CN104448311A - Polyimide based on 2,3,6,7-triptycene tetracarboxylic dianhydride and preparation method of polyimide - Google Patents

Polyimide based on 2,3,6,7-triptycene tetracarboxylic dianhydride and preparation method of polyimide Download PDF

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CN104448311A
CN104448311A CN201410591757.2A CN201410591757A CN104448311A CN 104448311 A CN104448311 A CN 104448311A CN 201410591757 A CN201410591757 A CN 201410591757A CN 104448311 A CN104448311 A CN 104448311A
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triptycene
polyimide
tetramethyl
preparation
tetracarboxylic dianhydride
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程琳
邵宇
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Huaqiao University
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Huaqiao University
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Abstract

The invention provides polyimide based on 2,3,6,7-triptycene tetracarboxylic dianhydride and a preparation method of polyimide. The molecular weight of polyimide is about 30000 Faltons (GPC), the intrinsic viscosity of polyimide is within 0.58-0.73dL/g, the glass-transition temperature of polyimide is greater than 300 DEG C, and the 5% decomposition temperature of polyimide is 450 DEG C, that is, very good thermal resistance is achieved; meanwhile a triptycene structure on a polymer main chain can be formed into a Z-shaped structure, so that the action force of molecular chains can be reduced, the solubility of the polymer is improved as the compact piling of chains is reduced, the color of a polymer film is greatly improved, i.e., polymer film is nearly colorless from the conventional golden yellow, and thus the polymer film has wide application prospect in high-tech fields such as micro-electronics, photoelectron and optical communication; in addition, the preparation method provided by the invention has the characteristics of being low in cost, simple in preparation process and easy to control.

Description

A kind of polyimide based on 2,3,6,7-triptycene tetracarboxylic dianhydride and preparation method thereof
[technical field]
The present invention relates to a kind of polymeric material field, be specifically related to a kind of polyimide based on 2,3,6,7-triptycene tetracarboxylic dianhydride and preparation method thereof.
[background technology]
Aromaticity polyimide has purposes widely as the structure and function material that a class is important in microelectronics, aerospace etc., owing to having very stable fragrant heterocycle structure in polyimide molecule, make it embody the incomparable excellent properties of other macromolecular materials, but the contradiction between high-performance and processibility greatly limit its application.Nowadays, synthesizing linear gathers the comparatively general method of fragrant imide is polycondensation between dianhydride and diamine monomer; Because the commercialization of diamines is very ripe, therefore start with from monomer molecule design and develop new dianhydride monomer, have very important meaning to the application expanding polyimide.
In recent years, constantly be developed based on the conjugated polymers of triptycene structure, aromatic polyester, urethane, not only achieve and apply widely, also imply that the prospect of triptycene polyimide, such as: Swager has synthesized serial synthesis triptycene structure linear polymer and developed the chemical sensor detecting trace TNT; Budd and Mckeown etc. have carried out about the research of triptycene structure nano porous polyarylether in polymkeric substance Chu Qing, develop the bridging property polyarylether material that hydrogen storage property in the synthetic polymer studied is best; Contain triptycene structural unit linear aromatic polyester, polymeric amide and the urethane etc. of Eastaman Kodak and the exploitation of Du Pont company have good thermotolerance and processing characteristics, the water white film of pourable formation.
But, rarely have report about the polyimide being main chain direction with three phenyl ring planes in triptycene due to the synthesis difficulty of monomer.
[summary of the invention]
Technical problem to be solved by this invention is the complete fragrant polyimide providing a kind of base 2,3,6,7-triptycene tetracarboxylic dianhydride, has excellent optical property and resistance toheat etc.
The present invention solves the problems of the technologies described above by the following technical programs:
A kind of polyimide based on 2,3,6,7-triptycene tetracarboxylic dianhydride, the chemical structural formula of this polyimide is:
Wherein Ar is:
in any one.
Above-mentioned based on 2,3, the average molecular weight of the polyimide of 6,7-triptycene tetracarboxylic dianhydride in about 30,000 Daltons (GPC), limiting viscosity between 0.58 ~ 0.73dL/g, second-order transition temperature more than 300 DEG C, 5% decomposition temperature is more than 450 DEG C.
