CN103739864A - Sulfuryl fluorine-containing diamine compound, polyimide film material and preparation method thereof - Google Patents
Sulfuryl fluorine-containing diamine compound, polyimide film material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a sulfuryl fluorine-containing diamine compound 2,2'-bis(trifluoromethyl)-4,4'-diamidophenylsulfone and a flexible transparent polyimide film prepared from the sulfuryl fluorine-containing diamine compound. The method for preparing the sulfuryl fluorine-containing diamine has the characteristics of simple synthetic route, mild reaction conditions, accessible reaction raw material sources, low cost, fewer varieties of organic solvents, and the like, and can maximally reduce the environmental pollution. The sulfuryl fluorine-containing diamine structure has sulfuryl and trifluoromethyl groups, can enhance the light transmittance of the material, increase the solubility and lower the dielectric constant and water absorptivity of the material in the polymer material preparation process, and therefore, is suitable for preparing the flexible transparent polyimide film.
Description
Technical field
The invention belongs to the technical field of macromolecular material, relate to a kind of novel sulfuryl fluorinated diamine compou nd synthesis method and the application in preparing transparent polyimide film.
Background technology
Polyimide is a kind of high performance material, in high-tech sectors such as space flight and aviation, electric and electronics, is used widely.In recent years, at optoelectronic areas, flexible display technologies and thin-film solar cells all obtain develop rapidly.Water white Kapton has application prospect comparatively widely at aspects such as photoelectric device and semi-conductors.Scientific research shows, adopts transparent polyimide film as flexible base, board, has not only realized the flexibility of device own, and has alleviated largely the weight of device.
In the document of exercise question " Flexible Organic Electroluminescent Devices Based on Fluorine-Containing Colorless Polyimide Subs trates ", author is usingd polyimide 6FDA-TFDB film as substrate, under differing temps, carry out evaporation ito thin film, obtain a series of preparation OLED transparency carriers, with the transparency carrier contrast obtaining at evaporation ito thin film on glass, result shows, transmitance average out to 75% at 400-700nm wave band, lower than glass substrate (83.4%), sheet resistance average out to 20 Ω/sq., and glass substrate sheet resistance is 9.28 Ω/sq.Adopt polyimide 6FDA-TFDB film to replace glass as substrate, OLED device is realized flexible, also lost the transparency of part simultaneously.
In the Chinese patent that is CN101127369A at publication number, reported a kind of three node flexible overlapping thin film solar battery for space, the flexible compound substrate that its device adopts is by transparent polyimide film, SiO
2-TiO
2or SiO
2-ZrO
2broadband anti-reflection film, polyhedral oligomeric silsesquioxane layer forms.In the Chinese patent that is CN101290955A at publication number, reported a kind of manufacturing process of flexible amorphous silicon solar cell, it has adopted thickness is that 0.3mm web-like transparent polyimide film is substrate, by magnetron sputtering production layer of ZnO x conductive film layer, its resistivity is less than 10 Ω/cm.
Tradition polyimide film tape look, light transmission rate is not high, is owing to there being stronger intermolecular and intramolecular interaction in molecular chain structure, easily forms charge transfer complex between electron donor(ED) diamines and electron acceptor(EA) dianhydride.The thinking that improves at present the transparency of Kapton mainly contains blocking-up polyimide molecule chain conjugation, reduces conjugated degree, reduces diamines electron donation and dianhydride electron-withdrawing power, increases molecular chain torsion resistance, reduces in molecule and piles up degree etc.Employing means have main company to introduce containing fluoro substituents or side group, adopt with alicyclic ring substituted benzene ring, introduce non-coplanar structure, introduce the bridged linkages such as sulfuryl.
In exercise question " novel alicyclic dicarboxylic anhydride monomer synthetic and in the application of colorless polyimide " document, with two kinds of aromatic series dianhydrides (DPM, HFBAPP) respectively with aromatic series dianhydride (PMDA), fluorine-containing be dianhydride (6FDA), new synthetic six kinds of polyimide of synthetic dianhydride (CMDA).Result of study shows alicyclic polyimides film tool high optical transparency, and more than 380nm, (at whole visible-range) maintains the penetration of 95-98%.Aspect thermal property, in three kinds of alicyclic polyimides, to have the highest Tg be 222 ℃ to CMDA/HFBAPP, and the highest Td (10%) is 547 ℃.This type of material weak point is that Tg is not high, at photoelectric field, uses and is restricted.
