CN102167824A - Polyimide film and preparation method and applications thereof - Google Patents
Polyimide film and preparation method and applications thereof Download PDFInfo
- Publication number
- CN102167824A CN102167824A CN2011100253105A CN201110025310A CN102167824A CN 102167824 A CN102167824 A CN 102167824A CN 2011100253105 A CN2011100253105 A CN 2011100253105A CN 201110025310 A CN201110025310 A CN 201110025310A CN 102167824 A CN102167824 A CN 102167824A
- Authority
- CN
- China
- Prior art keywords
- amino
- formula
- compound
- preparation
- gained
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses a polyimide film and a preparation method and applications thereof. The compound forming the polyimide film is the compound of which structural general formula is shown in the formula I. The preparation method of polyimide is as follows: aromatic dianhydride 2,3,3',4'-diphenyl ether tetracarboxylic acid dianhydride (aODPA) and a series of aromatic diamine monomers are used as raw materials to prepare polyimide resin through chemical imidization. The polyimide film prepared by the technology has good optical transparency, low solar absorptivity-emissivity ratio and good thermal stability, and can be used to prepare the thermal protection device of the spacecraft, the solar cell array substrate and the antenna reflector/collector or solar sail and have important application value.
Description
Technical field
The invention belongs to space environment stable polymers material field, relate to a kind of Kapton and preparation method thereof and application with high transparent and low sun absorptivity-emissivity ratio.
Background technology
Spacecraft often will be exposed in operational process in the complicated space environment, as the atomic oxygen in high cold cycle, ultraviolet and deep ultraviolet radiation, charged particle radiation, universe micronic dust and fragment and the Low Earth Orbit (LEO) etc.These rigorous environment can cause the degraded of spacecraft surface and inner polymeric material, thereby badly influence at the life-span of rail spacecraft (Dever J, Banks B, Groh K D, Miller S.Degradation of spacecraft materials, in Handbook of Environmental Degradation of Materials, Kuta M (ed.), William Andrew, New York, 2005, pp 465～501).In order to prolong, need to protect and reinforce spacecraft in the work-ing life of rail spacecraft.Polyimide (PI) film is exactly a base polymer of developing at the thermal protection of spacecraft assembly.But coventional type PI film, as poly-(pyromellitic acid anhydride-diaminodiphenyl oxide) (PMDA-ODA) owing to there is stronger conjugation in its molecular structure between molecular chain, thus film transparent relatively poor, sun uptake factor is higher.These unfavorable factors have all limited its thermal protection at the space vehicle optical module.
Generally speaking, be used for thermo-lag polymeric coating, its sun absorptivity-emissivity ratio is low more, big more (the Zhao Feiming of temperature drop degree that can realize then at aircraft surface, Zhang Lianzheng, Ceng Yibing, Wang Hui, Shi Suxing, low sun uptake factor, high thermal emissivity organosilicon thermal control coating progress, aerospace material technology, 1998,3:11～14,48).At coventional type PI the film relatively poor relatively transparency and high sun uptake factor, people have attempted multiple modification approach.For example, US National Aeronautics and Space Administration (NASA) has developed a series of high transparent PI films since the eighties in 20th century.Wherein the structure of LaRC-CP1 and CP2 is as shown below.This two classes material is at the space telescope of future generation (NGST) of NASA but plans and the PI material of steady operation under space environment of exploitation.Test result shows that the LaRC-CP1 film can be stablized use more than 10 years in geostationary orbits (GEO) environment.
2010, Japan succeeded in sending up IKAROS solar sail experimental spacecraft, and solar sail wherein is that the PI film of 7.5 μ m is made by thickness.This film is by 2,3,3 ', 4 '-phenyl ether tetracarboxylic dianhydride (aODPA) gets with 4 (ODA) polymerization.This material not only has good space and environment stability, and has a good thermoplastic feature, (the Yokota R that can adopt the technology of heat sealing to process, Suzuki M, Miyauchi M, Ishida Y.Heat sealable, novel asymmetric aromatic polyimide having excellent space environmental stability.The fourth international symposium on engineering plastics, Dalian, Liaoning, China, 2009, pp80～81).
Though the report of high transparent, space environment stability PI film has been arranged in the document at present.But all there is certain performance deficiency in the material of being reported.For example, though the LaRC-CP2 film has the good optical transparency, the second-order transition temperature of its film lower (209 ℃).Though aODPA-ODA type PI film has the better space environmental stability, the optical transparence of this film is relatively poor relatively, is difficult to satisfy the demand of space vehicle optical module.
Summary of the invention
The purpose of this invention is to provide a kind of Kapton and preparation method thereof and application.
Compound shown in the formula I general structure provided by the invention,
(formula I)
In the described formula I general structure, Ar is selected from any one in the following radicals:
N is the integer of 1-100, specifically can be the integer of 20-30 or the integer of 30-40, the integer of preferred 20-40.
