CN105646260A - Diacid monomer containing diphenylamine-fluorene, preparation method and application thereof for preparing polyamide - Google Patents
Diacid monomer containing diphenylamine-fluorene, preparation method and application thereof for preparing polyamide Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C229/52—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
- C07C229/54—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton with amino and carboxyl groups bound to carbon atoms of the same non-condensed six-membered aromatic ring
- C07C229/60—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton with amino and carboxyl groups bound to carbon atoms of the same non-condensed six-membered aromatic ring with amino and carboxyl groups bound in meta- or para- positions
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
- C07C227/18—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
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- 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/32—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from aromatic diamines and aromatic dicarboxylic acids with both amino and carboxylic groups aromatically bound
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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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/50—Physical properties
- C08G2261/54—Physical properties electrochromatic
Abstract
The invention belongs to the technical field of organic compounds, and relates to a diacid monomer containing a diphenylamine-fluorene structure, a preparation method and application thereof for preparing polyamide with the electrochromism performance. The synthetic method comprises the two steps that 2-aminofluorene with a substituent group at the bit 9 and p-fluorobenzonitrile are subjected to a nucleophilic substitution reaction under the effect of cesium fluoride to obtain a nitroamiline compound containing the diphenylamine-fluorene structure; then, under the effect of potassium hydroxide, basic hydrolysis is performed to obtain the diacid monomer containing the diphenylamine-fluorene structure. The diacid monomer and various diamine monomers are subjected to a reaction to obtain polyamide with the electrochromism performance. Due to the specific structure of the diacid monomer, the obtained polymer has the good solubility and unique photoelectric property; the diacid monomer and the polyamide prepared by the diacid monomer have the huge application prospect in the fields such as electrochromism.
Description
Technical field
The invention belongs to organic compound technical field, be specifically related to a class and contain diphenylamines-fluorene structured diacid monomer, preparation method and in preparation, there is the application in the polyamide of electrochromic property.
Background technology
The polyamide of fragrance has the process based prediction model of excellence. But, due to the skeleton of its rigidity and the strong interaction of molecule interchain, cause that it has the character of infusibility indissoluble, thus limiting its range of application. The main chain of polyamide introducing the group of the non-co-planar of large volume, it is possible to effectively stop the accumulation of strand, increasing free volume, thus increasing structure adaptability and film property.
Polyamide skeleton introduces the trianilino group of propeller shape, it is possible to while not losing hot property, increase structure adaptability and film property; And, triphenylamine easily forms stable single radical cation, in the process along with the change of color, it is possible to increase polyamide application (HsiaoSH, LiouGS in electrochromism field, KungYC, ChangYM, JournalofPolymerScience:PartA:PolymerChemistry, 2010,48,2798-2809).
But, integrate polyamide of less types of several functions, therefore, the diacid monomer containing triphenylamine units of design synthesizing new, and prepared polyamide by it and become very necessary.
Summary of the invention
It is an object of the invention to provide containing the novel diacid monomer of diphenylamines-fluorene structured, preparation method and the application in preparing polyamide thereof.
Diacid monomer containing diphenylamines-fluorene structured of the present invention, has the structure shown in formula I:
R in described formula I1��R2Identical or differ, for hydrogen, the alkyl of carbon number 1��10, aryl.
Diacid monomer preparation method containing diphenylamines-fluorene structured of the present invention, it specifically comprises the following steps that
1) No. 9 positions being 1:2��3:2��3 with mol ratio there is the 2-aminofluorene of substituent group, to fluorobenzonitrile, cesium fluoride for raw material, addition solvent makes the total solid content of reaction system be 10%��30%, under stirring, nitrogen protection, react 6��48h in 80��200 DEG C;After cooling, discharging is in frozen water, and crude product with water is washed 2��5 times, glacial acetic acid recrystallization, obtains the dicyano compound containing diphenylamines-fluorene structured;
2) by step 1) in the product that obtains and potassium hydroxide add in reaction vessel with the ratio of mol ratio 1:10��30, add the second alcohol and water that volume ratio is 1��3:1, making reaction system total solid content is 5%��30%, under agitation, reacts 30��120h in reflux temperature; After cooling, regulating pH=2��4 with concentrated hydrochloric acid, filter, the powder of gained washes with water 2��5 times, obtains the diacid monomer containing diphenylamines-fluorene structured of the present invention; The structure of gained compound is demonstrated through nuclear-magnetism test.