In exercise question " Highly Refractive and Transparent Polyimides Derived from4; 4 '-[m-Sulfonylbis (phenylenesulfanyl)] diphthalic Anhydride and Various Sulfur-Containing Aromatic Diamines " document, the dianhydride DPSDA that has synthesized a kind of novel sulfuryl bridging, the Kapton obtaining has good optical transparency, in 450nm place transmitance, surpasses 85%.The bridging of electronegativity sulfuryl and a position replace structure and have reduced CTC formation simultaneously, make polyimide have the higher transparency.Especially point out, diamines and dianhydride all contain sulfuryl bridged bond, hinder the formation of interchain CTC simultaneously, and the sulfuryl in diamines is because strong electron attraction has weakened its electron supplying capacity, and transparency is improved obviously.For this quasi-polyimide, too much introduce thioether bond bridging, main chain is flexible strong, causes Tg not high, 200 ℃ of left and right.
Therefore, the present invention adopts new diamine monomer, contains sulfuryl, trifluoromethyl that electronegativity is strong, preparation colorless polyimide film.
Summary of the invention
Task of the present invention provides a kind of sulfuryl fluorinated diamine compound and preparation method thereof.
Another task of the present invention is to provide a kind of flexible transparent polyimide film material and flexible transparent polyimide film its preparation method.
Realizing technical scheme of the present invention is:
Sulfuryl fluorinated diamine compound provided by the invention is to have with 2,2 ' of following formula (I) structure-bis-(trifluoromethyl)-4,4 '-diamino-phenyl sulfone,
Prepare sulfuryl fluorinated diamine compound 2 for two kinds provided by the invention, 2 '-bis-(trifluoromethyl)-4, the method for 4 '-diamino-phenyl sulfone, the first prepares 2,2 '-bis-(trifluoromethyl)-4, the method for 4 '-diamino-phenyl sulfone comprises the following steps:
The first step reaction: with the chloro-5-nitro-trifluoromethyl toluene of 2-, thioether coupling agent in molar ratio 1.5:1-3:1 is raw material, with strong polar non-proton organic solvent, dissolve, stirring and refluxing reaction 2-24 hour, cold filtration obtains yellow solid, first with clear water washing, removes desolventizing, then removes raw material with absolute ethanol washing, obtaining yellow solid powder, is 2-trifluoromethyl-4-nitrophenyl thioether;
Second step reaction: using acidic medium as solvent, by 2-trifluoromethyl-4-nitrophenyl thioether and oxygenant in molar ratio the ratio of 1:2-1:6 dissolve in described acidic medium solvent, be warming up to 30-120 ℃, reaction 1-10 hour, be cooled to room temperature, filter out solid impurity, reaction solution is poured in clear water and separated out, refilter, clear water washing head product, dehydrated alcohol recrystallization obtains faint yellow needle-like crystal, is 2, two (trifluoromethyl)-4 of 2-, 4 '-dinitrophenyl sulfone;
Three-step reaction: with 2, two (trifluoromethyl)-4 of 2-, 4 '-dinitrophenyl sulfone, hydrazine hydrate in molar ratio 1:4-1:10 is raw material, dehydrated alcohol is made solvent, and adding quality proportion is 0.5%-2% palladium-carbon catalyst, back flow reaction 1-10 hour, product is through heat filtering, solvent evaporated, obtains yellow solid powder, mixes the white needle-like crystals obtaining as solvent recrystallization be 2 with dehydrated alcohol and water, 2 '-bis-(trifluoromethyl)-4,4 '-diamino-phenyl sulfone.
