diphenols, 4,4 '-dihydroxydiphenylsulisomers, 4,4 '-dihydroxy benaophenonels, bisphenol-A, double
Phenol AF.
Catalyst is selected from one or both of potassium carbonate, sodium carbonate and cesium carbonate.
The main chain of the present invention contains the building-up process of connection pyrimidine structure polyarylether, can be indicated with following reaction equation：
Wherein, 0<M≤1, n are positive integer, repeateding unit number, 0<n<200；
For
Y is
R is H, CH3、OCH3、NO2And C6H5One kind in (phenyl),
X is F or Cl.
One kind prepared by the present invention is novel, and there are the active double fluorine monomers of necleophilic reaction largely to enrich connection
Pyrimidine derivates species, such double fluorine monomer is very different with previous connection pyrimidine monomers, because such monomer can be made
It goes to prepare polyarylether for nucleopilic reagent.The polyarylether prepared using such monomer it can be seen from Fig. 6 and Fig. 7 is with higher
Glass transition temperature, and decomposition temperature is up to 405 DEG C, has superior heat resistance performance, therefore can be used as high temperature resistant of new generation
Polyarylether material.
Description of the drawings
Fig. 1 is the nucleus magnetic hydrogen spectrum figure with the active double fluorine monomers of necleophilic reaction prepared by the embodiment of the present invention 1；
It can be seen from the figure that H1(hydrogen i.e. on methoxyl group) chemical shift is located at 3.85-3.90ppm；Due to methoxyl group
Electron donation it is strong, cause chemical shift to be moved to High-Field, therefore the H on the phenyl ring of methoxyl group ortho position2Positioned at 7.13-
7.20ppm；Chemical shift is that the corresponding hydrogen of 7.41-7.50ppm is H3, the hydrogen that chemical shift is 8.44-8.60ppm is H5With
H6；Since the electron-withdrawing ability of nitrogen-atoms is stronger, chemical shift is caused to be moved to low field, therefore H4Chemical shift be located at 8.68-
8.71ppm.To sum up, each hydrogen has good ownership, which is successfully prepared.
Fig. 2 is the infrared spectrum with the active double fluorine monomers of necleophilic reaction prepared by the embodiment of the present invention 1；
It can be seen from the figure that wave number is located at 1607-1506cm-1Absorption peak correspond to compound in C=C and C=
N keys, 1020cm-1The absorption peak at place corresponds to Ar-O-C keys.Infrared spectrum from demonstrate on the other hand target compound by
Work(synthesizes.
Fig. 3 is the DSC curve figure with the active double fluorine monomers of necleophilic reaction prepared by the embodiment of the present invention 1；
It can be seen from the figure that only there are one sharp endothermic peaks to exist in entire Range of measuring temp, which corresponds to
Temperature be exactly the compound fusing point.Analyze the compound 242 DEG C of fusing point, 5 DEG C of melting range.
Fig. 4 is the nucleus magnetic hydrogen spectrum figure of the polyarylether bpy-6AF containing connection pyrimidine structure prepared by the present invention；
It can be seen from the figure that H3Chemical shift 8.63-8.85ppm；It is positioned at the hydrogen at fluorine atom ortho position in monomer
H1, chemical shift to High-Field move, 7.05-7.65ppm is become by 8.44-8.60ppm, illustrates that fluorine atom is reacted；Change
Displacement study is that the hydrogen of 7.60-7.75ppm corresponds to the H in bisphenol AF structure7, and other hydrogen also have good ownership, to sum up
Polyarylether bpy-6AF is successfully prepared.
Fig. 5 is the infrared spectrum of the polyarylether bpy-6AF containing connection pyrimidine structure prepared by the present invention；
It can be seen from the figure that wave number is 1246cm-1Absorption vibration peak belong to Ar-O-Ar, prove from another point of view
Polyarylether bpy-6AF is successfully prepared.
Fig. 6 is the DSC curve figure of the polyarylether bpy-6AF containing connection pyrimidine structure prepared by the present invention；
It can be seen from the figure that the glass transition temperature of polyarylether bpy-6AF is 242 DEG C, hence it is evident that be higher than 4,4 '-dihalo-s
Benzophenone or 4, the homopolymer of 4 '-dihalo- diphenyl sulphone (DPS)s and bisphenol AF illustrate that polyarylether can be improved by introducing connection pyrimidine structure
Temperature in use.