Its synthetic reaction formula is as follows:
Wherein, the substituent R in 2-aminofluorene1��R2Identical or differ, for hydrogen, the alkyl of carbon number 1��10, aryl.
Step 1) in described solvent can be more than one in dimethyl sulfoxide, DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone.
Step 2) described in reaction vessel include magnetic stir bar and condensing tube.
Step 2) described in the concentration of concentrated hydrochloric acid be 6��12mol/L.
The diacid monomer containing diphenylamines-fluorene structured of the present invention application in preparing polyamide, is with this diacid monomer for reactant, prepares polyamide from different diamine monomer reactions.
Of the present invention containing the method that diphenylamines-fluorene structured diacid monomer prepares polyamide for reactant to be: with mol ratio be 1:1 diamine monomer and diacid monomer containing diphenylamines-fluorene structured for raw material, with N-Methyl pyrrolidone for solvent, reaction system total solid content is 15%��25%, then it is added thereto to and the triphenyl phosphite that diacid monomer mol ratio is 3��5:1 and 4��7:1 and pyridine, add and diacid monomer and diamine monomer quality and than the calcium chloride being 0.2��0.4:1, under nitrogen protection, 3��5h is reacted at 100��120 DEG C, product discharge is in methanol, again successively with ethanol, water and alcohol reflux washing, obtain polyamide powder after drying.
Wherein, diamine monomer be p-phenylenediamine, m-diaminobenzene., benzidine, 4,4 '-diaminodiphenyl ether, 2,2-double; two (4-aminophenyl) HFC-236fa, 4,4 '-diaminourea-3,3 '-dimethyl diphenyl, 1,1-bis-(4-aminophenyl) hexamethylene, 2,7 diamin of luorene, 9, double; two (4-aminophenyl) fluorenes of 9-, double; two (4-aminophenyl)-9, the 9-dimethyl fluorene of N, N-.
Polyamide synthetic reaction formula is as follows:
Wherein n is the integer between 10��70.
Ar is remaining group after aromatic diamine removal end amido, it is possible to but it is not limited to the one having in structure shown in formula 1��formula 10:
The mensuration of the electrochromic property of polyamide prepared by the present invention is adopted with the following method: polyamide powder is dissolved in N, N-dimethyl acetylamide is configured to the polymer solution that concentration is 5��20mg/mL, drop coating is on ito glass plate, drying obtains polyamide film (film thickness is 1��10 ��m) as working electrode, platinum filament is as to electrode, Ag/AgCl is as reference electrode, and the acetonitrile containing 0.1M tetrabutylammonium perchlorate (TBAP) is as electrolyte solution. Applied the voltage being incremented by by electrochemical workstation, observe the change of its color, in the process, detect the change of its absorption spectrum with ultraviolet-visual spectrometer, as shown in Figure 8, Figure 9.
The diacid monomer of the present invention contains diphenylamines-fluorene structured, prepare polyamide with it for monomer and can effectively stop the accumulation of strand, increase free volume, weaken the interaction force of molecule interchain, while keeping polyamide hot property, its dissolubility and film property can be improved; And the structure of this diphenylamines-fluorenes, it is possible to effectively stop the triphenylamine generation tail coupling reaction to tail, improve its electrochromic stability.In sum, containing diphenylamines-fluorene structured diacid monomer and in fields such as electrochromism, be there is huge application prospect by the polyamide of its synthesis.
Accompanying drawing explanation
Fig. 1: double; two (4-carboxyl phenyl)-9,9-dimethyl fluorene hydrogen nuclear magnetic spectrogram and carbon nuclear magnetic spectrograms of N, N-of embodiment 1 preparation, as can be seen from the figure the chemical shift ownership of H atom and C atom is clearly, and one_to_one corresponding, it was demonstrated that the structure of gained diacid;
Fig. 2: double; two (4-cyano-phenyl)-9,9-dimethyl fluorene infrared spectrum (a) of N, N-of embodiment 1 preparation, 2220cm-1Vibration absorption peak for C �� N; Double; two (4-carboxyl phenyl)-9,9-dimethyl fluorene infrared spectrum (b) of N, N-, 2700-3400cm-1For the vibration absorption peak of O-H, 1674cm-1For the vibration absorption peak of C=O, this figure illustrates successfully to have prepared dicyano monomer and dicarboxyl monomer.