Meanwhile, disclose this preparation method based on 2,3,6,7-triptycene-tetracarboxylic dianhydride polyimide, described preparation method comprises following operation steps:
(1) with o-Xylol, methylene dichloride under Catalyzed by Anhydrous Aluminium Chloride effect, after heating up, generate 2,3,6,7-tetramethyl-anthracene;
The benzyne of (2) 2,3,6,7-tetramethyl-anthracenes and anthranilic acid diazotization produced in situ under Isopentyl nitrite exists carries out Diels-Alder reaction, then generate crude product 2,3,6,7-tetramethyl-triptycene;
(3) crude product 2,3,6,7-tetramethyl-triptycene rinses via chromatographic separation and mixing eluent, obtains 2,3,6, the 7-tetramethyl-triptycenes that purity is greater than 99%;
(4) 2,3,6,7-tetramethyl-triptycenes are oxidized generation 2,3,6,7-triptycene tetracarboxylic acid in potassium permanganate and pyridine-water mixed solvent under reflux conditions;
(5) 2,3,6,7-triptycene tetracarboxylic acids first carry out Decompression Sublimation in vacuum tightness-0.085 ~-0.095Mpa, temperature 400 ~ 500 DEG C of conditions, obtain 2,3,6,7-triptycene tetracarboxylic acid dianhydride monomer;
(6) under protection of inert gas, the diamine monomer and 2 of equimolar ratio is added successively, 3,6,7-triptycene tetracarboxylic dianhydride monomer, and be solvent with meta-cresol, dry toluene is dewatering agent, isoquinoline 99.9 is catalyzer, dry toluene and material molar ratio are 7 ~ 15:1; Progressively heat up with the speed of 20 DEG C/20min ~ 20 DEG C/10min afterwards, toluene-water azeotrope is sloughed in 150 ~ 160 DEG C, again in 190 ~ 200 DEG C of reaction 4 ~ 6h, finally pour the polymers soln dilution of reaction gained in methanol solution sedimentation, namely suction filtration obtains described polyimide.
Further, the mol ratio of methylene dichloride and aluminum chloride is 2 ~ 3:1 in described step (1), and initial charge temperature is-5 ~ 5 DEG C, then with room temperature reaction 0 ~ 1 hour, then 60 ~ 70 DEG C of water-baths, the reaction times is 3 ~ 5 hours.
Further, in described step (2), the mol ratio of anthranilic acid and 2,3,6,7-tetramethyl-anthracene is 2.5 ~ 3.5:1, and the mol ratio of Isopentyl nitrite and anthranilic acid is 1 ~ 2:1; Dissolve 2,3,6, the solvent of 7-tetramethyl-anthracene and Isopentyl nitrite adopts ethylene dichloride, the solvent dissolving anthranilic acid adopts diethylene glycol dimethyl ether, and feed rate is 15 ~ 20 mls/hour, and return time is 3 ~ 5 hours, and reaction adds MALEIC ANHYDRIDE and removes unreacted anthracene, in order to improve subsequent columns chromatographic separation after product purity after terminating.
Further, in described step (3), chromatographic separation adopts silica gel column chromatography to be separated, and stationary phase is 200 ~ 400 order silica gel; Mixing eluent adopts sherwood oil and methylene dichloride, and sherwood oil is 18 ~ 25:1 with methylene chloride volume ratio; Drip washing disengaging time is 6 ~ 8h.
Further, in described step (4), pyridine is 6 ~ 7:1 with water mixed volume ratio, and potassium permanganate and 2,3,6,7-tetramethyl-triptycene mol ratio are 30 ~ 40:1; Reaction times is 24 ~ 30 hours.
Beneficial effect of the present invention is:
The present invention by the polymer backbone introduce rigidity there is the symmetric triptycene structure of special D3h, macromole chain rigidity is increased, macromolecular chain is difficult to the interior rotation drawn game portion sub-chain motion that side base occurs, thus the second-order transition temperature of polymkeric substance improved, make polymkeric substance have good resistance toheat; Simultaneously, triptycene structure on main polymer chain can form " it " font structure, contribute to reducing molecular chain intermolecular forces, reduce closely piling up thus improving structure adaptability of interchain, make the color of polymeric film have significantly to take on a new look simultaneously, become near colorless from golden yellow in the past, make it in microelectronics and the high-tech sector application prospect widely such as photoelectron and optical communication neck; In addition, preparation method of the present invention has that cost is low, preparation process is simple, manageable feature.
[accompanying drawing explanation]
The present invention is further illustrated in conjunction with the embodiments with reference to the accompanying drawings.
Fig. 1 is the IR spectrogram of the polyimide (I-PI) that in the present invention, embodiment one prepares.
Fig. 2 be in the present invention embodiment one prepare (I-PI) of polyimide 1h-NMR spectrogram.
[embodiment]
A kind of preparation method based on 2,3,6,7-triptycene-tetracarboxylic dianhydride polyimide of the present invention, described preparation method comprises following operation steps:
(1) with o-Xylol, methylene dichloride under Catalyzed by Anhydrous Aluminium Chloride effect, after heating up, generate 2,3,6,7-tetramethyl-anthracene;
The benzyne of (2) 2,3,6,7-tetramethyl-anthracenes and anthranilic acid diazotization produced in situ under Isopentyl nitrite exists carries out Diels-Alder reaction, then generate crude product 2,3,6,7-tetramethyl-triptycene;
(3) crude product 2,3,6,7-tetramethyl-triptycene rinses via chromatographic separation and mixing eluent, obtains 2,3,6, the 7-tetramethyl-triptycenes that purity is greater than 99%;
(4) 2,3,6,7-tetramethyl-triptycenes are oxidized generation 2,3,6,7-triptycene tetracarboxylic acid in potassium permanganate and pyridine-water mixed solvent under reflux conditions;
(5) 2,3,6,7-triptycene tetracarboxylic acids first carry out Decompression Sublimation in vacuum tightness-0.085 ~-0.095Mpa, temperature 400 ~ 500 DEG C of conditions, obtain 2,3,6,7-triptycene tetracarboxylic acid dianhydride monomer;
(6) under protection of inert gas, the diamine monomer and 2 of equimolar ratio is added successively, 3,6,7-triptycene tetracarboxylic dianhydride monomer, and be solvent with meta-cresol, dry toluene is dewatering agent, isoquinoline 99.9 is catalyzer, dry toluene and material molar ratio are 7 ~ 15:1; Progressively heat up with the speed of 20 DEG C/20min ~ 20 DEG C/10min afterwards, toluene-water azeotrope is sloughed in 150 ~ 160 DEG C, again in 190 ~ 200 DEG C of reaction 4 ~ 6h, finally under agitation pour the polymers soln of reaction gained in methanol solution sedimentation, namely suction filtration obtains described polyimide, and the structural formula of this polyimide is as follows:
Wherein Ar is:
in any one.