The method for preparing above-claimed cpd provided by the invention comprises the steps:
1) with aromatic diamine and aromatic series dianhydride 2,3,3 ', 4 '-phenyl ether tetracarboxylic dianhydride (aODPA) mixing in organic solvent reacts, reaction finishes and obtains the homogeneous liquid system;
2) adding diacetyl oxide and pyridine mixing react in described step 1) gained homogeneous liquid system, and reaction finishes and obtains compound shown in the described formula I.
In the step 1) of aforesaid method, described aromatic diamine is selected from 3,4-diaminodiphenyl oxide (3,4-ODA), 3,3 '-diaminodiphenyl oxide (3,3 '-ODA), 1, two (4 '-amino-benzene oxygen) benzene (1 of 4-, 4,4 '-APB), 1, two (4-amino-benzene oxygen) benzene (1,3 of 3-, 4-APB), 1, two (3 '-amino-benzene oxygen) benzene (1,3,3 '-APB) of 3-, 1, the two different propane of (4 '-amino-benzene oxygen) hexafluoro (BDAF) of 4-, 2,2 '-bis trifluoromethyl-4,4 '-benzidine (TFDB), 2, two [(4-amino-benzene oxygen) phenyl] diphenyl phosphine oxides (BADPO) of 5-, 3, at least a in two [(3-amino-benzene oxygen) phenyl] diphenyl phosphine oxides (m-BADPO) and 2 of 5-, 5-pair of [(4-amino-2-4-trifluoromethylphenopendant) phenyl] diphenyl phosphine oxide (BATFDPO); Described organic solvent is selected from N-Methyl pyrrolidone (NMP), meta-cresol, N, dinethylformamide (DMF), N, N-N,N-DIMETHYLACETAMIDE (DMAc), dimethyl sulfoxide (DMSO) (DMSO), cyclopentanone, pimelinketone, tetrahydrofuran (THF) and 1, at least a in the 2-ethylene dichloride, at least a in preferred N-Methyl pyrrolidone and the meta-cresol; Described aromatic series dianhydride 2,3,3 ', 4 '-phenyl ether tetracarboxylic dianhydride (aODPA) is 1.00 with the mol ratio of aromatic diamine: (0.95～1.00) is preferably 1.00: (0.99～1.00); In the reactions steps, the time is 10～30 hours, is preferably 20～25 hours, and temperature is 0-35 ℃, preferred 15-25 ℃;
Described step 2) in, described aromatic series dianhydride 2,3,3 ', 4 '-phenyl ether tetracarboxylic dianhydride (aODPA) is 1.00 with the mol ratio of described diacetyl oxide: (2.00～10.00), be preferably 1.00: 3.00, described aromatic series dianhydride 2,3,3 ', 4 '-phenyl ether tetracarboxylic dianhydride (aODPA) is 1.00 with the mol ratio of pyridine: (2.00～8.00) are preferably 1.00: 3.00; In the reactions steps, the time is 10～30 hours, is preferably 20～25 hours, and temperature is 0-35 ℃, preferred 15-25 ℃.
In actually operating, also can be as required with step 2) the product system of the described compound of gained formula I carries out following operation, to obtain corresponding resin product: with step 2) the products therefrom system reels off raw silk from cocoons in ethanol, obtains thread polyimide resin after the washing and drying; Also this resin product can be carried out film forming according to the film of routine, obtain corresponding film.
Resin or film that the described compound of formula I that is provided by the invention described above obtains; and this resin or the application of film in substrate, antenna reflector, antenna collector or the solar sail of the thermal protection device for preparing spacecraft, solar battery array, also belong to protection scope of the present invention.
The invention provides a kind of Kapton with high transparent and low sun absorptivity-emissivity ratio (being called for short the PI film) by aODPA and the preparation of a series of aromatic diamine monomer.This quasi-polyimide be with aromatic series dianhydride 2,3,3 ', 4 '-phenyl ether tetracarboxylic dianhydride (aODPA) and a series of aromatic diamine monomer are raw material, make by chemical imidization.At first, aODPA and aromatic diamine at polar aprotic solvent, are obtained polyamic acid as polymerization in the N-N-methyl-2-2-pyrrolidone N-(NMP), dehydration makes polyimide resin under diacetyl oxide/pyridine effect then.This resin dissolves in organic solvent, is obtained polyimide solution.This solution obtains flexible Kapton after applying, solidifying.PI film provided by the invention has asymmetric molecular structure on the one hand, and this structure has been destroyed the regularity of PI molecular structure effectively, thereby helps seeing through of visible light.In addition, it also contains flexible ehter bond, has further reduced the conjugation and the intermolecular strong interaction of its intramolecule electronic cloud, has further improved the transparency of PI film, has reduced its sun absorptivity-emissivity ratio.At last, this unsymmetrical structure can also be given PI good heat-resistant stability.Therefore, PI film provided by the invention is applicable to preparation lightweight, firm large size thin-film material, has important use and be worth in the spacecraft thermal control coating.
Description of drawings
Fig. 1 is the infrared spectra of embodiment 1 preparation gained Kapton.