Fig. 3: the infrared spectrum of 9,9-double; two (4-aminophenyl) fluorenes type polyamide of embodiment 7 preparation, 3413cm-1��1666cm-1Place is the characteristic oscillation absworption peak of amido link, it was demonstrated that the structure of gained polyamide.
Fig. 4: the DSC curve figure of 2,2-double; two (4-aminophenyl) HFC-236fa type polyamide of embodiment 6 preparation, glass transition temperature is 312 DEG C, and this figure illustrates that it has good hot property.
Fig. 5: the TGA curve chart of 9,9-double; two (4-aminophenyl) fluorenes type polyamide of embodiment 7 preparation, under nitrogen atmosphere, 10% weightless temperature is 496 DEG C; Under air atmosphere, 10% weightless temperature is 489 DEG C, illustrates that it has good heat-resistant stability.
Fig. 6: the cyclic voltammetry curve figure, this figure of paraphenylene diamine's polyamide of embodiment 4 preparation illustrate that its oxidation-reduction process is reversible.
Fig. 7: the cyclic voltammetry curve figure, this figure of double; two (4-aminophenyl)-9,9-dimethyl fluorene type polyamide of N, N-of embodiment 8 preparation illustrate that gained polyamide has two pairs of reversible oxidoreduction peaks.
Fig. 8: the 9 of embodiment 7 preparation, the electrochromism spectrogram of double; two (4-aminophenyl) the fluorenes type polyamide of 9-, when applied voltage rises to 1.3V from 0V, 356nm place absworption peak is gradually lowered, there is new absworption peak in 418nm, 890nm place, and being gradually increased along with the increase of applied voltage, the color from pale yellow complexion changed of thin film is bottle green simultaneously.
Fig. 9: the N of embodiment 8 preparation, double; two (the 4-aminophenyl)-9 of N-, the electrochromism spectrogram of 9-dimethyl fluorene type polyamide, when applied voltage rises to 0.9V from 0V, 361nm place absorption peak strength is gradually lowered, the absorption peak strength at 860nm place gradually rises, and the color of thin film becomes light green color from faint yellow simultaneously; When applied voltage rises to 1.3V from 0.9V, 361nm place absorption peak strength is gradually lowered, there is new absworption peak in 568nm source, and the increase along with applying electrical potential, absorption peak strength gradually rises, and new absworption peak occurs in 890nm source, and along with the increase of applying electrical potential, absorption peak strength is gradually lowered, and thin film color is from green to Lycoperdon polymorphum Vitt simultaneously.
Detailed description of the invention
The preparation of double; two (4-the carboxyl phenyl)-9,9-dimethyl fluorene of embodiment 1:N, N-
The first step is reacted: add the 2-amino-9 of 10.0g (48mmol) in equipped with churned mechanically 250mL three-neck flask; 9-dimethyl fluorene, 11.6g (96mmol) the cesium fluoride to fluorobenzonitrile, 14.6g (96mmol); add the dimethyl sulfoxide of 100mL as solvent; under stirring, nitrogen protection; at 170 DEG C, react 18h. After cooling, discharging is in frozen water, and crude product with water is washed 2 times, glacial acetic acid recrystallization, obtains double; two (4-cyano-phenyl)-9,9-dimethyl fluorene crystal 13.2g of N, N-of buff, productivity 67%.
Second step react: to equipped with magnetic stir bar, condensing tube 100mL three-neck flask in add the 8g first step prepare N, double; two (the 4-cyano-phenyl)-9 of N-, 9-dimethyl fluorene powder, 16.0g potassium hydroxide, add 20mL ethanol and 20mL water as solvent, heating, to backflow, continues return stirring 72h. After cooling, regulate pH close to 3 with concentrated hydrochloric acid (6mol/L), filter, the powder of gained washes with water 2 times, obtains double; two (the 4-carboxyl phenyl)-9 of flaxen N, N-, 9-dimethyl fluorene powder 4.1g, productivity is 47%, and products therefrom structural formula is as shown in Equation 11.
Fig. 1 is double; two (4-carboxyl phenyl)-9,9-dimethyl fluorene hydrogen nuclear magnetic spectrogram and the carbon nuclear magnetic spectrogram of N, N-, therefrom may determine that the compound obtained is double; two (4-carboxyl phenyl)-9, the 9-dimethyl fluorene of N, N-.