Fig. 7 is the TGA curve graphs of the polyarylether bpy-6AF containing connection pyrimidine structure prepared by the present invention；
It can be seen from the figure that the initial thermal weight loss of polymer is about at 405 DEG C, 5% thermal weight loss about at 475 DEG C, is said
Bright bpy-6AF has excellent thermal stability.
Specific implementation mode
Embodiment 1：It synthesizes 4,4'- bis--(4- fluorophenyls) -6,6'- two-(4- methoxyphenyls) -2,2'- and joins pyrimidine
The first step is reacted：13.81g is added in equipped with churned mechanically 500mL there-necked flasks to fluoro acetophenone, 13.62g
P-methoxybenzal-dehyde, 9.09g urea, 1.35g copper chlorides, 10.86g trim,ethylchlorosilanes and 150mL acetonitriles, in argon atmospher
Lower temperature rising reflux is enclosed, reacts 8 hours, after the reaction was complete, pours into 800mL deionized waters, is filtered, solid is washed with deionized water 4
Secondary, ethyl alcohol is washed 4 times, and 80 DEG C of vacuum dryings after ethyl alcohol recrystallization obtain yellow crystals 20.28g.
Second step reacts：Product 5.17g, 40mL phosphorus oxychloride of the first step and 0.6mL N,N' dimethyl anilines are added
Enter into 100mL there-necked flasks, magnetic agitation, be warming up to 130 DEG C under protection of argon gas, after reacting 6 hours, steams 30mL trichlorines
Oxygen phosphorus is cooled to room temperature, in discharging to 400mL ice water, filters, solid is washed with deionized water 5 times, and ethyl alcohol recrystallization obtains yellow
The chloro- 4- of crystal 3.98g, i.e. 2- (4- fluorophenyls) -6- (4- methoxyphenyls) pyrimidine.
Three-step reaction：Under argon atmosphere, 0.99g Dehydrated nickel chlorides, 7.88g triphenylphosphines and 0.7g zinc powders are added
Enter into anhydrous DMF, is stirred at 55 DEG C after sixty minutes, it is phonetic that 2- chloro- 4- (4- fluorophenyls) -6- (4- methoxyphenyls) are added dropwise
The DMF solution (2.36g is dissolved in 20mLDMF) of pyridine, reaction 7 hours, the mixed system of discharging to ammonium hydroxide and trichlorine after being added dropwise completely
In, liquid separation, trichlorine layer is washed with deionized water 3 times, and revolving, solid vacuum drying, column chromatography for separation is spin-dried for, obtains light yellow solid
Body 1.48g, i.e. 4,4'- bis--(4- fluorophenyls) -6,6'- bis--(4- methoxyphenyls) -2,2'- joins pyrimidine.
Embodiment 2：It synthesizes 4,4'- bis--(4- fluorophenyls) -6,6'- diphenyl -2,2'- and joins pyrimidine
The first step is reacted：13.81g is added in equipped with churned mechanically 500mL there-necked flasks to fluoro acetophenone, 10.62g
To phenyl benzaldehyde, 9.09g urea, 1.35g copper chlorides, 10.86g trim,ethylchlorosilanes and 150mL acetonitriles, in argon atmosphere
Lower temperature rising reflux is reacted 8 hours, after the reaction was complete, is poured into 800mL deionized waters, is filtered, and solid is washed with deionized water 4
Secondary, ethyl alcohol is washed 4 times, and 80 DEG C of vacuum dryings after acetone recrystallization obtain yellow crystals 20.28g.
Second step reacts：Product 4.65g, 40mL phosphorus oxychloride of the first step and 0.6mL N,N' dimethyl anilines are added
Enter into 100mL there-necked flasks, magnetic agitation, be warming up to 130 DEG C under protection of argon gas, after reacting 6 hours, steams 30mL trichlorines
Oxygen phosphorus is cooled to room temperature, in discharging to 400mL ice water, filters, solid is washed with deionized water 5 times, and acetone recrystallization obtains yellow
The chloro- 4- of crystal 3.56g, i.e. 2- (4- fluorophenyls) -6- phenyl pyrimidines.