Fig. 2 is the thermal weight loss spectrogram of embodiment 1 preparation gained Kapton.
Fig. 3 is the DSC spectrogram of embodiment 1 preparation gained Kapton.
Fig. 4 is the TMA spectrogram of embodiment 1 preparation gained Kapton.
Fig. 5 a and 5b are the ultraviolet-visible spectrum (thickness is respectively 10 μ m and 45 μ m) of embodiment 1 preparation gained Kapton.
Fig. 6 is the infrared spectra of embodiment 2 preparation gained Kaptons.
Fig. 7 is the thermal weight loss spectrogram of embodiment 2 preparation gained Kaptons.
Fig. 8 is the DSC spectrogram of embodiment 2 preparation gained Kaptons.
Fig. 9 is the TMA spectrogram of embodiment 2 preparation gained Kaptons.
Figure 10 a and 10b are the ultraviolet-visible spectrum (thickness is respectively 10 μ m and 45 μ m) of embodiment 2 preparation gained Kaptons.
Figure 11 is the infrared spectra of embodiment 3 preparation gained Kaptons.
Figure 12 is the thermal weight loss spectrogram of embodiment 3 preparation gained Kaptons.
Figure 13 is the DSC spectrogram of embodiment 3 preparation gained Kaptons.
Figure 14 is the TMA spectrogram of embodiment 3 preparation gained Kaptons.
Figure 15 a and 15b are the ultraviolet-visible spectrum (thickness is respectively 10 μ m and 45 μ m) of embodiment 3 preparation gained Kaptons.
Figure 16 is the infrared spectra of embodiment 4 preparation gained Kaptons.
Figure 17 is the thermal weight loss spectrogram of embodiment 4 preparation gained Kaptons.
Figure 18 is the DSC spectrogram of embodiment 4 preparation gained Kaptons.
Figure 19 is the TMA spectrogram of embodiment 4 preparation gained Kaptons.
Figure 20 a and 20b are the ultraviolet-visible spectrum (thickness is respectively 10 μ m and 45 μ m) of embodiment 4 preparation gained Kaptons.
Figure 21 is the infrared spectra of embodiment 5 preparation gained Kaptons.
Figure 22 is the thermal weight loss spectrogram of embodiment 5 preparation gained Kaptons.
Figure 23 is the DSC spectrogram of embodiment 5 preparation gained Kaptons.
Figure 24 is the TMA spectrogram of embodiment 5 preparation gained Kaptons.
Figure 25 a and 25b are the ultraviolet-visible spectrum (thickness is respectively 10 μ m and 45 μ m) of embodiment 5 preparation gained Kaptons
Embodiment
The present invention is further elaborated below in conjunction with specific embodiment, but the present invention is not limited to following examples.Described method is ordinary method if no special instructions.Described material all can get from open commercial sources if no special instructions.
Embodiment 1, by aODPA and 1, two (4-amino-benzene oxygen) benzene (144APB) preparation of 4-polyimide
1) in a 100ml there-necked flask of being furnished with nitrogen inlet, adds 0.01mol (2.9233g) 144APB and 15ml N-Methyl pyrrolidone (NMP).After stirring at room is dissolved it fully, add 0.01mol (3.1021g) aODPA, after 20 ℃ 24h is stirred in continuation down, obtain the homogeneous liquid system;
2) in step 1) gained homogeneous liquid system, add 0.03mol (2.86ml) diacetyl oxide and 0.03mol (2.45ml) pyridine, continue to stir 24h, reaction finishes and obtains polyimide compound shown in the formula II, this product system is yellow viscous solution, and the quality percentage composition of this target product is 18%;
3) with step 2) the yellow viscous solution of gained falls in 300ml ethanol, obtains white thread solid.Collect solid, and with after the washing with alcohol three times, in baking oven under the normal pressure 80 ℃ dried 12 hours, obtain thread polyimide resin;
4) take by weighing the thread polyimide resin solid 3g of step 3) gained, add NMP12g, treat that solid dissolves fully after, filter and obtain the polyimide solution that solid content is 20% (weight percent), this polymers soln is coated on the sheet glass, by 80 ℃/2h; 150 ℃/1h; 200 ℃/1h; 250 ℃/1h; 280 ℃/0.5h programmed heating heats up, be cooled to room temperature after, sheet glass is immersed in the water, peel off and obtain Kapton provided by the invention, structural formula is shown in the formula II:
(formula II)
Utilize the GPC method to predict, n is the integer of 20-30 in this compound.
The structure of above-mentioned Kapton and Performance Detection data are as follows:
Infrared spectra (cm
-1): 1779,1729,1493,1381,1114,745.
5% weightless temperature (℃, in the nitrogen): 531.
Second-order transition temperature (℃, DSC): 251.
Thermal expansivity (50-200 ℃, ppm/ ℃): 61.7.
Ultraviolet cut-on wavelength (nm): 354.
The transmittance at 500nm wavelength place (10 μ m, %): 92.5.
The transmittance at 500nm wavelength place (45 μ m, %): 63.5.