The preparation of double; two (4-the carboxyl phenyl)-9,9-diphenylfluorene of embodiment 2:N, N-
The first step is reacted: add the 2-amino-9 of 15.0g (45mmol) in equipped with churned mechanically 250mL three-neck flask; 9-diphenylfluorene, 10.9g (90mmol) the cesium fluoride to fluorobenzonitrile, 13.7g (90mmol); add the dimethyl sulfoxide of 120mL as solvent; under stirring, nitrogen protection; at 170 DEG C, react 26h. After cooling, discharging is in frozen water, and crude product with water is washed 2 times, glacial acetic acid recrystallization, obtains double; two (4-cyano-phenyl)-9,9-diphenylfluorene powder 15.2g of N, N-of buff, productivity 63%.
Second step react: to equipped with magnetic stir bar, condensing tube 100mL three-neck flask in add the 10g first step prepare N, double; two (the 4-cyano-phenyl)-9 of N-, 9-diphenylfluorene powder, 15.7g potassium hydroxide, add 25mL ethanol and 15mL water as solvent, heating, to backflow, continues return stirring 72h. After cooling, regulate pH close to 3 with concentrated hydrochloric acid (6mol/L), filter, the powder of gained washes with water 2 times, obtains double; two (the 4-carboxyl phenyl)-9 of flaxen N, N-, 9-diphenylfluorene powder 5.2g, productivity is 48%, and products therefrom structural formula is as shown in Equation 12.
The preparation of double; two (4-the carboxyl phenyl)-9,9-dihexyl fluorenes of embodiment 3:N, N-
The first step is reacted: add the 2-amino-9 of 15.0g (43mmol) in equipped with churned mechanically 250mL three-neck flask; 9-dihexyl fluorenes, 10.4g (86mmol) the cesium fluoride to fluorobenzonitrile, 13.1g (86mmol); add the dimethyl sulfoxide of 120mL as solvent; under stirring, nitrogen protection; at 170 DEG C, react 26h. After cooling, discharging is in frozen water, and crude product with water is washed 2 times, glacial acetic acid recrystallization, obtains double; two (4-cyano-phenyl)-9,9-dihexyl fluorenes powder 14.4g of N, N-of buff, productivity 61%.
Second step react: to equipped with magnetic stir bar, condensing tube 100mL three-neck flask in add the 10g first step prepare N, double; two (the 4-cyano-phenyl)-9 of N-, 9-dihexyl fluorenes powder, 15.0g potassium hydroxide, add 25mL ethanol and 15mL water as solvent, heating, to backflow, continues return stirring 72h. After cooling, regulate pH close to 3 with concentrated hydrochloric acid (6mol/L), filter, the powder of gained washes with water 2 times, obtains double; two (the 4-carboxyl phenyl)-9 of flaxen N, N-, 9-dihexyl fluorenes powder 4.5g, productivity is 42%, and products therefrom structural formula is as shown in Equation 13.
Double; two (4-the carboxyl phenyl)-9,9-dimethyl fluorene of embodiment 4:N, N-is polymerized with p-phenylenediamine prepares polyamide
To equipped with magneton, import and export of nitrogen, thermometer three-neck flask in pass into nitrogen, add 0.4495g (1mmol) N that embodiment 1 prepares, double; two (the 4-carboxyl phenyl)-9 of N-, the p-phenylenediamine of 9-dimethyl fluorene and 0.1081g (1mmol), add the N-Methyl pyrrolidone of 2.5mL, add 1.0mL triphenyl phosphite and 0.5mL pyridine, add the CaCl of 0.15g2, heat to 120 DEG C of reaction 3h.After completion of the reaction, being cooled to room temperature, discharging obtains product as yellow powder to methanol, and alcohol reflux washes 30min, water backflow washes one time, and alcohol reflux washes 30min, vacuum drying oven 100 DEG C drying, obtaining paraphenylene diamine's polyamide, be labeled as 5a, quality is 0.5016g.