Wherein, the mol ratio of methylene dichloride and aluminum chloride is 2 ~ 3:1 in step (1), and initial charge temperature is-5 ~ 5 DEG C, then with room temperature reaction 0 ~ 1 hour, then 60 ~ 70 DEG C of water-baths, the reaction times is 3 ~ 5 hours.In step (2), the mol ratio of anthranilic acid and 2,3,6,7-tetramethyl-anthracene is 2.5 ~ 3.5:1, and the mol ratio of Isopentyl nitrite and anthranilic acid is 1 ~ 2:1; Dissolve 2,3,6, the solvent of 7-tetramethyl-anthracene and Isopentyl nitrite adopts ethylene dichloride, the solvent dissolving anthranilic acid adopts diethylene glycol dimethyl ether, and feed rate is 15 ~ 20 mls/hour, and return time is 3 ~ 5 hours, and reaction adds MALEIC ANHYDRIDE and removes unreacted anthracene, in order to improve subsequent columns chromatographic separation after product purity after terminating.In step (3), chromatographic separation adopts silica gel column chromatography to be separated, and stationary phase is 200 ~ 400 order silica gel; Mixing eluent adopts sherwood oil and methylene dichloride, and sherwood oil is 18 ~ 25:1 with methylene chloride volume ratio; Drip washing disengaging time is 6 ~ 8h.In step (4), pyridine is 6 ~ 7:1 with water mixed volume ratio, and potassium permanganate and 2,3,6,7-tetramethyl-triptycene mol ratio are 30 ~ 40:1; Reaction times is 24 ~ 30 hours.
In addition, the reaction formula involved by step (1) ~ (5) is as follows:
Refer to shown in Fig. 1 and Fig. 2, and be explained in detail explanation in conjunction with following embodiment to the present invention.
Embodiment one:
Cryosel is bathed and under 400r/min mechanical agitation, in the 250mL there-necked flask being equipped with 120mL o-Xylol and 70mL methylene dichloride, is divided into four times and adds 60g aluminum chloride, guarantee system temperature 0 DEG C in reinforced process; Under room temperature, 0.5h is reacted, afterwards 65 DEG C of water-bath 4h again after reinforced; Then reaction gains are slowly poured into be scattered in 300mL5% hydrochloric acid ice water mixed liquid, pour in process and need to stir, then leave standstill, suction filtration (filter cake adopt anhydrous propanone wash), to dry, obtain white plates that is 2,3,6,7-tetramethyl-anthracene solid 20g, its fusing point is 299 DEG C, and its structure via 1hNMR characterizes confirmation.
1HNMR(400MHz,CDCl3):δ＝2.43(s,12H),7.68(s,4H),8.13(s,2H)。
Take 2g 2,3,6,7-tetramethyl-anthracene to add and be equipped with in the 500mL there-necked flask of 100mL ethylene dichloride, reflux, due to 2, 3, 6, the intermediate benzyne that 7-tetramethyl-anthracene and azoization generate reacts, so need two of azo kind of reagent anthranilic acid and Isopentyl nitrite be dropped in reaction system and backflow system simultaneously, particularly: get 4mL Isopentyl nitrite and 20mL ethylene dichloride is mixed to form mixed solution I, take 3.0g anthranilic acid and be dissolved in 20mL diethylene glycol dimethyl ether and form mixed solution II, then mixed solution I, mixed solution II is added dropwise in aforementioned backflow system simultaneously, and ensure mixed solution I, mixed solution II dropwises simultaneously, and feed rate is 15 mls/hour, after dropwising, then the 4h that refluxes, finally except desolventizing obtains the yellow-brown solid i.e. thick product 2.5g of 2,3,6,7-tetramethyl-triptycenes, calculate and learn that thick productive rate is 96%.
Take 2,3,6, the thick product 3g of 7-tetramethyl-triptycene, and the 40cm silicagel column be assembled in 400g 200 ~ 400 order silica gel is separated: eluent is sherwood oil and methylene dichloride mixed solution (sherwood oil and methylene chloride volume are than being 20:1), thin-layer chromatography Rf value is 0.70, and drip washing 6h under normal pressure; The separating obtained leacheate containing 2,3,6,7-tetramethyl-triptycene is carried out evaporate to dryness, obtains white crystal, dry and be weighed as 2.45g, learn by calculating, isolated yield is 81.6%, 2,3,6,7-tetramethyl-triptycene total recovery is 77%; And its fusing point is 240 ~ 241 DEG C.Product via 1hNMR, 13cNMR and MS characterizes, and confirms the structure of 2,3,6,7-tetramethyl-triptycene.