Below that the first prepares 2,2 '-bis-(trifluoromethyl)-4, the building-up reactions formula of 4 '-diamino-phenyl sulfone method:
The second prepares 2,2 '-bis-(trifluoromethyl)-4, and the method for 4 '-diamino-phenyl sulfone comprises the following steps step a, step b and step c:
Step a: with the chloro-5-nitro-trifluoromethyl toluene of 2-, thioether coupling agent in molar ratio 1.5:1-3:1 is raw material, with strong polar non-proton organic solvent, dissolve, stirring and refluxing reaction 2-24 hour, cold filtration obtains yellow solid, first with clear water washing, removes desolventizing, then removes raw material with absolute ethanol washing, obtaining yellow solid powder, is 2-trifluoromethyl-4-nitrophenyl thioether;
Step b: with 2-trifluoromethyl-4 nitrophenyl thioether, hydrazine hydrate in molar ratio 1:4-1:10 is raw material, dehydrated alcohol is made solvent, add that to take 2-trifluoromethyl-4 nitrophenyl thioether quality proportion be 0.5%-2% palladium-carbon catalyst, back flow reaction 1-10 hour, product is through heat filtering, solvent evaporated, obtaining yellow solid powder, with second alcohol and water, mix and obtain white crystal as solvent recrystallization, is 2-trifluoromethyl-4-aminophenyl-thioether;
Step c: 2-trifluoromethyl-4-aminophenyl-thioether and oxygenant are dissolved in the acidic medium of solvent, the consumption mol ratio of 2-trifluoromethyl-4-aminophenyl-thioether and oxygenant is 1:1.5-1:6, back flow reaction 1-10 hour, is cooled to room temperature, filters out solid impurity, reaction solution is poured in clear water and separated out, refilter, clear water washing head product, then be 2 with the white solid that toluene recrystallization obtains, 2 '-bis-(trifluoromethyl)-4,4 '-diamino-phenyl sulfone.
Below that the second prepares 2,2 '-bis-(trifluoromethyl)-4, the building-up reactions formula of 4 '-diamino-phenyl sulfone method:
Prepare 2,2 '-bis-(trifluoromethyl)-4 for above-mentioned two kinds, the strong polar non-proton organic solvent described in the method for 4 '-diamino-phenyl sulfone can be DMF, N,N-dimethylacetamide or N, N-dimethyl sulfoxide (DMSO).
Prepare 2,2 '-bis-(trifluoromethyl)-4 for above-mentioned two kinds, the acidic medium as solvent described in the method for 4 '-diamino-phenyl sulfone can be sulfuric acid, phosphoric acid, acetic acid or acetic anhydride.
Prepare 2 for above-mentioned two kinds, 2 '-bis-(trifluoromethyl)-4, the oxygenant described in the method for 4 '-diamino-phenyl sulfone can be Periodic acid, Manganse Dioxide, sodium dichromate 99, potassium bichromate, chromium trioxide, benzoyl hydroperoxide, hydrogen peroxide or lead tetra-acetate.
Flexible transparent polyimide film material provided by the invention, its general formula of molecular structure is as shown in following formula (II):
In formula (II), n represents the polymerization degree, and its span is n >=5, is preferably 5≤n≤500; R1 represents dianhydride residue, and described dianhydride residue is one or more in following listed dianhydride residue:
(1) full aromatic dianhydride residue
(2) fatty dianhydride residue
(3) bridging aromatic dianhydride residue
Wherein preferred dianhydride residue is
Or
Flexible transparent polyimide film provided by the invention, also referred to as sulfuryl fluorinated polyimide film, also can be described as the fluorine-containing flexible transparent polyimide film of sulfuryl, and its preparation method comprises the following steps one and step 2:
Step 1: with strong polar non-proton organic solvent by compound 2 claimed in claim 1,2 '-bis-(trifluoromethyl)-4,4 '-diamino-phenyl sulfone is dissolved in polymerization container completely, described strong polar non-proton organic solvent is N, dinethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO) or N-Methyl pyrrolidone; Slowly add again the dianhydride monomer of equimolar amount, the solid content of controlling reaction solution is 10-70%, under mechanical stirring, react 1-48 hour, obtain the fluorine-containing polyamic acid solution of transparent, thick sulfuryl, described dianhydride monomer is selected from one or two or more kinds in following A-Q compound:
Step 2: by the fluorine-containing polyamic acid solution of the sulfuryl of gained standing 1-48 hour after wherein bubble is eliminated, on clean substrate, film, first at 70-90 ℃, dry 1-3 hour, take again 20-50 ℃ as a ladder, be warmed up to 200-300 ℃ of baking 1-120 minute, then naturally cooling, puts into the sulfuryl fluorinated polyimide film that the standing 1-2 of water hour demoulding obtains and is flexible transparent polyimide film.
Technical problem solved by the invention is to provide a kind of synthetic route of sulfuryl fluorinated diamine compound, sulfuryl fluorinated diamine is applied to transparent polyimide film preparation simultaneously.The synthetic route providing is simple, and reaction conditions is gentle, reaction raw materials convenient sources, and cost is low, and organic solvent is used kind few, reduces to the full extent environmental pollution.