Three-step reaction：Under argon atmosphere, 0.99g Dehydrated nickel chlorides, 7.88g triphenylphosphines and 0.7g zinc powders are added
Enter into anhydrous DMF, is stirred at 55 DEG C after sixty minutes, the DMF solution of 2- chloro- 4- (4- fluorophenyls) -6- phenyl pyrimidines is added dropwise
(2.12g is dissolved in 25mLDMF), reaction 7 hours after being added dropwise completely, in discharging to ammonium hydroxide and the mixed system of trichlorine, liquid separation, trichlorine
Layer is washed with deionized water 3 times, rotates, and solid vacuum drying, column chromatography for separation is spin-dried for, and obtains solid 1.26g, i.e. 4,4'- bis--
(4- fluorophenyls) -6,6'- diphenyl -2,2'- joins pyrimidine.
Embodiment 3：It synthesizes 4,4'- bis--(4- fluorophenyls) -6,6'- two-(4- phenyls) -2,2'- and joins pyrimidine
The first step is reacted：13.81g is added in equipped with churned mechanically 500mL there-necked flasks to fluoro acetophenone, 18.22g
To phenyl benzaldehyde, 9.09g urea, 1.35g copper chlorides, 10.86g trim,ethylchlorosilanes and 150mL acetonitriles, in argon atmosphere
Lower temperature rising reflux is reacted 8 hours, after the reaction was complete, is poured into 800mL deionized waters, is filtered, and solid is washed with deionized water 4
Secondary, ethyl alcohol is washed 4 times, and 80 DEG C of vacuum dryings after acetone recrystallization obtain crystal 27.36g.
Second step reacts：Product 5.97g, 40mL phosphorus oxychloride of the first step and 0.6mL N,N' dimethyl anilines are added
Enter into 100mL there-necked flasks, magnetic agitation, be warming up to 130 DEG C under protection of argon gas, after reacting 6 hours, steams 30mL trichlorines
Oxygen phosphorus is cooled to room temperature, in discharging to 400mL ice water, filters, solid is washed with deionized water 5 times, and acetone recrystallization obtains crystal
The chloro- 4- of 5.37g, i.e. 2- (4- fluorophenyls) -6- (4- phenyls) pyrimidine.
Three-step reaction：Under argon atmosphere, 0.99g Dehydrated nickel chlorides, 7.88g triphenylphosphines and 0.7g zinc powders are added
Enter into anhydrous DMF, is stirred at 55 DEG C after sixty minutes, 2- chloro- 4- (4- fluorophenyls) -6- (4- phenyls) pyrimidine is added dropwise
DMF solution (2.71g is dissolved in 20mLDMF), reaction 7 hours after being added dropwise completely, discharging in ammonium hydroxide and the mixed system of trichlorine,
Liquid separation, trichlorine layer are washed with deionized water 3 times, and revolving, solid vacuum drying, column chromatography for separation is spin-dried for, and obtains shallow solid 1.65g,
That is 4,4'- bis--(4- fluorophenyls) -6,6'- two-(4- phenyls) -2,2'- joins pyrimidine.
Embodiment 4：It synthesizes 4,4'- bis--(4- fluorophenyls) -6,6'- two-(4- aminomethyl phenyls) -2,2'- and joins pyrimidine
The first step is reacted：13.81g is added in equipped with churned mechanically 500mL there-necked flasks to fluoro acetophenone, 12.01g
P-tolyl aldehyde, 9.09g urea, 1.35g copper chlorides, 10.86g trim,ethylchlorosilanes and 150mL acetonitriles, in argon atmosphere
Lower temperature rising reflux is reacted 8 hours, after the reaction was complete, is poured into 800mL deionized waters, is filtered, and solid is washed with deionized water 4
Secondary, ethyl alcohol is washed 4 times, and 80 DEG C of vacuum dryings after ethyl alcohol recrystallization obtain yellow crystals 20.36g.
Second step reacts：Product 4.63g, 40mL phosphorus oxychloride of the first step and 0.6mL N,N' dimethyl anilines are added
Enter into 100mL there-necked flasks, magnetic agitation, be warming up to 130 DEG C under protection of argon gas, after reacting 6 hours, steams 30mL trichlorines
Oxygen phosphorus is cooled to room temperature, in discharging to 400mL ice water, filters, solid is washed with deionized water 5 times, and ethyl alcohol recrystallization obtains yellow
The chloro- 4- of crystal 5.37g, i.e. 2- (4- fluorophenyls) -6- (4- aminomethyl phenyls) pyrimidine.