1HNMR(400MHz,CDCl3):
δ＝2.13(s,12H),5.26(s,2H),6.92-6.95(m,2H),7.14(s,4H),7.29-7.32(m,2H)。
13CNMR(100.6MHz,CDCl3):
δ＝19.5,53.2,123.3,124.9,124.9,132.7,143.2,145.8ppm。
MS(EI,70eV):m/z(％)＝310(75,[M+]),295(100),280(47),265(10)。
Take 1.5g 2,3,6,7-tetramethyl-triptycene solid adds and is equipped with in the there-necked flask of mechanical stirrer, then adds 75mL pyridine and 12mL water, when being heated to vigorous reflux, gradation adds the 120mL aqueous solution (this aqueous temperature is 90 DEG C) being dissolved with 30g potassium permanganate, each 8mL, then system takes off brilliant violet look, and from adding potassium permanganate solution at first, calculate common backflow 24h; Treat that solution cools after backflow terminates, carry out suction filtration afterwards, and adopt the sodium hydroxide solution flush cake of 100mL 10%, gained filtrate is steamed to about 30mL, then solution is transferred to beaker, the hydrochloric acid soln acidifying with 10%, until PH<3, is then filtered and is obtained white solid 2,3,6,7-triptycene tetracarboxylic acid 1.84g, fusing point is greater than 360 DEG C, and calculate learn that productive rate is 88.5%, and its structure via 1hNMR, 13cNMR and MS characterizes confirmation.
1HNMR(400MHz,DMSO-d6)；
δ＝5.96(s,2H),7.04-7.06(m,2H),7.48-7.51(m,2H),8.00(brs,4H)。
13CNMR(100.6MHz,DMSO-d6):；
δ＝51.8,124.4,125.8,131.6,144.0,147.0,168.2ppm。
MS(EI,70eV):m/z(％)＝394(5,[M+－2H2O]),350(3)。
Take 2,3,6,7-triptycene tetracarboxylic acid 0.5g, and Decompression Sublimation is carried out under vacuum tightness-0.095MPa, temperature 400 DEG C of conditions, obtain light yellow crystal that is 2,3,6,7-triptycene tetracarboxylic dianhydride monomer 0.35g, fusing point is greater than 300 DEG C, and calculate know that its productive rate is 70%, its structure via 1hNMR characterizes confirmation.
1HNMR(400MHz,DMSO-d6)；
δ:6.36(s,2H),7.11-7.14(m,2H),7.57-7.59(m,2H),8.17(s,4H)。
Under argon shield, in the 25mL there-necked flask that water trap is housed, add diamine monomer 4, 4'-diamino-2, 2'-bis trifluoromethyl biphenyl 0.65mmol (i.e. 0.2080g), meta-cresol 2mL, 2 are added successively after stirring 30mim, 3, 6, 7-triptycene tetracarboxylic dianhydride monomer 0.65mmol (i.e. 0.2563g), meta-cresol 2mL, isoquinoline 99.9 5 (0.1mL), and dry toluene 1.5mL, at room temperature magnetic agitation 1h afterwards, then with the ramp of 20 DEG C/15min, toluene-water azeotrope is sloughed when being warming up to 150 DEG C, take off completely to the greatest extent until toluene and be warming up to 190 DEG C of reaction 6h again, then the polymers soln of reaction gained is under agitation poured in 200mL methyl alcohol and carry out sedimentation, then the thread polyimide obtaining white is filtered, product and thread polyimide are dissolved in DMAc and pour sedimentation in methyl alcohol again into, exquisite 2 times repeatedly, obtain dry white flocculent polymer 0.4224g.
Wherein, the structural formula of diamine monomer 4,4'-diamino-2,2'-bis trifluoromethyl biphenyl is:
The structural formula of the white flocculent polymer of final acquisition is:
Embodiment two:
Cryosel is bathed and under 500r/min mechanical agitation, in the 250mL there-necked flask being equipped with 120mL o-Xylol and 70mL methylene dichloride, is divided into four times and adds 73g aluminum chloride, guarantee system temperature-5 DEG C in reinforced process; Under room temperature, 0.75h is reacted, afterwards 60 DEG C of water-bath 3h again after reinforced; Then reaction gains are slowly poured into and are scattered in the hydrochloric acid ice water mixed liquid of 300mL 5%, pour in process and need to stir, then leave standstill, suction filtration (filter cake adopt anhydrous propanone wash), to dry, obtain white plates that is 2,3,6,7-tetramethyl-anthracene solid 24g, its fusing point is 299 DEG C, and its structure via 1hNMR characterizes confirmation.