Sun absorption coefficient
S=0.33.
Hemispherical emissivity=0.67.
Absorptivity-emissivity ratio α
S/ ε
H=0.49.
Fig. 1 to Fig. 4 is respectively infrared spectra, thermal weight loss spectrogram, DSC spectrogram and the TMA spectrogram that this embodiment prepares the gained Kapton.Fig. 5 a and 5b prepare the ultraviolet-visible spectrum (thickness is respectively 10m and 45m) of gained Kapton for this embodiment.
As from the foregoing, this compound structure is correct, and has good thermostability, high transparent and low sun uptake factor.
Embodiment 2, by aODPA and 1, two (3-amino-benzene oxygen) benzene (133APB) preparation of 3-polyimide
1) in a 100ml there-necked flask of being furnished with nitrogen inlet, adds 0.01mol (2.9233g) 133APB and 15ml meta-cresol.After stirring at room is dissolved it fully, add 0.01mol (3.1021g) aODPA, after 25 ℃ 25h is stirred in continuation down, obtain the homogeneous liquid system;
2) in step 1) gained homogeneous liquid system, add 0.03mol (2.86ml) diacetyl oxide and 0.03mol (2.45ml) pyridine, continue to stir 25h, reaction finishes and obtains polyimide compound shown in the formula III, this product system is yellow viscous solution, and the quality percentage composition of this target product is 25%;
3) with step 2) the yellow viscous solution of gained falls in 300ml ethanol, obtains white thread solid, collect solid, and with after the washing with alcohol three times, normal pressure dried 12 hours in baking oven, obtained thread polyimide resin for 80 ℃;
4) take by weighing the thread polyimide resin solid 3g of step 3) gained, add meta-cresol 9g, treat that solid dissolves fully after, filter and obtain the polyimide solution that solid content is 25% (weight percent).This polymers soln is coated on the sheet glass, by 80 ℃/2h; 150 ℃/1h; 200 ℃/1h; 250 ℃/1h; 280 ℃/0.5h programmed heating.After being cooled to room temperature, sheet glass is immersed in the water, peels off and obtain Kapton provided by the invention, structural formula is shown in the formula III:
(formula III)
Utilize the GPC method to predict, n is the integer of 20-30 in this compound.
The structure of above-mentioned Kapton and Performance Detection data are as follows:
Infrared spectra (cm
-1): 1779,1721,1478,1377,1104,745.
5% weightless temperature (℃, in the nitrogen): 510.
Second-order transition temperature (℃, DSC): 185.
Thermal expansivity (50～200 ℃, ppm/ ℃): 54.4.
Ultraviolet cut-on wavelength (nm): 353.
The transmittance at 500nm wavelength place (10 μ m, %): 97.4.
The transmittance at 500nm wavelength place (45 μ m, %): 61.5.
Sun absorption coefficient
S=0.31.
Hemispherical emissivity ε
H=0.66.
Absorptivity-emissivity ratio α
S/ ε
H=0.47
Fig. 6 to Fig. 9 is respectively infrared spectra, thermal weight loss spectrogram, DSC spectrogram and the TMA spectrogram that this embodiment prepares the gained Kapton.Figure 10 a and 10b prepare the ultraviolet-visible spectrum (thickness is respectively 10 μ m and 45 μ m) of gained Kapton for this embodiment.
As from the foregoing, this compound structure is correct, and has good thermostability, high transparent and low sun uptake factor.
Embodiment 3, by aODPA and two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa (BDAF) preparation polyimide
1) in a 100ml there-necked flask of being furnished with nitrogen inlet, adds 0.01mol (5.1845g) BDAF and 15ml N-Methyl pyrrolidone (NMP).After stirring at room is dissolved it fully, add 0.01mol (3.1021g) aODPA, after 25 ℃ 20h is stirred in continuation down, obtain the homogeneous liquid system;
2) in step 1) gained homogeneous liquid system, add 0.03mol (2.86ml) diacetyl oxide and 0.03mol (2.45ml) pyridine, continue to stir 20h, reaction finishes and obtains polyimide compound shown in the formula IV, this product system is yellow viscous solution, and the quality percentage composition of target product is 18% shown in this formula IV;
3) with step 2) the yellow viscous solution of gained falls in 300ml ethanol, obtains white thread solid.Collect solid, and with after the washing with alcohol three times, in baking oven under the normal pressure 80 ℃ dried 12 hours, obtain thread polyimide resin;
4) take by weighing the thread polyimide resin solid 3g of step 3) gained, add NMP12g, treat that solid dissolves fully after, filter and obtain the polyimide solution that solid content is 20% (weight percent).This polymers soln is coated on the sheet glass, by 80 ℃/2h; 150 ℃/1h; 200 ℃/1h; 250 ℃/1h; 280 ℃/0.5h programmed heating.After being cooled to room temperature, sheet glass is immersed in the water, peels off and obtain Kapton provided by the invention, structural formula is shown in the formula IV:
Utilize the GPC method to predict, n is the integer of 20-30 in this compound.