Sulfuryl fluorinated diamine provided by the invention---2,2 '-bis-(trifluoromethyl)-4,4 '-diamino-phenyl sulfone, the sulfuryl that contains strong electronegativity, not only can block the conjugation of polyimide macromolecular chain, and two amine unit electron donations have been weakened, thereby weaken the formation of charge transfer complex (CTC), between amino, position introducing trifluoromethyl group has larger free volume, can make the evacuation of piling up between molecular chain, make macromolecular chain carry out non-copline arrangement, and the strong electron attraction of trifluoromethyl also can weaken two amine unit electron donations.This diamines molecular structure is simple, and synthetic route is short, and productive rate is high, the exploitation of transparent polyimide film is had to widespread use and be worth.
The invention provides a kind of novel sulfuryl fluorinated diamine compound and synthesis technique thereof, synthetic route is simple, and reaction conditions is gentle, reaction raw materials convenient sources, and cost is low, and environmental pollution degree is low.In sulfuryl fluorinated diamine structure of the present invention, there is sulfuryl, trifluoromethyl, in preparing polymer materials, can improve the transmittance of material, increase solvability, reduce specific inductivity and the water-intake rate of material, be therefore applicable to prepare flexible transparent polyimide film.
Accompanying drawing explanation
Fig. 1 is the nucleus magnetic hydrogen spectrum figure of the synthetic 2-trifluoromethyl-4-nitrophenyl thioether of embodiment 1 the first step;
Fig. 2 is the nucleus magnetic hydrogen spectrum figure of the synthetic 2-trifluoromethyl-4-aminophenyl-thioether of embodiment 4 second steps;
Fig. 3 is 2,2 ' synthetic-bis-(trifluoromethyl)-4 of embodiment 1 the 3rd step, the nucleus magnetic hydrogen spectrum figure of 4 '-diamino-phenyl sulfone;
Fig. 4 is the infared spectrum that embodiment 6 prepares polyimide (STFA/6FDA);
Fig. 5 is the infared spectrum that embodiment 7 prepares polyimide (STFA/CHDA);
Fig. 6 is the DSC collection of illustrative plates that embodiment 6 prepares polyimide (STFA/6FDA);
Fig. 7 is the DSC collection of illustrative plates that embodiment 7 prepares polyimide (STFA/CHDA);
Fig. 8 is the TGA collection of illustrative plates that embodiment 6 prepares polyimide (STFA/6FDA);
Fig. 9 is the TGA collection of illustrative plates that embodiment 7 prepares polyimide (STFA/CHDA);
Figure 10 is compound 2,2 ' provided by the invention-bis-(trifluoromethyl)-4, the structural formula of 4 '-diamino-phenyl sulfone;
Figure 11 is the general structure of flexible transparent polyimide film material provided by the invention;
Figure 12 is the structural formula of flexible transparent polyimide film material, and in formula, R1 represents dianhydride residue; N represents the polymerization degree, and its span is: n >=5.
embodiment
The first step: in there-necked flask, add the chloro-5 nitro-trifluoromethyl toluene 22.6g (0.1mol) of 2-, nine hydrated sodium sulfide 12g (0.05mol), N, N-N,N-DIMETHYLACETAMIDE 200mL, open and stir, be warmed up to 165 ℃ of back flow reaction 12 hours under nitrogen protection, cold filtration obtains yellow solid, use respectively clear water and washing with alcohol, obtaining product, is 2-trifluoromethyl-4-nitrophenyl thioether, and yield is 92%;
Second step: in there-necked flask, add 2-trifluoromethyl-4-nitrophenyl thioether 41.2g (0.1mol), then add acetic acid 500mL, under stirring, slowly add Manganse Dioxide 34.7g (0.4mmol) in batches, be warming up to 80 ℃ of reactions 2 hours, be cooled to room temperature, filter out solid impurity, splash in pure water and separate out thick product, after filtering, clear water washing is three times, dry rear with ethyl alcohol recrystallization, obtain 2,2 '-bis-(trifluoromethyl)-4,4 '-dinitrophenyl sulfone, yield is 88%.
The 3rd step: in there-necked flask, add 2-trifluoromethyl-4 nitrophenyl sulfone 44.43g (0.1mol), palladium-carbon catalyst 0.45g; pour ethanol 500mL into; open and stir, under nitrogen protection, drip hydrazine hydrate 40g (0.8mol), heating reflux reaction 3 hours; product is through heat filtering; solvent evaporated, obtains head product, with aqueous ethanolic solution, makes solvent recrystallization; obtain the finished product 2-trifluoromethyl-4-aminophenyl sulfone, yield is 90%.