1HNMR(400MHz,CDCl3):δ＝2.43(s,12H),7.68(s,4H),8.13(s,2H)。
Take 2g 2,3,6,7-tetramethyl-anthracene to add and be equipped with in the 500mL there-necked flask of 100mL ethylene dichloride, reflux, due to 2, 3, 6, the intermediate benzyne that 7-tetramethyl-anthracene and azoization generate reacts, so need two of azo kind of reagent anthranilic acid and Isopentyl nitrite be dropped in reaction system and backflow system simultaneously, particularly: get 5.8mL Isopentyl nitrite and 20mL ethylene dichloride is mixed to form mixed solution I, take 3.5g anthranilic acid and be dissolved in 26mL diethylene glycol dimethyl ether and form mixed solution II, then by mixed solution I, mixed solution II drops in aforementioned backflow system, and ensure mixed solution I, mixed solution II dropwises simultaneously, and feed rate is 18 mls/hour, after dropwising, then the 4h that refluxes, finally except desolventizing obtains the yellow-brown solid i.e. thick product 2.4g of 2,3,6,7-tetramethyl-triptycenes, calculate and learn that thick productive rate is 93%.
Take 2,3,6, the thick product 3g of 7-tetramethyl-triptycene, and the 40cm silicagel column be assembled in 400g 200 ~ 400 order silica gel is separated: eluent is sherwood oil and methylene dichloride mixed solution (volume ratio of sherwood oil and methylene dichloride is 18:1), thin-layer chromatography Rf value is 0.75, and drip washing 7h under normal pressure; The separating obtained leacheate containing 2,3,6,7-tetramethyl-triptycene is carried out evaporate to dryness, obtains white crystal, dry and be weighed as 2.5g, learn by calculating, isolated yield is 83%, 2,3,6,7-tetramethyl-triptycene total recovery is 75%; And fusing point is 240 ~ 241 DEG C.Product via 1hNMR, 13cNMR and MS characterizes, and confirms the structure of 2,3,6,7-tetramethyl-triptycene.
1HNMR(400MHz,CDCl3)；
δ＝2.13(s,12H),5.26(s,2H),6.92-6.95(m,2H),7.14(s,4H),7.29-7.32(m,2H)。
13CNMR(100.6MHz,CDCl3)；
δ＝19.5,53.2,123.3,124.9,124.9,132.7,143.2,145.8ppm。
MS(EI,70eV):m/z(％)＝310(75,[M+]),295(100),280(47),265(10)。
Take 1.5g 2,3,6,7-tetramethyl-triptycene solid adds and is equipped with in the there-necked flask of mechanical stirrer, then adds 75mL pyridine and 12.5mL water, when being heated to vigorous reflux, gradation adds the 96mL aqueous solution (this aqueous temperature is 98 DEG C) being dissolved with 24g potassium permanganate, each 8mL, then system takes off brilliant violet look, and from adding potassium permanganate solution at first, calculate common backflow 27h; Treat that solution cools after backflow terminates, carry out suction filtration afterwards, and adopt the sodium hydroxide solution flush cake of 100mL 10%, gained filtrate is steamed to about 30mL, then solution is transferred to beaker, the hydrochloric acid soln acidifying with 10%, until PH<3, is then filtered and is obtained white solid 2,3,6,7-triptycene tetracarboxylic acid 1.77g, fusing point is greater than 360 DEG C, and calculating learns that productive rate is 85%, its structure characterizes via 1HNMR, 13CNMR and MS and confirms.
1HNMR(400MHz,DMSO-d6):
δ＝5.96(s,2H),7.04-7.06(m,2H),7.48-7.51(m,2H),8.00(brs,4H)。
13CNMR(100.6MHz,DMSO-d6):
δ＝51.8,124.4,125.8,131.6,144.0,147.0,168.2ppm。
MS(EI,70eV):m/z(％)＝394(5,[M+－2H2O]),350(3)。
Take 2,3,6,7-triptycene tetracarboxylic acid 0.5g, and Decompression Sublimation is carried out under vacuum tightness-0.090MPa, temperature 450 DEG C of conditions, obtain light yellow crystal that is 2,3,6,7-triptycene tetracarboxylic dianhydride monomer 0.32g, fusing point is greater than 300 DEG C, and calculate know that its productive rate is 64%, its structure via 1hNMR characterizes confirmation.
1HNMR(400MHz,DMSO-d6)；
δ:6.36(s,2H),7.11-7.14(m,2H),7.57-7.59(m,2H),8.17(s,4H)。
Under nitrogen protection, in the 25mL there-necked flask that water trap is housed, add diamine monomer 3, 3', 5, 5'-tetramethyl benzidine 0.65mmol (i.e. 0.1562g), meta-cresol 2mL, 2 are added successively after stirring 30mim, 3, 6, 7-triptycene tetracarboxylic dianhydride monomer 0.65mmol (i.e. 0.2563g), meta-cresol 2mL, isoquinoline 99.9 5 (0.1mL), and dry toluene 0.5mL, at room temperature magnetic agitation 1h afterwards, then with the ramp of 20 DEG C/10min, toluene-water azeotrope is sloughed when being warming up to 160 DEG C, take off completely to the greatest extent until toluene and be warming up to 200 DEG C of reaction 4h again, then the polymers soln of reaction gained is under agitation poured in 200mL methyl alcohol and carry out sedimentation, then the thread polyimide obtaining white is filtered, product and thread polyimide are dissolved in DMAc and pour sedimentation in methyl alcohol again into, exquisite 2 times repeatedly, obtain dry white flocculent polymer 0.4011g.
