CN1640914A - Method for preparing aniline oligomer/polyimide gradient film - Google Patents
Method for preparing aniline oligomer/polyimide gradient film Download PDFInfo
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- CN1640914A CN1640914A CN 200410011354 CN200410011354A CN1640914A CN 1640914 A CN1640914 A CN 1640914A CN 200410011354 CN200410011354 CN 200410011354 CN 200410011354 A CN200410011354 A CN 200410011354A CN 1640914 A CN1640914 A CN 1640914A
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- polyimide
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Abstract
The present invention is the preparation process of gradient aniline oligomer/polyimide film. The preparation process includes: 1) dissolving diamine in organic solvent to obtain transparent liquid, adding maleic anhydride in the molar amount of 0.1-5 time that of diamine to solid content in the solution of 1-50 %, stirring at room temperature for 2-24 hr to obtain transparent ropy polyamido acid solution; 2) adding aniline oligomer of 0.005-0.1 weight of the polyamido acid, ultrasound mixing for 10-30 hr to obtain greenish-black transparent ropy liquid; and 3) scraping film on support board, vacuum stoving at 20-400 deg.c in a temperature program to obtain the gradient aniline oligomer/polyimide film. The film has excellent electric anisotropy in two sides and may find wide application in microelectronic material.
Description
Technical field:
The invention belongs to polymeric material field, be specifically related to the preparation method of a kind of novel aniline oligomer/polyimide gradient film, the gradient film that is prepared by this method has application widely aspect the high-performance electromagnetic material.
Background technology:
Conducting polymer is an emerging field of polymer science, especially eigenmode conductive conjugated polymer has wide application prospect in fields such as chemical power source, electromagnetic shielding, antistatic, information storage and processing, electrochromic material, transmitter, stealth materials.In many conductive conjugated polymers, the polyaniline raw material is cheap and easy to get, preparation is simple and convenient, chemical property is excellent and chemical stability good, is considered to the conductive polymers that most possibly is applied in practice.But polyaniline has the inflexible conjugated chain causes its workability poor, and thermal degradation and can not melting can not be by the processing of means such as conventional extrusion molding, injection molding; Polyaniline (the polymkeric substance of aniline in addition, molecular weight is higher) the non-constant of solvability in organic solvent, can not find optimum solvent dissolves it fully, and there is defective in its polymer molecule, compare with it, (oligopolymer also is the polymkeric substance of aniline to the oligopolymer of monodispersed conductive polymers, and the polymerization degree is very low, molecular formula is as Scheme 1 hereinafter) molecular weight ratio is less, thereby can be dissolved in some ordinary organic solvents preferably; On the other hand from application point of view, the oligopolymer of monodispersed conductive polymers a kind of novel material that has application prospect of himself also can yet be regarded as, the oligopolymer that the research of oligopolymer has been disclosed conductive polymers should have the better application prospect than its polymkeric substance.
Polyaniline oligomer has as above multiple excellent properties, but it has only dopant states just to have electroconductibility, and polyaniline oligomer normal temperature is down the Powdered mechanical property that almost out of the question has, can't directly use, people have explored number of ways, wherein blending and modifying is simple and easy to do, easily is applied to again produce.Polyimide is owing to have the excellent comprehensive performance, as high second-order transition temperature, excellent solvent resistance, low relatively dielectricity, excellent electric insulating and mechanical property etc., be widely used in electronics, microelectronics, photoelectricity and aerospace field.The present invention is based on these excellent properties and the good application background of aniline oligomer that polyimide has, select polyimide as base material, aniline oligomer is compound in the polyamic acid, through the hot imidization process, make aniline oligomer be gathered in the film surface by solvent evaporation, thereby (being component concentration changes in gradient from the end to end of film to form the gradient gradual change, and be continuous variation), the new special mould material of double-sided anisotropic, not only kept the excellent specific property of polyimide but also given that it is functional.
Summary of the invention:
The objective of the invention is to prepare the new type functional material of a kind of two sides electricity opposite sex, have the excellent specific property of the two sides electricity opposite sex, aspect microelectronic material, have widely and use by this material of gradient film of this method preparation.