Product 2-trifluoromethyl-4-nitrophenyl thioether of synthesized, 2,2 '-bis-(trifluoromethyl)-4, the nuclear magnetic spectrum of 4 '-dinitrophenyl sulfone, 2-trifluoromethyl-4-aminophenyl sulfone is shown in accompanying drawing 1,2,4.
The first step: in there-necked flask, add the chloro-5 nitro-trifluoromethyl toluene 22.6g (0.1mol) of 2-, Sodium sulphate anhydrous, 99min 3.9g (0.05mol), N, N-N,N-DIMETHYLACETAMIDE 200mL, open and stir, be warmed up to 165 ℃ of back flow reaction 10 hours under nitrogen protection, cold filtration obtains yellow solid, use respectively clear water and washing with alcohol, obtaining product, is 2-trifluoromethyl-4-nitrophenyl thioether, and yield is 95%;
Second step: in there-necked flask, add 2-trifluoromethyl-4-nitrophenyl thioether 41.2g (0.1mol), then add acetic acid 500mL, under stirring, slowly add potassium periodate 34.7g (0.4mmol) in batches, be warming up to 80 ℃ of reactions 2 hours, be cooled to room temperature, filter out solid impurity, splash in pure water and separate out thick product, after filtering, clear water washing is three times, dry rear with ethyl alcohol recrystallization, obtain 2,2 '-bis-(trifluoromethyl)-4,4 '-dinitrophenyl sulfone, yield is 89%.
The 3rd step: in there-necked flask, add 2-trifluoromethyl-4 nitrophenyl sulfone 44.43g (0.1mol), palladium-carbon catalyst 0.45g; pour ethanol 500mL into; open and stir, under nitrogen protection, drip hydrazine hydrate 50.06g (1mol), heating reflux reaction 5 hours; product is through heat filtering; solvent evaporated, obtains head product, with aqueous ethanolic solution, makes solvent recrystallization; obtain the finished product 2-trifluoromethyl-4-aminophenyl sulfone, yield is 92%.
Product 2-trifluoromethyl-4-nitrophenyl thioether of synthesized, 2,2 '-bis-(trifluoromethyl)-4, the nuclear magnetic spectrum of 4 '-dinitrophenyl sulfone, 2-trifluoromethyl-4-aminophenyl sulfone is shown in accompanying drawing 1,2,4.
The first step: in there-necked flask, add the chloro-5 nitro-trifluoromethyl toluene 22.6g (0.1mol) of 2-, sulphur 2.56g (0.08mol), N, N-dimethyl sulfoxide (DMSO) 150mL, open and stir, be warmed up to 165 ℃ of back flow reaction 12 hours under nitrogen protection, cold filtration obtains yellow solid, use respectively clear water and washing with alcohol, obtaining product, is 2-trifluoromethyl-4-nitrophenyl thioether, and yield is 90%;
Second step: in there-necked flask, add 2-trifluoromethyl-4-nitrophenyl thioether 41.2g (0.1mol), add again 40% sulfuric acid 300mL, under stirring, slowly add sodium dichromate 99 89.39g (0.3mmol) in batches, be warming up to 100 ℃ of reactions 2 hours, be cooled to room temperature, filter out solid impurity, splash in pure water and separate out thick product, after filtering, clear water washing is three times, dry rear with ethyl alcohol recrystallization, obtain 2,2 '-bis-(trifluoromethyl)-4,4 '-dinitrophenyl sulfone, yield is 96%.
The 3rd step: in there-necked flask, add 2-trifluoromethyl-4 nitrophenyl sulfone 44.43g (0.1mol), palladium-carbon catalyst 0.45g; pour ethanol 500mL into; open and stir, under nitrogen protection, drip hydrazine hydrate 50.06g (1mol), heating reflux reaction 5 hours; product is through heat filtering; solvent evaporated, obtains head product, with aqueous ethanolic solution, makes solvent recrystallization; obtain the finished product 2-trifluoromethyl-4-aminophenyl sulfone, yield is 92%.
Product 2-trifluoromethyl-4-nitrophenyl thioether of synthesized, 2,2 '-bis-(trifluoromethyl)-4, the nuclear magnetic spectrum of 4 '-dinitrophenyl sulfone, 2-trifluoromethyl-4-aminophenyl sulfone is shown in accompanying drawing 1,2,4.