Wherein, diamine monomer 3,3', the structural formula of 5,5'-tetramethyl benzidine is:
The structural formula of the white flocculent polymer of final acquisition is:
Embodiment three
Cryosel bath and 300r/min mechanical stirringunder condition, in the 250mL there-necked flask being equipped with 120mL o-Xylol and 70mL methylene dichloride, be divided into four times and add 50g aluminum chloride, guarantee system temperature 5 DEG C in reinforced process; Under room temperature, 1.0h is reacted, afterwards 70 DEG C of water-bath 5h again after reinforced; Then reaction gains are slowly poured into and are scattered in the hydrochloric acid ice water mixed liquid of 300mL 5%, pour in process and need to stir, then leave standstill, suction filtration (filter cake anhydrous propanone is washed), dry, obtain white plates that is 2,3,6,7-tetramethyl-anthracene solid 19g, its fusing point is 299 DEG C, its its structure via 1hNMR characterizes confirmation.
1HNMR(400MHz,CDCl 3):δ＝2.43(s,12H),7.68(s,4H),8.13(s,2H)。
Take 2g 2,3,6,7-tetramethyl-anthracene to add and be equipped with in the 500mL there-necked flask of 100mL ethylene dichloride, reflux, due to 2, 3, 6, the intermediate benzyne that 7-tetramethyl-anthracene and azoization generate reacts, so need two of azo kind of reagent anthranilic acid and Isopentyl nitrite be dropped in reaction system and backflow system simultaneously, particularly: get 7.6mL Isopentyl nitrite and 20mL ethylene dichloride is mixed to form mixed solution I, take 4.0g anthranilic acid to be dissolved in 28mL diethylene glycol dimethyl ether and to form mixed solution II, then mixed solution I, mixed solution II is added dropwise in aforementioned backflow system simultaneously, and ensure mixed solution I, mixed solution II dropwises simultaneously, and feed rate is 20 mls/hour, after dropwising, then the 4h that refluxes, finally except desolventizing obtains the yellow-brown solid i.e. thick product 2.3g of 2,3,6,7-tetramethyl-triptycenes, calculate and learn that thick productive rate is 90%.
Take 2,3,6, the thick product 3g of 7-tetramethyl-triptycene, and the 40cm silicagel column be assembled in 400g 200 ~ 400 order silica gel is separated: eluent is sherwood oil and methylene dichloride mixed solution (volume ratio of sherwood oil and methylene dichloride is 25:1), thin-layer chromatography Rf value is 0.65, and drip washing 8h under normal pressure; The separating obtained leacheate containing 2,3,6,7-tetramethyl-triptycene is carried out evaporate to dryness, obtains white crystal, dry and be weighed as 2.6g, learn by calculating, isolated yield is 86.7%, 2,3,6,7-tetramethyl-triptycene total recovery is 74.8%; And its fusing point is 240 ~ 241 DEG C.Product via 1hNMR, 13cNMR and MS characterizes, and confirms the structure of 2,3,6,7-tetramethyl-triptycene.
1HNMR(400MHz,CDCl3)；
δ＝2.13(s,12H),5.26(s,2H),6.92-6.95(m,2H),7.14(s,4H),7.29-7.32(m,2H)。
13CNMR(100.6MHz,CDCl3)；
δ＝19.5,53.2,123.3,124.9,124.9,132.7,143.2,145.8ppm。
MS(EI,70eV):m/z(％)＝310(75,[M+]),295(100),280(47),265(10)。
Take 1.5g 2,3,6,7-tetramethyl-triptycene solid adds and is equipped with in the there-necked flask of mechanical stirrer, then adds 75mL pyridine and 10mL water, when being heated to vigorous reflux, gradation adds the 112mL aqueous solution (this aqueous temperature is 95 DEG C) being dissolved with 28g potassium permanganate, each 8mL, then system takes off brilliant violet look, and from adding potassium permanganate solution at first, calculate common backflow 30h; Treat that solution cools after backflow terminates, carry out suction filtration afterwards, and adopt the sodium hydroxide solution flush cake of 100mL 10%, gained filtrate is steamed to about 30mL, then solution is transferred to beaker, the hydrochloric acid soln acidifying with 10%, until PH<3, is then filtered and is obtained white solid 2,3,6,7-triptycene tetracarboxylic acid 1.95g, fusing point is greater than 360 DEG C, and calculate learn that productive rate is 94%, and its structure via 1hNMR, 13cNMR and MS characterizes confirmation.