The structure of above-mentioned Kapton and Performance Detection data are as follows:
Infrared spectra (cm
-1): 1781,1730,1474,1380,1114,745.
5% weightless temperature (℃, in the nitrogen): 525.
Second-order transition temperature (℃, DSC): 239.
Thermal expansivity (50～200 ℃, ppm/ ℃): 66.4.
Ultraviolet cut-on wavelength (nm): 355.
The transmittance at 500nm wavelength place (10 μ m, %): 97.6.
The transmittance at 500nm wavelength place (45 μ m, %): 78.3.
Sun absorption coefficient
S=0.29.
Hemispherical emissivity ε
H=0.66.
Absorptivity-emissivity ratio α
S/ ε
H=0.44.
Figure 11 to Figure 14 is respectively infrared spectra, thermal weight loss spectrogram, DSC spectrogram and the TMA spectrogram that this embodiment prepares the gained Kapton.Figure 15 a and 15b prepare the ultraviolet-visible spectrum (thickness is respectively 10 μ m and 45 μ m) of gained Kapton for this embodiment.
As from the foregoing, this compound structure is correct, and has good thermostability, high transparent and low sun uptake factor.
Embodiment 4, by aODPA and 2,2 '-bis trifluoromethyl-4,4 '-benzidine (TFDB) preparation polyimide
1) in a 100ml there-necked flask of being furnished with nitrogen inlet, adds 0.01mol (3.2023g) TFDB and 15mlN-methyl-2-pyrrolidone (NMP).After stirring at room is dissolved it fully, add 0.01mol (3.1021g) aODPA, after 25 ℃ 24h is stirred in continuation down, obtain the homogeneous liquid system;
2) in step 1) gained homogeneous liquid system, add 0.03mol (2.86ml) diacetyl oxide and 0.03mol (2.45ml) pyridine, continue to stir 24h, reaction finishes and obtains polyimide compound shown in the formula V, this product system is yellow viscous solution, and the quality percentage composition of this target product is 15%;
3) with step 2) the yellow viscous solution of gained falls in 300ml ethanol, obtains white thread solid.Collect solid, and with after the washing with alcohol three times, in baking oven under the normal pressure 80 ℃ dried 12 hours, obtain thread polyimide resin;
4) take by weighing the thread polyimide resin solid 3g of step 3) gained, add NMP17g, treat that solid dissolves fully after, filter and obtain the polyimide solution that solid content is 15% (weight percent).This polymers soln is coated on the sheet glass, by 80 ℃/2h; 150 ℃/1h; 200 ℃/1h; 250 ℃/1h; 280 ℃/0.5h programmed heating.After being cooled to room temperature, sheet glass is immersed in the water, peels off and obtain Kapton provided by the invention, structural formula is shown in the formula V:
(formula V)
Utilize the GPC method to predict, n is the integer of 30-40 in this compound.
The structure of above-mentioned Kapton and Performance Detection data are as follows:
Infrared spectra (cm
-1): 1782,1734,1491,1312,1176,744.
5% weightless temperature (℃, in the nitrogen): 546.
Second-order transition temperature (℃, DSC): 294.
Thermal expansivity (50～200 ℃, ppm/ ℃): 52.7.
Ultraviolet cut-on wavelength (nm): 355.
The transmittance at 500nm wavelength place (10 μ m, %): 93.4.
The transmittance at 500nm wavelength place (45 μ m, %): 81.6.
Sun absorption coefficient
S=0.33.
Hemispherical emissivity ε
H=0.80.
Absorptivity-emissivity ratio α
S/ ε
H=0.41.
Figure 16 to Figure 19 is respectively infrared spectra, thermal weight loss spectrogram, DSC spectrogram and the TMA spectrogram that this embodiment prepares the gained Kapton.Figure 20 a and 20b prepare the ultraviolet-visible spectrum (thickness is respectively 10 μ m and 45 μ m) of gained Kapton for this embodiment.
As from the foregoing, this compound structure is correct, and has good thermostability, high transparent and low sun uptake factor.
Embodiment 5, by aODPA and [2,4-two (3-amino-benzene oxygen) phenyl] diphenyl phosphine oxide (BADPO) preparation polyimide
1) in a 100ml there-necked flask of being furnished with nitrogen inlet, adds 0.01mol (4.925g) TFDB and 15ml N-Methyl pyrrolidone (NMP).After stirring at room is dissolved it fully, add 0.01mol (3.1021g) aODPA, after 25 ℃ 24h is stirred in continuation down, obtain the homogeneous liquid system;
2) in step 1) gained homogeneous liquid system, add 0.03mol (2.86ml) diacetyl oxide and 0.03mol (2.45ml) pyridine, continue to stir 24h, reaction finishes and obtains polyimide compound shown in the formula VI, this product system is yellow viscous solution, and the quality percentage composition of this target product is 25%;
3) with step 2) the yellow viscous solution of gained falls in 300ml ethanol, obtains white thread solid.Collect solid, and with after the washing with alcohol three times, in baking oven under the normal pressure 80 ℃ dried 12 hours, obtain thread polyimide resin;
4) take by weighing the thread polyimide resin solid 3g of step 3) gained, add NMP12g, treat that solid dissolves fully after, filter and obtain the polyimide solution that solid content is 20% (weight percent).Polymers soln is coated on the sheet glass, by 80 ℃/2h; 150 ℃/1h; 200 ℃/1h; 250 ℃/1h; 280 ℃/0.5h programmed heating.After being cooled to room temperature, sheet glass is immersed in the water, peels off and obtain Kapton provided by the invention, its structural formula is shown in the formula VI:
Utilize the GPC method to predict, n is the integer of 20-30 in this compound.