The first step: in there-necked flask, add the chloro-5 nitro-trifluoromethyl toluene 22.6g (0.1mol) of 2-, nine hydrated sodium sulfide 12g (0.05mol), N, N-N,N-DIMETHYLACETAMIDE 200mL, open and stir, be warmed up to 165 ℃ of back flow reaction 12 hours under nitrogen protection, cold filtration obtains yellow solid, use respectively clear water and washing with alcohol, obtaining product, is 2-trifluoromethyl-4-nitrophenyl thioether, and yield is 92%;
Second step: in there-necked flask, add 2-trifluoromethyl-4 nitrophenyl thioether 41.23g (0.1mol), palladium-carbon catalyst 0.41g, pour ethanol 400mL into, open and stir, under nitrogen protection, drip hydrazine hydrate 50.06g (1mol), heating reflux reaction 10 hours, product is through heat filtering, solvent evaporated, obtains head product, with aqueous ethanolic solution, makes solvent recrystallization, obtain 2-trifluoromethyl-4-aminophenyl-thioether, yield is 90%;
The 3rd step: in there-necked flask, add 2-trifluoromethyl-4-aminophenyl-thioether 35.23g (0.1mol), then add 200mL acetic acid, under stirring, add chromium trioxide 60g (0.6mol) in batches, be heated to 50 ℃ of reactions 3 hours, be cooled to room temperature, filter out solid impurity, reaction solution splashes in pure water and separates out thick product, and clear water washing head product, uses toluene recrystallization after being dried again, obtain 2, two (trifluoromethyl)-4 of 2-, 4 '-diamino-phenyl sulfone, yield is 86%.
The nuclear magnetic spectrum of product 2-trifluoromethyl-4-nitrophenyl thioether of synthesized, 2-trifluoromethyl-4-aminophenyl-thioether, 2-trifluoromethyl-4-aminophenyl sulfone is shown in accompanying drawing 1,3,4.
The first step: in there-necked flask, add the chloro-5 nitro-trifluoromethyl toluene 22.6g (0.1mol) of 2-, nine hydrated sodium sulfide 12g (0.05mol), N, N-N,N-DIMETHYLACETAMIDE 200mL, open and stir, be warmed up to 165 ℃ of back flow reaction 12 hours under nitrogen protection, cold filtration obtains yellow solid, use respectively clear water and washing with alcohol, obtaining product, is 2-trifluoromethyl-4-nitrophenyl thioether, and yield is 92%;
Second step: in there-necked flask, add 2-trifluoromethyl-4 nitrophenyl thioether 41.23g (0.1mol), palladium-carbon catalyst 0.41g, pour ethanol 400mL into, open and stir, under nitrogen protection, drip hydrazine hydrate 50.06g (1mol), heating reflux reaction 10 hours, product is through heat filtering, solvent evaporated, obtains head product, with aqueous ethanolic solution, makes solvent recrystallization, obtain 2-trifluoromethyl-4-aminophenyl-thioether, yield is 90%;
The 3rd step: in there-necked flask, add 2-trifluoromethyl-4-aminophenyl-thioether 35.23g (0.1mol), then add 300mL acetic acid, under stirring, add potassium periodate 34.7g (0.4mmol) in batches, be heated to 50 ℃ of reactions 3 hours, be cooled to room temperature, filter out solid impurity, reaction solution splashes in pure water and separates out thick product, and clear water washing head product, uses toluene recrystallization after being dried again, obtain 2, two (trifluoromethyl)-4 of 2-, 4 '-diamino-phenyl sulfone, yield is 92%.
The nuclear magnetic spectrum of product 2-trifluoromethyl-4-nitrophenyl thioether of synthesized, 2-trifluoromethyl-4-aminophenyl-thioether, 2-trifluoromethyl-4-aminophenyl sulfone is shown in accompanying drawing 1,3,4.