Polyamide is prepared in double; two (4-the carboxyl phenyl)-9,9-dimethyl fluorene of embodiment 5:N, N-and the polymerization of 4,4 '-diaminodiphenyl ether
To equipped with magneton, import and export of nitrogen, thermometer three-neck flask in pass into nitrogen, add 0.4495g (1mmol) N that embodiment 1 prepares, double; two (the 4-carboxyl phenyl)-9 of N-, the 4 of 9-dimethyl fluorene and 0.2002g (1mmol), 4 '-diaminodiphenyl ether, add the N-Methyl pyrrolidone of 2.5mL, add 1.0mL triphenyl phosphite and 0.5mL pyridine, add the CaCl of 0.15g2Heat to 120 DEG C of reaction 3h, reacting the complete room temperature that is cooled to, discharging obtains product as yellow powder to methanol, and alcohol reflux washes 30min, water backflow washes one time, alcohol reflux washes 30min, vacuum drying oven 100 DEG C drying, obtains diaminodiphenyl ether type polyamide, being labeled as 5b, quality is 0.5837g.
Double; two (4-the carboxyl phenyl)-9,9-dimethyl fluorene of embodiment 6:N, N-is polymerized with double; two (4-aminophenyl) HFC-236fa of 2,2-and prepares polyamide
To equipped with magneton, import and export of nitrogen, thermometer three-neck flask in pass into nitrogen, add 0.4495g (1mmol) N that embodiment 1 prepares, the 2 of double; two (4-the aminophenyl)-4-piperidines aniline of N-and 0.3343g (1mmol), double; two (4-aminophenyl) HFC-236fa of 2-, add the N-Methyl pyrrolidone of 3.0mL, add 1.0mL triphenyl phosphite and 0.5mL pyridine, add the CaCl of 0.2g2Heating to 120 DEG C of reaction 3h, react the complete room temperature that is cooled to, discharging obtains product as yellow powder to methanol, alcohol reflux washes 30min, water backflow washes one time, and alcohol reflux washes 30min, vacuum drying oven 100 DEG C drying, obtain 2, double; two (4-aminophenyl) the HFC-236fa type polyamide of 2-, is labeled as 5c, and quality is 0.7105g.
Double; two (4-the carboxyl phenyl)-9,9-dimethyl fluorene of embodiment 7:N, N-is polymerized with double; two (4-aminophenyl) fluorenes of 9,9-and prepares polyamide
To equipped with magneton, import and export of nitrogen, thermometer three-neck flask in pass into nitrogen, add 0.4495g (1mmol) N that embodiment 1 prepares, double; two (the 4-carboxyl phenyl)-9 of N-, the 9 of 9-dimethyl fluorene and 0.3484g (1mmol), double; two (4-aminophenyl) fluorenes of 9-, add the N-Methyl pyrrolidone of 3.0mL, add 1.0mL triphenyl phosphite and 0.5mL pyridine, add the CaCl of 0.2g2Heating to 120 DEG C of reaction 3h, react the complete room temperature that is cooled to, discharging obtains product as yellow powder to methanol, alcohol reflux washes 30min, water backflow washes one time, and alcohol reflux washes 30min, vacuum drying oven 100 DEG C drying, obtain 9, double; two (4-aminophenyl) the fluorenes type polyamide of 9-, is labeled as 5d, and quality is 0.7172g.
Polyamide is prepared in double; two (4-carboxyl phenyl)-9, the 9-dimethyl fluorene of embodiment 8:N, N-and double; two (4-aminophenyl)-9, the 9-dimethyl fluorene polymerization of N, N-
To equipped with magneton, import and export of nitrogen, thermometer three-neck flask in pass into nitrogen, add 0.4495g (1mmol) N that embodiment 1 prepares, double; two (the 4-carboxyl phenyl)-9 of N-, the N of 9-dimethyl fluorene and 0.3915 (1mmol), double; two (4-aminophenyl)-9, the 9-dimethyl fluorene of N-, adds the N-Methyl pyrrolidone of 3.0mL, add 1.0mL triphenyl phosphite and 0.5mL pyridine, add the CaCl of 0.2g2, heat to 120 DEG C of reaction 3h, react complete and be cooled to room temperature, discharging obtains product as yellow powder to methanol, alcohol reflux washes 30min, and water backflow is washed one time, and alcohol reflux washes 30min, vacuum drying oven 100 DEG C drying, obtain double; two (4-aminophenyl)-9, the 9-dimethyl fluorene type polyamide of N, N-, being labeled as 5e, quality is 0.7577g.