The structure of above-mentioned Kapton and Performance Detection data are as follows:
Infrared spectra (cm
-1): 1779,1724,1472,1381,1221,746.
5% weightless temperature (℃, in the nitrogen): 518.
Second-order transition temperature (℃, DSC): 242.
Thermal expansivity (50～200 ℃, ppm/ ℃): 53.7.
Ultraviolet cut-on wavelength (nm): 365.
The transmittance at 500nm wavelength place (10 μ m, %): 78.8.
The transmittance at 500nm wavelength place (45 μ m, %): 58.6.
Sun absorption coefficient
S=0.41.
Hemispherical emissivity ε
H=0.79.
Absorptivity-emissivity ratio α
S/ ε
H=0.52.
Figure 21 to Figure 24 is respectively infrared spectra, thermal weight loss spectrogram, DSC spectrogram and the TMA spectrogram that this embodiment prepares the gained Kapton.Figure 25 a and 25b prepare the ultraviolet-visible spectrum (thickness is respectively 10 μ m and 45 μ m) of gained Kapton for this embodiment.
As from the foregoing, this compound structure is correct, and has good thermostability, high transparent and low sun uptake factor.
Claims (9)
1. compound shown in the formula I general structure,
(formula I)
In the described formula I general structure, Ar is selected from any one in the following radicals:
N is the integer of 1-100.
2. compound according to claim 1 is characterized in that: in the described formula I general structure, n is the integer of 20-40.
3. compound according to claim 1 and 2 is characterized in that: the described compound of described formula I general structure is to get according to the arbitrary described method preparation of claim 4-7.
4. a method for preparing claim 1 or 2 described compounds comprises the steps:
1) with aromatic diamine and 2,3,3 ', 4 '-phenyl ether tetracarboxylic dianhydride mixing in organic solvent reacts, and reaction finishes and obtains the homogeneous liquid system;
2) adding diacetyl oxide and pyridine mixing react in described step 1) gained homogeneous liquid system, and reaction finishes and obtains claim 1 or 2 described compounds.
5. method according to claim 4, it is characterized in that: in the described step 1), described aromatic diamine is selected from 3, the 4-diaminodiphenyl oxide, 3,3 '-diaminodiphenyl oxide, 1, two (4 '-amino-benzene oxygen) benzene of 4-, 1, two (4-amino-benzene oxygen) benzene of 3-, 1, two (3 '-amino-benzene oxygen) benzene of 3-, 1, the two different propane of (4 '-amino-benzene oxygen) hexafluoro of 4-, 2,2 '-bis trifluoromethyl-4,4 '-benzidine, 2, two [(4-amino-benzene oxygen) phenyl] diphenyl phosphine oxides of 5-, 3, two [(3-amino-benzene oxygen) phenyl] diphenyl phosphine oxides and 2 of 5-, at least a in two [(4-amino-2-4-trifluoromethylphenopendant) phenyl] diphenyl phosphine oxides of 5-; Described organic solvent is selected from N-Methyl pyrrolidone, meta-cresol, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO), cyclopentanone, pimelinketone, tetrahydrofuran (THF) and 1, at least a in the 2-ethylene dichloride, at least a in preferred N-Methyl pyrrolidone and the meta-cresol.
6. according to claim 4 or 5 described methods, it is characterized in that: in the described step 1), described 2,3,3 ', 4 '-mol ratio of phenyl ether tetracarboxylic dianhydride and aromatic diamine is 1.00: (0.95～1.00) is preferably 1.00: (0.99～1.00);
Described step 2) in, described 2,3,3 ', 4 '-mol ratio of phenyl ether tetracarboxylic dianhydride and described diacetyl oxide is 1.00: (2.00～10.00), be preferably 1.00: 3.00, described 2,3,3 ', 4 '-mol ratio of phenyl ether tetracarboxylic dianhydride and pyridine is 1.00: (2.00～8.00) are preferably 1.00: 3.00.
7. according to the arbitrary described method of claim 4-6, it is characterized in that: in the described step 1) reactions steps, the time is 10～30 hours, is preferably 20～25 hours, and temperature is 0-35 ℃, preferred 15-25 ℃;
Described step 2) in the reactions steps, the time is 10～30 hours, is preferably 20～25 hours, and temperature is 0-35 ℃, preferred 15-25 ℃.