Three-step reaction：Under argon atmosphere, 0.99g Dehydrated nickel chlorides, 7.88g triphenylphosphines and 0.7g zinc powders are added
Enter into anhydrous DMF, is stirred at 55 DEG C after sixty minutes, 2- chloro- 4- (4- fluorophenyls) -6- (4- aminomethyl phenyls) pyrimidine is added dropwise
DMF solution (2.24g is dissolved in 20mLDMF), reaction 7 hours after being added dropwise completely, discharging in ammonium hydroxide and the mixed system of trichlorine,
Liquid separation, trichlorine layer are washed with deionized water 3 times, and revolving, solid vacuum drying, column chromatography for separation is spin-dried for, and obtains light yellow solid
1.25g, i.e. 4,4'- bis--(4- fluorophenyls) -6,6'- bis--(4- aminomethyl phenyls) -2,2'- joins pyrimidine
Embodiment 5：It synthesizes 4,4'- bis--(4- fluorophenyls) -6,6'- two-(4- nitrobenzophenones) -2,2'- and joins pyrimidine
The first step is reacted：13.81g is added in equipped with churned mechanically 500mL there-necked flasks to fluoro acetophenone, 15.10g
Paranitrobenzaldehyde, 9.09g urea, 1.35g copper chlorides, 10.86g trim,ethylchlorosilanes and 150mL acetonitriles, in argon atmosphere
Lower temperature rising reflux is reacted 8 hours, after the reaction was complete, is poured into 800mL deionized waters, is filtered, and solid is washed with deionized water 4
Secondary, ethyl alcohol is washed 4 times, and 80 DEG C of vacuum dryings after acetone recrystallization obtain yellow crystals 24.66g.
Second step reacts：Product 5.43g, 40mL phosphorus oxychloride of the first step and 0.6mL N,N' dimethyl anilines are added
Enter into 100mL there-necked flasks, magnetic agitation, be warming up to 130 DEG C under protection of argon gas, after reacting 6 hours, steams 30mL trichlorines
Oxygen phosphorus is cooled to room temperature, in discharging to 400mL ice water, filters, solid is washed with deionized water 5 times, and acetone recrystallization obtains yellow
The chloro- 4- of crystal 5.13g, i.e. 2- (4- fluorophenyls) -6- (4- nitrobenzophenones) pyrimidine.
Three-step reaction：Under argon atmosphere, 0.99g Dehydrated nickel chlorides, 7.88g triphenylphosphines and 0.7g zinc powders are added
Enter into anhydrous DMF, is stirred at 55 DEG C after sixty minutes, 2- chloro- 4- (4- fluorophenyls) -6- (4- nitrobenzophenones) pyrimidine is added dropwise
DMF solution (2.47g is dissolved in 20mLDMF), reaction 7 hours after being added dropwise completely, discharging in ammonium hydroxide and the mixed system of trichlorine,
Liquid separation, trichlorine layer are washed with deionized water 3 times, and revolving, solid vacuum drying, column chromatography for separation is spin-dried for, and obtains light yellow solid
1.45g, i.e. 4,4'- bis--(4- fluorophenyls) -6,6'- bis--(4- nitrobenzophenones) -2,2'- joins pyrimidine
Embodiment 6：Polyarylether bpy-6AF of the synthesis containing connection pyrimidine structure
(4,4'- bis--(4- fluorophenyls) -6,6'- two-(4- methoxyl groups are put into equipped with churned mechanically 25mL there-necked flasks
Phenyl) -2,2'- connection pyrimidine 1.6758g (0.003mol), bisphenol AF 1.0087g (0.003mol), potassium carbonate 0.4975g
(0.0036mol), solvent sulfolane 6.5mL, toluene 5mL are azeotropy dehydrant.It is reacted under protection of argon gas, 155 DEG C of bands
Toluene is evaporated off after 3 hours in water, is warming up to 220 DEG C and reacts 6 hours, discharges in deionized water, obtain strip solid, use deionization
Water and ethyl alcohol wash each 5 times, 80 DEG C of vacuum dryings, obtain the polyarylether bpy-6AF that main chain contains connection pyrimidine structure.
Embodiment 7：The polyarylether bpy-PES-80 of double fluorine monomer contents 80% of the synthesis containing connection pyrimidine structure
By in embodiment 7 (4,4'- bis--(4- fluorophenyls) -6,6'- two-(4- methoxyphenyls) -2,2'- joins pyrimidine
Dosage is changed to 1.3406g (0.0024mol), and 4,4 '-difluorodiphenyl sulfone 0.1526g (0.0006mol), bisphenol AF and carbonic acid is added
Potassium feeds intake constant, i.e., the molar ratio that novel double fluorine monomers account for all double fluorine monomers becomes 0.8, and other conditions are constant, repeats real
Example 2 is applied, another polyarylether bpy-PES-80 is obtained.