Preparation method of the present invention is as follows:
(1) getting diamines is dissolved in (induction stirring) organic solvent and obtains colourless transparent liquid, slow again adding and diamines mol ratio are 0.1～5: 1 dianhydride, solid content 1～50% in the solvent, and then stirring at room 2～24h obtains light yellow transparent thick liquid-polyamic acid solution;
(2) get above-mentioned product, the polyamic acid mass ratio is 0.005～0.1: 1 aniline oligomer in adding and the solution, and ultrasonic mixing 10～30 hours obtains blackish green transparent thick liquid;
(3) method that goes up with blade coating in back up pad (as sheet glass, iron plate, steel plate, alloy sheets etc.) prepares film (as scraping out with scraper, scraper is the instrument that a kind of commonly used being used for prepares film), put into baking oven and under vacuum condition, carry out the temperature programming processing, thereby obtain aniline oligomer/polyimide gradient film 20 ℃～400 ℃ temperature ranges.
Diamines described in the aforesaid method is 4,4 '-diamines yl diphenyl ether, 3,4 '-diaminodiphenyl oxide, 3,3 '-diaminodiphenyl oxide or 1,4,-(3-amino-benzene oxygen) benzene, 1,4 ,-(4-amino-benzene oxygen) benzene, 1,3,-(3-amino-benzene oxygen) benzene or 1,3, a kind of in-(4-amino-benzene oxygen) benzene.
Described dianhydride is 3,3 ', 4,4 '-BPDA, 2,3 ', 3,4 '-BPDA, 2,3 ', 2, a kind of in 3 '-BPDA, pyromellitic acid dianhydride (PMDA) or the phenyl ether tetracarboxylic dianhydride (ODPA).
Described organic solvent is N, a kind of in dinethylformamide (DMF), N,N-dimethylacetamide (DMAc) or the N-Methyl pyrrolidone (NMP) or two or three mixed solvent wherein.
Described aniline oligomer can be benzene end-blocking or the end capped aniline oligomer of amine, and wherein the end capped aniline oligomer effect of benzene is relatively good, especially the end capped aniline tetramer of benzene.
As preferred implementation of the present invention, in the aforesaid method, the mol ratio of dianhydride and diamines consumption is 0.2～2.5: 1; Solid content is 3～20% in the solvent; Benzene ended aniline tetramer and polyamic acid mass ratio are 0.008～0.08: 1.
As further again preferred implementation of the present invention, in the aforesaid method, the mol ratio of dianhydride and diamines consumption is 0.8～1.5: 1; Solid content is 7～15% in the solvent; Benzene ended aniline tetramer and polyamic acid mass ratio are 0.01～0.05: 1.
The characteristics of patent of the present invention:
1, the present invention selects the end capped aniline tetramer of benzene (Scheme 1), and this compounds has satisfactory stability in polyamic acid, not with diamines and dianhydride monomer reaction, and solvable (being dissolved in DMF, DMAc or THF equal solvent).
2, polyimide preparation involved in the present invention comprises following two steps: synthetic and temperature programming hot imidization two portions of polyamic acid.
Polyimide is to be raw material with diamines and dianhydride, and as solvent, its structure and preparation method are with strong polar aprotic solvent such as DMF, DMAc, NMP etc.:
3, patent of the present invention is to add a certain amount of aniline tetramer in polyamic acid, make it to be distributed to uniformly in the polyamic acid, prepare mould material then, by temperature programming with the polyamic acid imidization, aniline is taken to surface one side of film by solvent in temperature-rise period, aniline oligomer is enriched in the surface of film, distribution gradient in Kapton.
4, the film that obtains of the present invention has double-sided anisotropic (aniline oligomer has conduction property, and polyimide is a megohmite, the gradient film two sides electric property that obtains has very big-difference), in the premium properties that has kept polyimide (as thermal characteristics and mechanical property), also have some performances (as conductivity, antiseptic property etc.) of aniline concurrently.