Trianilino group owing to introducing the non-co-planar of large volume in polyamide can effectively stop the accumulation of strand, increasing the free volume of molecule interchain, weakening the interaction force of molecule interchain, thus improving structure adaptability, as shown in table 1. Polyamide 5a-5e, in polar solvent such as NMP, DMAc, DMF, DMSO, all shows good dissolubility. Comparatively speaking, polyamide 5c is at THF, CHCl3Also showing good dissolubility in the solvent that polarity is more weak, this is owing to introducing large volume of-CF in polyamide 5c3Group, reduces the interaction force of molecule interchain further. Because these polyamide have good dissolubility, it is possible to be easily applied as high performance thin film, increase its range of application.
Table 1: the polyamide of embodiment 4��8 preparation dissolubility in 6 kinds of common solvents.
Note:aIt is 10mg/mL for measuring deliquescent solution concentration
++: solvable under room temperature; +: heat solvable; +-: part is solvable;-: heating insoluble polyamide 5a��5e and show good heat stability, hot property data are as shown in table 2.
Table 2: the hot property data of the polyamide of embodiment 4��8 preparation
Note:aHeating rate is 10 DEG C/min, and what scan temperature ranges for 50��350 DEG C, and atmosphere is nitrogen;
bHeating rate is 10 DEG C/min, and what scan temperature ranges for 100��800 DEG C, and atmosphere is nitrogen;
cHeating rate is 10 DEG C/min, and what scan temperature ranges for 100��800 DEG C, and atmosphere is air.
Claims (9)
1. a class contains the diacid monomer of diphenylamines-fluorene structured, and its structural formula is as follows:
R1��R2Identical or differ, it is the alkyl or aryl of 1��10 for hydrogen, carbon number.
2. the preparation method that the class described in claim 1 contains the diacid monomer of diphenylamines-fluorene structured, its step is as follows:
1) No. 9 positions being 1:2��3:2��3 with mol ratio there is the 2-aminofluorene of substituent group, to fluorobenzonitrile, cesium fluoride for raw material, addition solvent makes the total solid content of reaction system be 10%��30%, under stirring, nitrogen protection, react 6��48h in 80��200 DEG C; After cooling, discharging is in frozen water, and crude product with water is washed 2��5 times, glacial acetic acid recrystallization, obtains the dicyano compound containing diphenylamines-fluorene structured;
2) by step 1) in the product that obtains and potassium hydroxide add in reaction vessel with the ratio of mol ratio 1:10��30, add the second alcohol and water that volume ratio is 1��3:1, making reaction system total solid content is 5%��30%, under agitation, reacts 30��120h in reflux temperature; After cooling, regulating pH=2��4 with concentrated hydrochloric acid, filter, the powder of gained washes with water 2��5 times, obtains the diacid monomer containing diphenylamines-fluorene structured, and wherein the structural formula of the 2-aminofluorene that No. 9 positions have substituent group is as follows,
R1��R2Identical or differ, for hydrogen, the alkyl of carbon number 1��10, aryl.
3. the preparation method that a class as claimed in claim 2 contains the diacid monomer of diphenylamines-fluorene structured, it is characterized in that: step 1) in described solvent be dimethyl sulfoxide, N, more than one in dinethylformamide, N,N-dimethylacetamide, N-Methyl pyrrolidone.
4. the preparation method that a class as claimed in claim 2 contains the diacid monomer of diphenylamines-fluorene structured, it is characterised in that: step 2) described in reaction vessel include magnetic stir bar and condensing tube.
5. the preparation method that a class as claimed in claim 2 contains the diacid monomer of diphenylamines-fluorene structured, it is characterised in that: step 2) described in concentrated hydrochloric acid concentration be 6��12mol/L.
6. the diacid monomer that the class described in claim 1 contains diphenylamines-fluorene structured has the application in the polyamide of electrochromic property in preparation.
7. the diacid monomer that a class as claimed in claim 6 contains diphenylamines-fluorene structured has the application in the polyamide of electrochromic property in preparation, it is characterised in that: it is with this diacid monomer for reactant, prepares polyamide with diamine monomer reaction.