Embodiment 8：Polyarylether bpy-NO of the synthesis containing connection pyrimidine structure2-6AF
(4,4'- bis--(4- fluorophenyls) -6,6'- two-(4- nitrobenzenes are put into equipped with churned mechanically 25mL there-necked flasks
Base) -2,2'- connection pyrimidine 1.7656g (0.003mol), bisphenol AF 1.0087g (0.003mol), potassium carbonate 0.4975g
(0.0036mol), solvent sulfolane 6.5mL, toluene 5mL are azeotropy dehydrant.It is reacted under protection of argon gas, 155 DEG C of bands
Toluene is evaporated off after 3 hours in water, is warming up to 220 DEG C and reacts 6 hours, discharges in deionized water, obtain strip solid, use deionization
Water and ethyl alcohol wash each 5 times, 80 DEG C of vacuum dryings, obtain the polyarylether bpy-NO that main chain contains connection pyrimidine structure2-6AF。
Embodiment 9：The polyarylether bpy-NO of double fluorine monomer contents 80% of the synthesis containing connection pyrimidine structure2-PES-80
By (the use of 4,4'- bis--(4- fluorophenyls) -6,6'- two-(4- nitrobenzophenones) -2,2'- connection pyrimidines in embodiment 8
Amount is changed to 1.4125g (0.0024mol), and 4,4 '-difluorodiphenyl sulfone 0.1526g (0.0006mol), bisphenol AF and potassium carbonate is added
It feeds intake constant, i.e., the molar ratio that novel double fluorine monomers account for all double fluorine monomers becomes 0.8, and other conditions are constant, repeats to implement
Example 2 obtains another polyarylether bpy-NO2-PES-80。
Embodiment 10：The preparation of other polymers
In embodiment 6 and embodiment 8, with hydroquinone, 4,4 '-'-biphenyl diphenols, 4,4 '-dihydroxydiphenylsulisomers, 4,4 '-
Dihydroxy benaophenonel or bisphenol-A replace bisphenol AF；With (4,4'- bis--(4- fluorophenyls) -6,6'- two-(4-R bases phenyl) -2,
2'- joins pyrimidine (R H, CH3And C6H5One kind in (phenyl)) replace (4,4'- bis--(4- fluorophenyls) -6,6'- two-(4- first
Phenyl) -2,2'- connection pyrimidines.The main chain that counter structure can equally be made contains the polyarylether of connection pyrimidine structure.
In embodiment 7 and embodiment 9, with 4,4 '-difluoro benzophenones, 4,4 '-dichloro benzophenones, 4,4 '-dichloros
Diphenyl sulphone (DPS) replaces 4,4 '-difluorodiphenyl sulfones；With hydroquinone, 4,4 '-'-biphenyl diphenols, 4,4 '-dihydroxydiphenylsulisomers, 4,4 '-two
Dihydroxy benaophenonel or bisphenol-A replace bisphenol AF.The main chain that counter structure can equally be made contains the poly- virtue of connection pyrimidine structure
Ether.
Claims (5)
1. one kind has the active double fluorine monomers of necleophilic reaction, structural formula as follows：
Wherein, R H, CH3、OCH3、NO2、C6H5One kind in (phenyl).