Description of drawings
Fig. 1: the two sides reflection ultraviolet-visible light spectrogram of gradient film
Fig. 1 (1) is the two sides reflection ultraviolet-visible light spectrogram of 1% gradient film for doping,
Fig. 1 (2) is the two sides reflection ultraviolet-visible light spectrogram of 2% gradient film for doping,
Fig. 1 (3) is the two sides reflection ultraviolet-visible light spectrogram of 5% gradient film for doping;
Fig. 2: doping is 1% gradient film side sem photograph;
Fig. 3: doping is the DSC scintigram of 1% gradient film;
Fig. 4: the thermal weight loss of gradient film (TGA) graphic representation under air;
Fig. 4 (1) is thermal weight loss (TGA) graphic representation of not doping,
Fig. 4 (2) is thermal weight loss (TGA) graphic representation of 1% gradient film for doping;
Table 1: contact angle numerical value (HARVEY, the MAIN﹠amp of gradient film; CO.LTD. FT 200 types of Sheng Chaning)
Air surface 74.90 67.84 74.47 69.75
Glass surface 75.30 73.45 80.27 65.27
Table 2: the mechanics Elongation test result of gradient film (the AG-I type electronic universal experimental machine that adopts Tianjin, island company to produce)
Tetramer modulus breaking tenacity elongation at break
Content GPa MPa %
0％ 2.7 103 32.8
1％ 2.9 107 25.3
2％ 2.8 104 14.9
5％ 2.9 106 11.2
As shown in Figure 1, the ultraviolet on Gradient Film two sides-visible absorbance figure is different, proves in four of air one side Aggressiveness content is more, and is lower at the content of glass plate one side, proved the component content difference on two sides, wherein 1% and 2% difference is apparent in view, and the double-sided anisotropic of Gradient Film is obvious.
It is 1%, 2%, 5% film that Fig. 1 (1), (2), (3) represent respectively doping, curve 1 representative Doping is the absorption curve of 0% film; Curve 2 represents the absorption curve of the air surface of film; Curve 3 representatives The absorption curve of the glass surface of film; Curve 4 represents the absorption curve of air.
Fig. 2 is the side sem photograph of 1% Gradient Film, can see that the two sides is obviously different.
Table 1 is the contact angle test result of Gradient Film, and it is obviously poor that we can see that two sides contact angle numerical value has Not, and parallel numerical difference between is few, visible two sides difference.
To sum up, by reflection ultraviolet-visible, ESEM and four kinds of characterization methods of contact angle, proved target Product---aniline oligomer/polyimide gradient film two sides constituent and content difference thereof are obvious.
As shown in Figure 3, be the DSC scintigram of aniline oligomer-polyimide gradient film, by this figure we The glass transition temperature that can find out 1% Gradient Film is 272 ℃, has proved that this Gradient Film has kept the polyamides Asia The hot property that amine is good has higher serviceability temperature.
Fig. 4 is the hot weightless picture of aniline oligomer/polyimide gradient film under air, Fig. 4 (1) and Fig. 4 (2) shown in, be respectively the TGA curve map of 0% and 1% Gradient Film under air, visible 1% Gradient Film 5% thermal weight loss temperature under air can reach about 530 ℃, and this has shown that this material has the thermally-stabilised of excellence Property and thermo oxidative stability.
Table 2 is the mechanical stretch The performance test results of aniline oligomer/polyimide gradient film, can see this Gradient Film has kept the good mechanical property of polyimide matrix material.
To sum up, by DSC, TGA and three kinds of characterization methods of mechanical stretch test, proved target product---The hot property that aniline oligomer/polyimide gradient film is good and mechanical property.
To sum up, by Gradient Film is carried out performance test, prove aniline oligomer/polyamides that we are prepared The imines Gradient Film is dispersed, and better double-sided anisotropic is obvious, and mechanics and thermal property are fine, has the good application can Energy and prospect.
Embodiment
The preparation embodiment of aniline oligomer-polyimide gradient film:
Embodiment 1:
At electromagnetic mixing apparatus, in the beaker 4,4 '-diaminodiphenyl oxide (4,4 '-ODA) 8g (0.04mol) is dissolved in 150ml N, N-N,N-DIMETHYLACETAMIDE (DMAc) obtains colourless transparent liquid, slowly adds 3,3 ' again, 4,4 '-BPDA (s-BPDA, 11.76g, 0.04mol), then stirring at room is 4 hours, obtains light yellow transparent thick liquid-polyamic acid solution.
(wherein the polyamic acid solid content is 10% to get the above-mentioned polyamic acid solution of 10.30g, be 1.03g) sneak into 10.3mg benzene ended aniline tetramer, utilize ultrasonic mixing 20h, obtain blackish green transparent thick liquid [w (the aniline tetramer)/w (polyamic acid)=1%].
Scrape 300 μ m thick films with scraper on sheet glass, put into baking oven, temperature programming is handled: (40 ℃/1 hour, 60 ℃/1 hour, 80 ℃/1 hour, 150 ℃/1 hour, 200 ℃/1 hour, 250 ℃/1 hour, under the vacuum), obtain doping that thickness is about 30 μ m and be 1% gradient film.