Embodiment 6
In this example, adopt two (trifluoromethyl)-4 of 2,2-, 4 '-diamino-phenyl sulfone (SFTA), hexafluorodianhydride (6FDA) carry out polyreaction, prepare Kapton, comprise the following steps:
The first step: with N, dinethylformamide is by diamines 2, two (trifluoromethyl)-4 of 2-, 4 '-diamino-phenyl sulfone 1.9215g (0.005mol) is dissolved in polyreaction bottle completely, under nitrogen protection, dianhydride hexafluorodianhydride 2.2212g (0.005mol) is added in batches, controlling solid content is 20%, reacts 12 hours under mechanical stirring, obtains transparent, thick polyamic acid solution;
Second step: standing 10 hours of the polyamic acid solution of gained, after wherein bubble is eliminated, is filmed on clean substrate, first dry at 80 ℃ 1 hour, take again 30 ℃ as a ladder, be warmed up to 280 ℃ of bakings 60 minutes, naturally cooling then, demoulding obtains Kapton.
In this embodiment, resulting Kapton structural formula is:
Polymkeric substance is carried out to molecular weight test, and to obtain polymerization degree n be 19.
The Kapton obtaining is carried out to Fourier infrared, the tests such as DSC, TGA.Fourier's infrared test the results are shown in accompanying drawing 5, in infared spectrum at 1787cm
-1, 1732cm
-1occur bimodally, prove the existence of the imide ring on molecular chain.DSC test result is shown in accompanying drawing 7, and recording second-order transition temperature is 229.43 ℃.TGA test result is shown in accompanying drawing 9, and the temperature that thermal weight loss is 10% is 500 ℃.The UV, visible light light transmission cutoff wavelength that mensuration obtains film is 337nm, in 400nm place transmitance, is 83%.
In example, adopt two (trifluoromethyl)-4 of 2,2-, 4 '-diamino-phenyl sulfone (SFTA), 1,2,4,5-hexanaphthene dianhydride (CHDA) carries out polyreaction, prepares Kapton, comprises the following steps:
The first step: with N, N-N,N-DIMETHYLACETAMIDE is by diamines 2, two (trifluoromethyl)-4 of 2-, 4 '-diamino-phenyl sulfone 1.9215g (0.005mol) is dissolved in polyreaction bottle completely, under nitrogen protection by dianhydride 1,2,4,5-hexanaphthene dianhydride 1.1208g (0.005mol) adds in batches, and controlling solid content is 24%, under mechanical stirring, react 12 hours, obtain transparent, thick polyamic acid solution;
Second step: standing 10 hours of the polyamic acid solution of gained, after wherein bubble is eliminated, is filmed on clean substrate, first dry at 80 ℃ 1 hour, take again 30 ℃ as a ladder, be warmed up to 280 ℃ of bakings 60 minutes, naturally cooling then, demoulding obtains Kapton.
In this embodiment, resulting Kapton structural formula is:
Polymkeric substance is carried out to molecular weight test, and to obtain polymerization degree n be 16.
The Kapton obtaining is carried out to Fourier infrared, the tests such as DSC, TGA.Fourier's infrared test the results are shown in accompanying drawing 5, in infared spectrum at 1789cm
-1, 1713cm
-1occur bimodally, prove the existence of the imide ring on molecular chain.DSC test result is shown in accompanying drawing 7, and recording second-order transition temperature is 287.31 ℃.TGA test result is shown in accompanying drawing 9, and the temperature that thermal weight loss is 10% is 498 ℃.The UV, visible light light transmission cutoff wavelength that mensuration obtains film is 310nm, in 400nm place transmitance, is 87%.
Claims (2)
1. a preparation method for flexible transparent polyimide film, comprises the following steps:
Step a: with strong polar non-proton organic solvent by compound 2 claimed in claim 1,2 '-bis-(trifluoromethyl)-4,4 '-diamino-phenyl sulfone is dissolved in polymerization container completely, slowly add again the dianhydride monomer of equimolar amount, the solid content of controlling reaction solution is 10-70%, under mechanical stirring, react 1-48 hour, obtain the fluorine-containing polyamic acid solution of transparent, thick sulfuryl, described dianhydride monomer is selected from one or two or more kinds in following A-Q compound:
Step b: by the fluorine-containing polyamic acid solution of the sulfuryl of gained standing 1-48 hour after wherein bubble is eliminated, on clean substrate, film, first at 70-90 ℃, dry 1-3 hour, take again 20-50 ℃ as a ladder, be warmed up to 200-300 ℃ of baking 1-120 minute, then naturally cooling, puts into the sulfuryl fluorinated polyimide film that the standing 1-2 of water hour demoulding obtains and is flexible transparent polyimide film.
2. the preparation method of flexible transparent polyimide film according to claim 1, is characterized in that, strong polar non-proton organic solvent used is DMF, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO) or N-Methyl pyrrolidone.
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