2. a kind of preparation method with the active double fluorine monomers of necleophilic reaction described in claim 1, its step are as follows：
(1) under atmosphere of inert gases, using to fluoro acetophenone, to R benzaldehydes and urea as reactant, trim,ethylchlorosilane and
Copper chloride is catalyst, and acetonitrile is solvent, and mixing under stiring is warming up to reflux, reacts 6~12 hours；Then discharging to go from
It in sub- water, and is washed with deionized water 3~6 times, ethyl alcohol is washed 3~6 times, and it is phonetic to be recrystallized to give 6- (4- phenyl) -4- (4-R bases phenyl)
Pyridine -2 (1 hydrogen) -one；Wherein to fluoro acetophenone, to the molar ratio of R benzaldehydes, urea, copper chloride and trim,ethylchlorosilane
It is 1：0.9~1.1：1.2~3：0.05~0.5：0.9~1.1；Every mole to fluoro acetophenone 500~3000mL of acetonitrile；
(2) using 6- (4- phenyl) -4- (4-R bases phenyl) pyrimidine -2 (1 hydrogen) -one and phosphorus oxychloride as reactant, N, N'- dimethyl
Aniline is catalyst, is mixed under inert gas shielding and magnetic agitation；90~170 DEG C are warming up to, reaction is steamed after 3~9 hours
Go out most of phosphorus oxychloride, be cooled to room temperature, be subsequently poured into ice water, yellow solid is precipitated, filter, solid is washed with deionized water
3~8 times；It is recrystallized to give the chloro- 4- of 2- (4- fluorophenyls) -6- (4-R bases phenyl) pyrimidine；Wherein, 6- (4- phenyl) -4- (4-R bases
Phenyl) pyrimidine -2 (1 hydrogen) -one, phosphorus oxychloride and N,N' dimethyl aniline amount ratio be 1g：3~10mL：0.02~0.2mL；
(3) under atmosphere of inert gases, Dehydrated nickel chloride, triphenylphosphine and zinc powder are added to anhydrous DMF (N, N- dimethyl methyl
Amide) in, after being stirred 20~120 minutes at 40~70 DEG C, 2- chloro- 4- (4- fluorophenyls) -6- (4-R bases phenyl) pyrimidine is added dropwise
DMF solution, be added dropwise completely after reaction 3~9 hours；It discharges into the mixed system of ammonium hydroxide and chloroform, liquid separation, three chloromethanes
Alkane layer is washed with water 2~6 times, and revolving, solid vacuum drying, column chromatography for separation is spin-dried for, and obtains 4,4'- bis--(4- fluorophenyls) -6,
6'- bis--(4-R bases phenyl) -2,2'- joins pyrimidine；Wherein Dehydrated nickel chloride, triphenylphosphine, zinc powder and 2- chloro- 4- (4- fluorobenzene
Base) -6- (4-R bases phenyl) pyrimidine molar ratio be 1：3~8：1~2：0.5~2.
A kind of there are the active double fluorine monomers of necleophilic reaction to contain connection pyrimidine structure preparing main chain 3. described in claim 1
The structural formula that application in polyarylether, wherein main chain contain the polyarylether of connection pyrimidine structure is as follows,
Wherein, 0<M≤1, n are positive integer, repeateding unit number, 0<n<200；
For
Y is
R is H, CH3、OCH3、NO2、C6H5One kind in (phenyl).
4. as claimed in claim 3 a kind of there are the active double fluorine monomers of necleophilic reaction to contain connection pyrimidine structure preparing main chain
Polyarylether in application, it is characterised in that：It is by 4,4'- bis--(4- fluorophenyls) -6,6'- two-(4-R bases phenyl) -2,2'-
Connection pyrimidine, double halogen monomers and biphenol monomer are added to the container as reactant, wherein 4,4'- bis--(4- fluorophenyls) -6,6'- bis- -
The dosage molar ratio that (4-R bases phenyl) -2,2'- joins pyrimidine, biphenol monomer and double halogen monomers is m：(1-m)：1,0<m≤1；It is added
The catalyst of double 1.1~1.2 times of moles of halogen monomer, be added solvent, make reaction system include catalyst solid content be 15~
40%, add the azeotropy dehydrant of solvent volume 20%~90%；Under inert atmosphere protection, mechanical agitation is warming up to altogether
Dehydrating agent reflux is boiled, reacts 2~6 hours, steams azeotropy dehydrant, being warming up to 170~220 DEG C, the reaction was continued 5~12 hours；Go out
Expect and obtain strip solid in deionized water, washed 3~6 times with deionized water and ethyl alcohol, vacuum drying obtains main chain pyrimidine containing connection
The polyarylether of structure.
5. as claimed in claim 4 a kind of there are the active double fluorine monomers of necleophilic reaction to contain connection pyrimidine structure preparing main chain
Polyarylether in application, it is characterised in that：Azeotropy dehydrant is toluene or dimethylbenzene；Solvent is dimethyl sulfoxide (DMSO), ring
Fourth sulfone (TMS) or N-Methyl pyrrolidone (NMP)；Double halogen monomers are 4,4 '-dihalo- benzophenone or 4,4 '-dihalo- diphenyl sulphone (DPS)s,
Halogen is fluorine or chlorine；Biphenol monomer is hydroquinone, 4,4 '-'-biphenyl diphenols, 4,4 '-dihydroxydiphenylsulisomers, 4,4 '-dihydroxy two
Benzophenone, bisphenol-A or bisphenol AF；Catalyst is one or both of potassium carbonate, sodium carbonate, cesium carbonate.
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