1HNMR(400MHz,DMSO-d6):
δ＝5.96(s,2H),7.04-7.06(m,2H),7.48-7.51(m,2H),8.00(brs,4H)。
13CNMR(100.6MHz,DMSO-d6):
δ＝51.8,124.4,125.8,131.6,144.0,147.0,168.2ppm。
MS(EI,70eV):m/z(％)＝394(5,[M+－2H2O]),350(3)。
Take 2,3,6,7-triptycene tetracarboxylic acid 0.5g, and Decompression Sublimation is carried out under vacuum tightness-0.085MPa, temperature 500 DEG C of conditions, obtain light yellow crystal that is 2,3,6,7-triptycene tetracarboxylic dianhydride monomer 0.36g, fusing point is greater than 300 DEG C, and calculate know that its productive rate is 72%, its structure via 1hNMR characterizes confirmation.
1HNMR(400MHz,DMSO-d6):
δ:6.36(s,2H),7.11-7.14(m,2H),7.57-7.59(m,2H),8.17(s,4H)。
Under nitrogen protection, in the 25mL there-necked flask that water trap is housed, add diamine monomer 3, 3 '-tolidine 0.65mmol (i.e. 0.1380g), meta-cresol 1.3mL, 2 are added successively after stirring 30mim, 3, 6, 7-triptycene tetracarboxylic dianhydride monomer 0.65mmol (i.e. 0.2563g), meta-cresol 2mL, isoquinoline 99.9 5 (0.1mL), dry toluene 1.0mL, at room temperature magnetic agitation 1h afterwards, then with the ramp of 20 DEG C/15min, toluene-water azeotrope is sloughed when being warming up to 155 DEG C, take off completely to the greatest extent until toluene and be warming up to 195 DEG C of reaction 5h again, then the polymers soln of reaction gained is under agitation poured in 200mL methyl alcohol and carry out sedimentation, then the thread polyimide obtaining white is filtered, product and thread polyimide are dissolved in DMAc and pour sedimentation in methyl alcohol again into, exquisite 2 times repeatedly, obtain dry white flocculent polymer 0.3706g.
Wherein, diamine monomer 3, the structural formula of 3 '-tolidine is:
The structural formula of the white flocculent polymer of final acquisition is:
Embodiment four
The present embodiment is with compared with example three, and unique difference is, the diamine monomer used is 2,2 '-tolidine, and its structural formula is:
The structural formula of white flocculent polymer that then the present embodiment finally obtains is:
Embodiment five
The present embodiment is with compared with example three, and unique difference is, the diamine monomer used is 4,4 '-p-diaminodiphenyl, and its structural formula is:
The structural formula of white flocculent polymer that then the present embodiment finally obtains is:
For the above embodiments one, namely with diamine monomer 4,4'-diamino-2,2'-bis trifluoromethyl biphenyl and 2, it is example that 3,6,7-triptycene tetracarboxylic dianhydride is polymerized the polyimide (I-PI) obtained, adopt the polyimide of IR spectrographic determination embodiment one gained, then measurement result as shown in Figure 1: GPC:Mn (Daltons) 31235; Mw (Daltons) 49543.
As shown in Figure 1: wherein 1780cm -1and 1726cm -1the asymmetric and symmetrical stretching vibration absorption peak of carbonyl, 1368cm -1imide C-N key stretching vibration absorption peak, 754cm -1it is imide ring absorption peak.Simultaneously this polyimide via 1hNMR characterizes confirmation, obtains (I-PI) as shown in Figure 2 1h-NMR spectrogram, and:
1HNMR(400MHz,DMSO-d6)；
δ:8.09～8.13(m,4H)，7.94～7.97(m,2H)，7.85～7.79(m,2H)，7.55～7.62(m,2H)，7.08～7.15(m,2H)，6.91～7.00(m,2H)，5.36～5.38(m,2H)。Therefore, can judge that polymer architecture skeleton is in the main true.
Namely confirm that the structural formula of the polyimide that embodiment one obtains is accurate by above-mentioned.
In addition, known by physical and chemical determination, 5 kinds of polyimide that above-mentioned five embodiments prepare gained are at room temperature dissolved in N,N-dimethylacetamide, N-Methyl pyrrolidone all entirely, and heating energy is dissolved in meta-cresol entirely, and can be swelling in chloroform; The PI wherein utilizing diamines TFMB to synthesize can at room temperature be dissolved in THF; The gained series polymer i.e. molecular weight of 5 kinds of polyimide, all between 1w to 4w, is defined as high molecular polymer; And the second-order transition temperature of the polyimide of gained is greater than 300 DEG C, the decomposition temperature of 5% is greater than 450 DEG C, its limiting viscosity is between 0.58 ~ 0.73dL/g, and therefore, polyimide prepared by the present invention can be used for preparing performance function film field.
The rigidity triptycene structure of the present invention by introducing in the polymer backbone, macromole chain rigidity is increased, macromolecular chain is difficult to the interior rotation drawn game portion sub-chain motion that side base occurs, thus the second-order transition temperature of polymkeric substance improved, make polymkeric substance have good resistance toheat.Simultaneously, triptycene structure on main polymer chain can reduce molecular chain intermolecular forces, reduce closely piling up thus improving structure adaptability and the color depth of its film that significantly takes on a new look of interchain, namely the present invention prepares light color even colorless and transparent film under the prerequisite not affecting thermal characteristics, in other words, polyimide of the present invention prepares the Kapton of gained and existing commercialization polyimide film material comparatively speaking, have the advantages that film is of light color, transparency is high, it has been broken traditionthe method preparing colorless and transparent film as: introduce halogen, introduce unsymmetrical structure, adopt aliphatic monomer etc., the present invention adopts complete fragrant type rigid unitary synthesis, prepare film color from this series polyimide and become near colorless from golden yellow in the past, make it in microelectronics and the high-tech sector application prospect widely such as photoelectron and optical communication neck.