8. the diacid monomer that a class as claimed in claim 7 contains diphenylamines-fluorene structured has the application in the polyamide of electrochromic property in preparation, it is characterized in that: with mol ratio be 1:1 diamine monomer and diacid monomer containing diphenylamines-fluorene structured for raw material, with N-Methyl pyrrolidone for solvent, reaction system total solid content is 15%��25%, then it is added thereto to and the triphenyl phosphite that diacid monomer mol ratio is 3��5:1 and 4��7:1 and pyridine, add and diacid monomer and diamine monomer quality and than the calcium chloride being 0.2��0.4:1, under nitrogen protection, 3��5h is reacted at 100��120 DEG C, product discharge is in methanol, again successively with ethanol, water and alcohol reflux washing, obtain polyamide powder after drying.
9. the diacid monomer that a class as claimed in claim 7 or 8 contains diphenylamines-fluorene structured has the application in the polyamide of electrochromic property in preparation, it is characterized in that: diamine monomer be p-phenylenediamine, m-diaminobenzene., benzidine, 4,4 '-diaminodiphenyl ether, 2, double; two (4-aminophenyl) HFC-236fa of 2-, 4,4 '-diaminourea-3,3 '-dimethyl diphenyl, 1,1-bis-(4-aminophenyl) hexamethylene, 2,7-N-2-Fluorenylamine, 9, double; two (4-aminophenyl) fluorenes of 9-or double; two (4-aminophenyl)-9, the 9-dimethyl fluorene of N, N-.
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| CN201610031199.3A CN105646260B (en) | 2016-01-18 | 2016-01-18 | Diacid monomer, preparation method and its application in polyamide is prepared of the fluorenes containing diphenylamines |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018070475A (en) * | 2016-10-26 | 2018-05-10 | 株式会社リコー | Electrochromic compound, electrochromic composition, and electrochromic element |
| CN109491147A (en) * | 2017-09-11 | 2019-03-19 | 夏普株式会社 | The manufacturing method of alignment films, liquid crystal display panel and liquid crystal display panel |
| CN109627212A (en) * | 2018-12-12 | 2019-04-16 | 吉林大学 | A kind of diacid monomer and preparation method thereof and polyamide and preparation method thereof |
| JP2020140053A (en) * | 2019-02-27 | 2020-09-03 | 株式会社リコー | Electrochromic device, display device, lighting control device, electrochromic composition, and cured film |
| CN113388104A (en) * | 2021-07-02 | 2021-09-14 | 黑龙江大学 | Triarylamine polyamide containing fluorenyl directly bonded with triphenylamine, and preparation method and application thereof |
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| CN101114085A (en) * | 2006-07-28 | 2008-01-30 | Jsr株式会社 | Liquid crystal aligning agent, liquid crystal aligning film and liquid crystal display device |
| CN105085281A (en) * | 2015-08-07 | 2015-11-25 | 吉林大学 | Diamine monomer containing diphenylamine-fluorene, preparation method and application of same in polyimide preparation |
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| CN101114085A (en) * | 2006-07-28 | 2008-01-30 | Jsr株式会社 | Liquid crystal aligning agent, liquid crystal aligning film and liquid crystal display device |
| CN105085281A (en) * | 2015-08-07 | 2015-11-25 | 吉林大学 | Diamine monomer containing diphenylamine-fluorene, preparation method and application of same in polyimide preparation |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018070475A (en) * | 2016-10-26 | 2018-05-10 | 株式会社リコー | Electrochromic compound, electrochromic composition, and electrochromic element |
| CN109491147A (en) * | 2017-09-11 | 2019-03-19 | 夏普株式会社 | The manufacturing method of alignment films, liquid crystal display panel and liquid crystal display panel |
| CN109627212A (en) * | 2018-12-12 | 2019-04-16 | 吉林大学 | A kind of diacid monomer and preparation method thereof and polyamide and preparation method thereof |
| CN109627212B (en) * | 2018-12-12 | 2020-03-10 | 吉林大学 | Diacid monomer and preparation method thereof, and polyamide and preparation method thereof |
| JP2020140053A (en) * | 2019-02-27 | 2020-09-03 | 株式会社リコー | Electrochromic device, display device, lighting control device, electrochromic composition, and cured film |
| CN113388104A (en) * | 2021-07-02 | 2021-09-14 | 黑龙江大学 | Triarylamine polyamide containing fluorenyl directly bonded with triphenylamine, and preparation method and application thereof |
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| CN105646260B (en) | 2018-04-13 |
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