Prove that after tested this new membrane dispersion of materials is better, the film double-sided anisotropic that obtains is obvious, and mechanics and thermal property are fine, has broad application prospects, and as seen the film that obtains under this processing condition is better.
Embodiment 2:
Method such as embodiment 1 bring up to 20.6mg with adulterated benzene ended aniline tetramer, obtain its doping and be 2% gradient film.
Embodiment 3:
Method such as embodiment 1 bring up to 51.5mg with adulterated benzene ended aniline tetramer, and its doping is 5% gradient film.
Embodiment 4:
Method such as embodiment 1 replace N,N-dimethylacetamide (DMAc) with N-Methyl pyrrolidone (NMP) 150ml, and the gained mould material is better dispersed, and the film double-sided anisotropic that obtains is obvious, and mechanics and thermal property are fine.
Embodiment 5:
Method such as embodiment 1 use N, and dinethylformamide (DMF) 150ml replaces N,N-dimethylacetamide (DMAc), and the gained mould material is better dispersed, and the film double-sided anisotropic that obtains is obvious, and mechanics and thermal property are fine.
Embodiment 6:
Method such as embodiment 1, with 3,4 '-diaminodiphenyl oxide (3,4 '-ODA, 0.04mol 8g) replaces 4,4 '-diaminodiphenyl oxide (4,4 '-ODA, 0.04mol 8g).Glass transition temperature Tg decline 5 degree of film.
Embodiment 7:
Method such as embodiment 1, with 3,3 '-diaminodiphenyl oxide (3,3 '-ODA, 0.04mol 8g) replaces 4,4 '-diaminodiphenyl oxide (4,4 '-ODA, 0.04mol 8g).Being changed into by crystal habit of Kapton is unformed, and second-order transition temperature decline 12 degree.
Embodiment 8:
Method such as embodiment 1, with 1,4 ,-(3-amino-benzene oxygen) benzene (1,4,3-APB, 0.04mol 11.76g) replaces 4,4 '-diaminodiphenyl oxide (4,4 '-ODA, 0.04mol 8g).Being changed into by crystal habit of Kapton is unformed, and second-order transition temperature decline 20 degree.
Embodiment 9:
Method such as embodiment 1, with 1,4 ,-(4-amino-benzene oxygen) benzene (1,4,4-APB, 0.04mol 11.76g) replaces 4,4 '-diaminodiphenyl oxide (4,4 '-ODA, 0.04mol 8g).Second-order transition temperature decline 5 degree.
Embodiment 10:
Method such as embodiment 1, with 1,3 ,-(3-amino-benzene oxygen) benzene (1,3,3-APB, 0.04mol 11.76g) replaces 4,4 '-diaminodiphenyl oxide (4,4 '-ODA, 0.04mol 8g).Being changed into by crystal habit of Kapton is unformed, and second-order transition temperature decline 60 degree.
Embodiment 11:
Method such as embodiment 1, with 2,3 ', 3,4 '-BPDA (a-BPDA, 11.76g 0.04mol) replace 3,3 ', 4, and 4 '-BPDA (s-BPDA, 11.76g, 0.04mol).Being changed into by crystal habit of Kapton is unformed, and second-order transition temperature increases by 50 degree.
Embodiment 12:
Method such as embodiment 1, with 2,3 ', 2,3 '-BPDA (i-BPDA, 11.76g 0.04mol) replace 3,3 ', 4, and 4 '-BPDA (s-BPDA, 11.76g, 0.04mol).Being changed into by crystal habit of Kapton is unformed, and second-order transition temperature increases by 70 degree.
Embodiment 13:
Method such as embodiment 1, with pyromellitic acid dianhydride (PMDA, 8.72g 0.04mol) replace 3,3 ', 4,4 '-BPDA (s-BPDA, 11.76g, 0.04mol).The Kapton color burn.
Embodiment 14:
Method such as embodiment 1, with the phenyl ether tetracarboxylic dianhydride (ODPA, 12.4g 0.04mol) replace 3,3 ', 4,4 '-BPDA (s-BPDA, 11.76g, 0.04mol).The Kapton color shoals, and second-order transition temperature decline 8 degree.