Although the foregoing describe the specific embodiment of the present invention; but be familiar with those skilled in the art to be to be understood that; specific embodiment described by us is illustrative; instead of for the restriction to scope of the present invention; those of ordinary skill in the art, in the modification of the equivalence done according to spirit of the present invention and change, should be encompassed in scope that claim of the present invention protects.

Claims (6)

1. one kind based on the polyimide of 2,3,6,7-triptycene tetracarboxylic dianhydride, it is characterized in that: the chemical structural formula of this polyimide is:
Wherein Ar is:
in any one.
2. one kind based on the preparation method of 2,3,6,7-triptycene-tetracarboxylic dianhydride polyimide, it is characterized in that: this preparation method comprises following operation steps:
(1) with o-Xylol, methylene dichloride under Catalyzed by Anhydrous Aluminium Chloride effect, after heating up, generate 2,3,6,7-tetramethyl-anthracene;
The benzyne of (2) 2,3,6,7-tetramethyl-anthracenes and anthranilic acid diazotization produced in situ under Isopentyl nitrite exists carries out Diels-Alder reaction, then generate crude product 2,3,6,7-tetramethyl-triptycene;
(3) crude product 2,3,6,7-tetramethyl-triptycene rinses via chromatographic separation and mixing eluent, obtains 2,3,6, the 7-tetramethyl-triptycenes that purity is greater than 99%;
(4) 2,3,6,7-tetramethyl-triptycenes are oxidized generation 2,3,6,7-triptycene tetracarboxylic acid in potassium permanganate and pyridine-water mixed solvent under reflux conditions;
(5) 2,3,6,7-triptycene tetracarboxylic acids first carry out Decompression Sublimation in vacuum tightness-0.085 ~-0.095Mpa, temperature 400 ~ 500 DEG C of conditions, obtain 2,3,6,7-triptycene tetracarboxylic acid dianhydride monomer;
(6) under protection of inert gas, the diamine monomer and 2 of equimolar ratio is added successively, 3,6,7-triptycene tetracarboxylic dianhydride monomer, and be solvent with meta-cresol, dry toluene is dewatering agent, isoquinoline 99.9 is catalyzer, dry toluene and material molar ratio are 7 ~ 15:1; Progressively heat up with the speed of 20 DEG C/20min ~ 20 DEG C/10min afterwards, toluene-water azeotrope is sloughed in 150 ~ 160 DEG C, again in 190 ~ 200 DEG C of reaction 4 ~ 6h, finally under agitation pour the polymers soln of reaction gained in methanol solution sedimentation, namely suction filtration obtains polyimide according to claim 1.
3. one according to claim 2 is based on 2,3,6, the preparation method of 7-triptycene-tetracarboxylic dianhydride polyimide, it is characterized in that: the mol ratio of methylene dichloride and aluminum chloride is 2 ~ 3:1 in described step (1), and initial charge temperature is-5 ~ 5 DEG C, then with room temperature reaction 0 ~ 1 hour, 60 ~ 70 DEG C of water-baths again, the reaction times is 3 ~ 5 hours.
4. one according to claim 2 is based on 2,3,6, the preparation method of 7-triptycene-tetracarboxylic dianhydride polyimide, it is characterized in that: anthranilic acid and 2 in described step (2), 3,6, the mol ratio of 7-tetramethyl-anthracene is 2.5 ~ 3.5:1, and the mol ratio of Isopentyl nitrite and anthranilic acid is 1 ~ 2:1; Dissolve 2,3,6, the solvent of 7-tetramethyl-anthracene and Isopentyl nitrite adopts ethylene dichloride, the solvent dissolving anthranilic acid adopts diethylene glycol dimethyl ether, feed rate is 15 ~ 20 mls/hour, and return time is 3 ~ 5 hours, and reaction adds MALEIC ANHYDRIDE and removes unreacted anthracene after terminating.
5. one according to claim 2 is based on the preparation method of 2,3,6,7-triptycene-tetracarboxylic dianhydride polyimide, it is characterized in that: in described step (3), chromatographic separation adopts silica gel column chromatography to be separated, and stationary phase is 200 ~ 400 order silica gel; Mixing eluent adopts sherwood oil and methylene dichloride, and sherwood oil is 18 ~ 25:1 with methylene chloride volume ratio; Drip washing disengaging time is 6 ~ 8h.
6. one according to claim 2 is based on 2,3,6, the preparation method of 7-triptycene-tetracarboxylic dianhydride polyimide, it is characterized in that: in described step (4), pyridine is 6 ~ 7:1 with water mixed volume ratio, potassium permanganate and 2,3,6,7-tetramethyl-triptycene mol ratio is 30 ~ 40:1; Reaction times is 24 ~ 30 hours.
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