8. the resin or the film that obtain of claim 1 or 2 described compound.
9. described resin of claim 8 or the film application in substrate, antenna reflector, antenna collector or the solar sail of the thermal protection device for preparing spacecraft, solar battery array.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110025310.5A CN102167824B (en) | 2011-01-24 | 2011-01-24 | Polyimide film and preparation method and applications thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110025310.5A CN102167824B (en) | 2011-01-24 | 2011-01-24 | Polyimide film and preparation method and applications thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102167824A true CN102167824A (en) | 2011-08-31 |
| CN102167824B CN102167824B (en) | 2014-10-29 |
Family
ID=44489156
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110025310.5A Active CN102167824B (en) | 2011-01-24 | 2011-01-24 | Polyimide film and preparation method and applications thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102167824B (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532543A (en) * | 2011-12-20 | 2012-07-04 | 中国科学院化学研究所 | Copolymerization hot-sealing polyimide and preparation method and application thereof |
| CN102690415A (en) * | 2012-06-05 | 2012-09-26 | 中国科学院化学研究所 | Polyimide microspheres and preparation method and application thereof |
| JP2013237762A (en) * | 2012-05-14 | 2013-11-28 | Dexerials Corp | Polyimide, polyimide resin composition, and polyimide film |
| CN103467985A (en) * | 2013-09-22 | 2013-12-25 | 株洲时代电气绝缘有限责任公司 | Polyimide thin film |
| CN103904220A (en) * | 2012-12-31 | 2014-07-02 | 中原工学院 | Polyimide film for thin-film solar cell and manufacturing method of polyimide film |
| CN103904221A (en) * | 2012-12-31 | 2014-07-02 | 中原工学院 | Polyimide film for thin-film solar cell and preparation method thereof |
| CN105131284A (en) * | 2015-07-16 | 2015-12-09 | 中国科学院化学研究所 | High-heat-resistant thermal-sealable polyimide thin film, preparation method and application thereof |
| CN108424647A (en) * | 2018-03-13 | 2018-08-21 | 苏州柔彩新材料科技有限公司 | It is a kind of for the clear, colorless Kapton of AMOLED, preparation method and AMOLED devices |
| CN109476913A (en) * | 2016-08-03 | 2019-03-15 | 日产化学株式会社 | Composition is used in peeling layer formation |
| CN114717751A (en) * | 2021-12-09 | 2022-07-08 | 中国地质大学（北京） | Atomic oxygen resistant polyimide nanofiber membrane and preparation method and application thereof |
| CN114989430A (en) * | 2022-07-01 | 2022-09-02 | 桂林电子科技大学 | Fluorine-free transparent polyimide film and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002322280A (en) * | 2001-04-26 | 2002-11-08 | Hitachi Cable Ltd | Colorless transparent polyimide, method for producing the same and laminated component |
| JP2003155343A (en) * | 2001-11-19 | 2003-05-27 | Kanegafuchi Chem Ind Co Ltd | Polyimide resin and polyimide resin composition |
| JP2004285103A (en) * | 2003-03-19 | 2004-10-14 | Kanegafuchi Chem Ind Co Ltd | Thermoplastic polyimide and adhesive comprising the same |
| CN101307004A (en) * | 2007-05-16 | 2008-11-19 | 中国科学院化学研究所 | Polyfluorphenyl substituted aromatic diamine, polymers thereof and method for preparing same |
-
2011
- 2011-01-24 CN CN201110025310.5A patent/CN102167824B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002322280A (en) * | 2001-04-26 | 2002-11-08 | Hitachi Cable Ltd | Colorless transparent polyimide, method for producing the same and laminated component |
| JP2003155343A (en) * | 2001-11-19 | 2003-05-27 | Kanegafuchi Chem Ind Co Ltd | Polyimide resin and polyimide resin composition |
| JP2004285103A (en) * | 2003-03-19 | 2004-10-14 | Kanegafuchi Chem Ind Co Ltd | Thermoplastic polyimide and adhesive comprising the same |
| CN101307004A (en) * | 2007-05-16 | 2008-11-19 | 中国科学院化学研究所 | Polyfluorphenyl substituted aromatic diamine, polymers thereof and method for preparing same |
Non-Patent Citations (1)
| Title |
|---|
| 《Journal of Polymer Science：Part A：Polymer Chemistry》 20031231 QINGXUAN LI etc. Polyimides from Isomeric Oxydiphthalic Anhydrides 第3253页左栏第1段和右栏第1段，第3254页图2，第3256页左栏第1段和表1 1-9 第41卷, * |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532543A (en) * | 2011-12-20 | 2012-07-04 | 中国科学院化学研究所 | Copolymerization hot-sealing polyimide and preparation method and application thereof |
| CN102532543B (en) * | 2011-12-20 | 2014-01-29 | 中国科学院化学研究所 | Copolymerization hot-sealing polyimide and preparation method and application thereof |
| JP2013237762A (en) * | 2012-05-14 | 2013-11-28 | Dexerials Corp | Polyimide, polyimide resin composition, and polyimide film |
| CN102690415A (en) * | 2012-06-05 | 2012-09-26 | 中国科学院化学研究所 | Polyimide microspheres and preparation method and application thereof |