Claims (7)
1, the preparation method of a kind of aniline oligomer/polyimide gradient film, its step is as follows:
(1) get diamines and be dissolved in and obtain colourless transparent liquid in the solvent, slowly adding with the diamines mol ratio is 0.1～5: 1 dianhydride again, and solid content 1～50% in the solvent, and then stirring at room 2～24h obtains light yellow transparent thick liquid-polyamic acid solution;
(2) get above-mentioned product, the polyamic acid mass ratio is 0.005～0.1: 1 aniline oligomer in adding and the solution, and ultrasonic mixing 10～30 hours obtains blackish green transparent thick liquid;
(3) method with blade coating prepares film on back up pad, puts into baking oven and carry out the temperature programming processing 20 ℃～400 ℃ temperature ranges under vacuum condition, thereby obtain aniline oligomer/polyimide gradient film.
2, the preparation method of aniline oligomer as claimed in claim 1/polyimide gradient film, it is characterized in that: diamines is 4,4 '-diamines yl diphenyl ether, 3,4 '-diaminodiphenyl oxide, 3,3 '-diaminodiphenyl oxide or 1,4 ,-(3-amino-benzene oxygen) benzene, 1,4,-(4-amino-benzene oxygen) benzene, 1,3 ,-(3-amino-benzene oxygen) benzene or 1,3, a kind of in-(4-amino-benzene oxygen) benzene.
3, the preparation method of aniline oligomer as claimed in claim 1/polyimide gradient film, it is characterized in that: dianhydride is 3,3 ', 4,4 '-BPDA, 2,3 ', 3,4 '-BPDA, 2,3 ', 2, a kind of in 3 '-BPDA, pyromellitic acid dianhydride (PMDA) or the phenyl ether tetracarboxylic dianhydride (ODPA).
4, the preparation method of aniline oligomer as claimed in claim 1/polyimide gradient film is characterized in that: aniline oligomer is the end capped aniline tetramer of benzene.
5, the preparation method of aniline oligomer as claimed in claim 1/polyimide gradient film, it is characterized in that: employed organic solvent is N, a kind of or wherein two or three mixing in dinethylformamide, N,N-dimethylacetamide or the N-Methyl pyrrolidone.
6, as the preparation method of any one described aniline oligomer of claim 1-5/polyimide gradient film, it is characterized in that: the mol ratio of dianhydride and diamines consumption is 0.2～2.5: 1; Solid content is 3～20% in the solvent; Benzene ended aniline tetramer and polyamic acid mass ratio are 0.008～0.08: 1.
7, the preparation method of aniline oligomer as claimed in claim 6/polyimide gradient film, it is characterized in that: the mol ratio of dianhydride and diamines consumption is 0.8～1.5: 1; Solid content is 7～15% in the solvent; Benzene ended aniline tetramer and polyamic acid mass ratio are 0.01～0.05: 1.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103552196A (en) * | 2013-11-25 | 2014-02-05 | 河南理工大学 | Preparation method of macromolecular layered material |
| CN105419350A (en) * | 2015-12-22 | 2016-03-23 | 齐鲁工业大学 | Monoepoxy-blocked polysiloxane modified gelatin gradient film prepared by substrate adjusting method |
| CN105542204A (en) * | 2015-12-22 | 2016-05-04 | 齐鲁工业大学 | Method for preparing single-epoxy terminated polysiloxane modified gelatin amphiphilic film |
| CN105906813A (en) * | 2016-06-05 | 2016-08-31 | 吉林大学 | Method for preparing regular block copolymerization polyimide siloxane single-layer film |
-
2004
- 2004-12-15 CN CN 200410011354 patent/CN1246370C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103552196A (en) * | 2013-11-25 | 2014-02-05 | 河南理工大学 | Preparation method of macromolecular layered material |
| CN105419350A (en) * | 2015-12-22 | 2016-03-23 | 齐鲁工业大学 | Monoepoxy-blocked polysiloxane modified gelatin gradient film prepared by substrate adjusting method |
| CN105542204A (en) * | 2015-12-22 | 2016-05-04 | 齐鲁工业大学 | Method for preparing single-epoxy terminated polysiloxane modified gelatin amphiphilic film |
| CN105419350B (en) * | 2015-12-22 | 2018-06-08 | 齐鲁工业大学 | Substrate adjusts method and prepares monocyclic oxygen terminated polysiloxane modified gelatin Gradient Film |
| CN105906813A (en) * | 2016-06-05 | 2016-08-31 | 吉林大学 | Method for preparing regular block copolymerization polyimide siloxane single-layer film |
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