| CN102690415B (en) * | 2012-06-05 | 2014-07-16 | 中国科学院化学研究所 | Polyimide microspheres and preparation method and application thereof |
| CN103904220A (en) * | 2012-12-31 | 2014-07-02 | 中原工学院 | Polyimide film for thin-film solar cell and manufacturing method of polyimide film |
| CN103904221A (en) * | 2012-12-31 | 2014-07-02 | 中原工学院 | Polyimide film for thin-film solar cell and preparation method thereof |
| CN103467985A (en) * | 2013-09-22 | 2013-12-25 | 株洲时代电气绝缘有限责任公司 | Polyimide thin film |
| CN105131284A (en) * | 2015-07-16 | 2015-12-09 | 中国科学院化学研究所 | High-heat-resistant thermal-sealable polyimide thin film, preparation method and application thereof |
| CN109476913A (en) * | 2016-08-03 | 2019-03-15 | 日产化学株式会社 | Composition is used in peeling layer formation |
| CN109476913B (en) * | 2016-08-03 | 2022-03-01 | 日产化学株式会社 | Composition for forming release layer |
| CN108424647A (en) * | 2018-03-13 | 2018-08-21 | 苏州柔彩新材料科技有限公司 | It is a kind of for the clear, colorless Kapton of AMOLED, preparation method and AMOLED devices |
| CN108424647B (en) * | 2018-03-13 | 2021-05-25 | 苏州柔彩半导体柔性材料科技有限公司 | Transparent colorless polyimide film for AMOLED, preparation method and AMOLED device |
| CN114717751A (en) * | 2021-12-09 | 2022-07-08 | 中国地质大学（北京） | Atomic oxygen resistant polyimide nanofiber membrane and preparation method and application thereof |
| CN114717751B (en) * | 2021-12-09 | 2023-06-20 | 中国地质大学（北京） | Atomic oxygen-resistant polyimide nanofiber membrane and preparation method and application thereof |
| CN114989430A (en) * | 2022-07-01 | 2022-09-02 | 桂林电子科技大学 | Fluorine-free transparent polyimide film and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102167824B (en) | 2014-10-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102167824B (en) | Polyimide film and preparation method and applications thereof | |
| CN102634022B (en) | Colorless highly-transparent polyimide film as well as preparation method and application thereof | |
| CN102532895B (en) | Copolyimide solution, copolyimide, display element, and solar cell | |
| Zhuang et al. | Colorless partially alicyclic polyimides based on Tröger’s base exhibiting good solubility and dual fluorescence/phosphorescence emission | |
| CN107722314B (en) | Preparation method of thermoplastic polyimide composite material | |
| CN101580637B (en) | Alicyclic-containing polyimide film and preparation method thereof | |
| KR20210063447A (en) | Polyimide precursor composition, polyimide production method, polyimide, polyimide film, and substrate | |
| CN102976983B (en) | A kind of sulfuryl fluorinated diamine compound and polyimide film material and method for making thereof | |
| KR20140054301A (en) | Thermally stable, low birefringent copolyimide films | |
| KR20170089585A (en) | Composition for preparing polyimide or poly(amide-imide) copolymer, article obtained therefrom, and display device including same | |
| CN110698670B (en) | Carborane modified polyimide film and preparation method thereof | |
| CN101597428B (en) | Full aromatic fluorine containing transparent polyimide film and preparation method thereof | |
| KR102198357B1 (en) | Preparation method for polyimide | |
| CN107531902A (en) | Polyimide resin and the film using the polyimide resin | |
| CN105017534A (en) | Preparation method of soluble, colorless, transparent and low-thermal-expansion-coefficient polyamide imide film | |
| CN101787129A (en) | Soluble and high-temperature resistant aromatic polyimide and preparation method thereof | |
| CN104151823A (en) | Polyimide film and preparation methods thereof | |
| CN105037727A (en) | Polyimide film material capable of serving as conducting film substrate and preparing method of polyimide film material | |
| CN101531678B (en) | Phosphine-containing aromatic diamine compound, preparation method and application thereof | |
| CN105131286A (en) | Polyimide film as well as preparation method, flexible substrate and application thereof | |
| Bottino et al. | Synthesis, characterization, and study of the thermal properties of new poly (arylene ether 1, 3, 4-oxadiazole) s | |
| Wang et al. | Preparation and Properties of Novel Cross‐Linked Fluorinated Poly (aryl ether) with Low Dielectric Constant and High Thermal Stability | |
| CN103694475A (en) | Colorless transparent polyimide film and preparation method thereof | |
| CN112646183A (en) | Polyimide material and preparation method and application thereof | |
| Liu et al. | Colorless Polyamide–Imide Films with Enhanced Thermal and Dimensional Stability and Their Application in Flexible OLED Devices |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |