CN103059298B - Polyamic acid and polyimide, and preparation methods and applications thereof - Google Patents

Polyamic acid and polyimide, and preparation methods and applications thereof Download PDF

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CN103059298B
CN103059298B CN201310004420.2A CN201310004420A CN103059298B CN 103059298 B CN103059298 B CN 103059298B CN 201310004420 A CN201310004420 A CN 201310004420A CN 103059298 B CN103059298 B CN 103059298B
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hydrogen atom
straight
carbonatoms
represent hydrogen
polyamic acid
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CN103059298A (en
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肖昂
朱海波
宋省勳
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BOE Technology Group Co Ltd
Beijing BOE Optoelectronics Technology Co Ltd
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Beijing BOE Optoelectronics Technology Co Ltd
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Abstract

The invention relates to polyamic acid and polyimide, and preparation methods and applications thereof. The structure of polyamic acid is represented by the general formula (I), and the structure of polyimide is represented by the general formula (II). R1-R4 and R'1-R'4 respectively independently represent hydrogen, C1-C4 straight-chain or branched-chain alkyl, or C1-C4 straight-chain or branched-chain alkoxy; R1 and R2 are not simultaneously hydrogen; R5-R8 respectively independently represent hydrogen, C1-C3 straight-chain or branched-chain alkyl, or C1-C3 straight-chain or branched-chain alkoxy; and both the number-average molecular weights of polyamic acid and polyimide are 4000-6000. The polyamic acid is obtained through a polycondensation reaction of corresponding naphthalene tetracarboxylic dianhydride and diaminodiphenyl methane. The polyimide is obtained by further shrinking of the polyamic acid.

Description

Polyamic acid, polyimide and its preparation method and application
Technical field
The present invention relates to polyamic acid, polyimide and its preparation method and application.Particularly relate to the polyamic acid, polyimide and its preparation method and application for the liquid crystal orientation film in liquid-crystal display.
Background technology
In the making processes of FFS type TFT-LCD, for obtaining good picture display effect, usually using polyimide to prepare liquid crystal orientation film, aligning so that the liquid crystal molecule making to be present in liquid crystal orientation film surface is homogeneous.The polyimide of current use has structural formula as follows.
Wherein, Ar can be phenyl, benzophenone based, diphenylmethane group, hexichol ether and dibenzenesulfonyl etc.Two carboxyls forming acid anhydride in this polyimide are in ortho position, such as, can be generated by 2,3,6,7-naphthalenetetracarbacidic acidic dianhydride and aromatic diamines condensation.
The transmissivity of polyimide liquid crystal direct action membrane self and all can affect the effect of picture display on the orientation property of liquid crystal molecule.It is printing-type that alignment film of polyimide commonly uses one of coating method, as shown in Figure 1.Alignment film of polyimide forms solution and instills from device 1 in anilox roll 2, and the effect of anilox roll 2 is the alignment film of polyimide transmitting uniform thickness.Scraper 3 regulates the thickness that can control alignment film of polyimide by pressure.Such alignment film of polyimide is formed solution and can be transferred to equably in APR version (alignment films transfer printing board) 4 by anilox roll 2 and scraper 3.APR version 4 has tiny netted aperture, making transfer printing alignment film of polyimide thereon form solution can distribute equably.Alignment film of polyimide in APR version 4 forms the rotation of solution by running roller 5, is coated in the surface of substrate 6 equably.Generally be coated with alignment film of polyimide on upper and lower base plate surface, through friction process, make alignment film of polyimide surface form orderly orientation, thus make the liquid crystal molecule Orienting ordered arrangement being attached to its surface, and then reach good display effect.
Therefore, in order to improve display brightness and the display effect of liquid-crystal display, the alignment film of polyimide that a kind of transmissivity is high is required.In addition, consider operability, also require that the precursor of alignment film of polyimide and polyamic acid have good solubility in conventional industrial solvent, thus can even spread be realized.
Summary of the invention
In view of above-mentioned the problems of the prior art, namely, require the polyimide that a kind of transmissivity is high and in conventional industrial solvent, have the polyamic acid of good solubility, the invention provides polyamic acid, polyimide and its preparation method and application, concrete technical scheme is as follows.
A kind of polyamic acid, its structure as shown in following general formula (I),
In logical formula I, R 1~ R 4, R ' 1~ R ' 4separately represent hydrogen atom, carbonatoms be 1 ~ 4 straight or branched alkyl or carbonatoms be 1 ~ 4 straight or branched alkoxyl group, and R 1, R 2be asynchronously hydrogen atom, R 5~ R 8separately represent hydrogen atom, carbonatoms be 1 ~ 3 straight or branched alkyl or carbonatoms be 1 ~ 3 straight or branched alkoxyl group,
The number-average molecular weight of described polyamic acid is 4000 ~ 6000.
Preferably R ' in logical formula I 1~ R ' 4separately represent hydrogen atom, and R 5~ R 8separately represent hydrogen atom.
Preferred in above-mentioned logical formula I further, R 1, R 4represent respectively carbonatoms be 1 ~ 4 straight or branched alkyl or carbonatoms be 1 ~ 4 straight or branched alkoxyl group, simultaneously R 2, R 3represent hydrogen atom respectively; Or R 2, R 3represent respectively carbonatoms be 1 ~ 4 straight or branched alkyl or carbonatoms be 1 ~ 4 straight or branched alkoxyl group, simultaneously R 1, R 4represent hydrogen atom respectively.
Further preferred in above-mentioned logical formula I, R 1, R 4represent methyl, sec.-propyl or methoxyl group respectively, simultaneously R 2, R 3represent hydrogen atom respectively; Or R 2, R 3represent methyl, sec.-propyl or methoxyl group respectively, simultaneously R 1, R 4represent hydrogen atom respectively.
The invention still further relates to a kind of polyimide, its structure as shown in following general formula (II),
In logical formula II, R 1~ R 4, R ' 1~ R ' 4separately represent hydrogen atom, carbonatoms be 1 ~ 4 straight or branched alkyl or carbonatoms be 1 ~ 4 straight or branched alkoxyl group, and R 1, R 2be asynchronously hydrogen atom, R 5~ R 8separately represent hydrogen atom, carbonatoms be 1 ~ 3 straight or branched alkyl or carbonatoms be 1 ~ 3 straight or branched alkoxyl group,
The number-average molecular weight of described polyamic acid is 4000 ~ 6000.
Preferably in logical formula II, R ' 1~ R ' 4separately represent hydrogen atom, and R 5~ R 8separately represent hydrogen atom.
Preferred in logical formula II further, R 1, R 4represent respectively carbonatoms be 1 ~ 4 straight or branched alkyl or carbonatoms be 1 ~ 4 straight or branched alkoxyl group, simultaneously R 2, R 3represent hydrogen atom respectively; Or R 2, R 3represent respectively carbonatoms be 1 ~ 4 straight or branched alkyl or carbonatoms be 1 ~ 4 straight or branched alkoxyl group, simultaneously R 1, R 4represent hydrogen atom respectively.
Further preferred in logical formula II, R 1, R 4represent methyl, sec.-propyl or methoxyl group respectively, simultaneously R 2, R 3represent hydrogen atom respectively; Or R 2, R 3represent methyl, sec.-propyl or methoxyl group respectively, simultaneously R 1, R 4represent hydrogen atom respectively.
The invention still further relates to the preparation method of above-mentioned polyamic acid, the diaminodiphenylmethane that the naphthalenetetracarbacidic acidic dianhydride represented by making following logical formula III and logical formula IV represent is carried out polycondensation and obtains polyamic acid,
Wherein, R 1~ R 4, R ' 1~ R ' 4, R 5~ R 8have and above-mentioned R 1~ R 4, R ' 1~ R ' 4, R 5~ R 8identical definition.
Preferably in above-mentioned preparation method, R 5~ R 8separately represent hydrogen atom, and the diaminodiphenylmethane that logical formula IV represents is 3,3 '-dimethyl-4,4 '-diaminodiphenylmethane, 3,3 '-di-isopropyl-4,4 '-diaminodiphenylmethane or 3,3 '-dimethoxy-4 ', 4 '-diaminodiphenylmethane.
The invention still further relates to the preparation method of polyimide, undertaken obtaining after shrink is reacted by polyamic acid of the present invention.
The invention still further relates to polyamic acid or the application in liquid crystal orientation film prepared by polyimide.
The present invention also provides a kind of liquid crystal orientation film, and it is prepared by polyimide of the present invention.
The present invention further provides a kind of display panels, it comprises above-mentioned liquid crystal orientation film.
Utilize polyimide of the present invention to form liquid crystal orientation film, the transmissivity of alignment film of polyimide can be improved, and the orientation uniformity of alignment film of polyimide to liquid crystal molecule is good.In addition, the favorable solubility of polyamic acid of the present invention in industrial solvent, thus it can be coated on substrate equably.
Accompanying drawing explanation
Fig. 1 represents the schematic diagram forming alignment film of polyimide.
Embodiment
Technical scheme of the present invention is as follows.
A kind of polyamic acid, its structure as shown in following general formula (I),
In logical formula I, R 1~ R 4, R ' 1~ R ' 4separately represent hydrogen atom, carbonatoms be 1 ~ 4 straight or branched alkyl or carbonatoms be 1 ~ 4 straight or branched alkoxyl group, and R 1, R 2be asynchronously hydrogen atom, R 5~ R 8separately represent hydrogen atom, carbonatoms be 1 ~ 3 straight or branched alkyl or carbonatoms be 1 ~ 3 straight or branched alkoxyl group,
The number-average molecular weight of described polyamic acid is 4000 ~ 6000.
Described carbonatoms be 1 ~ 4 straight or branched alkyl can be methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl; Described carbonatoms be 1 ~ 4 straight or branched alkoxyl group can be methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, isobutoxy, tert.-butoxy.Work as R 1~ R 4, R ' 1~ R ' 4during for above-mentioned group, can provide on the one hand required sterically hindered, the naphthalenetetracarbacidic acidic dianhydride in structural formula is made to be in different planes from diaminodiphenylmethane, do not affect the polycondensation of naphthalenetetracarbacidic acidic dianhydride and diaminodiphenylmethane on the other hand, if the substituent carbochain of diaminodiphenylmethane is long, then likely hinder the polycondensation of naphthalenetetracarbacidic acidic dianhydride and diaminodiphenylmethane, such as, reduce condensation polymerization speed.Described carbonatoms be 1 ~ 3 straight or branched alkyl can be methyl, ethyl, n-propyl, sec.-propyl; Described carbonatoms be 1 ~ 3 straight or branched alkoxyl group can be methoxyl group, oxyethyl group, positive propoxy, isopropoxy.Work as R 5~ R 8during for above-mentioned group, because carbochain is shorter, so do not affect the two dimensional structure of naphthalenetetracarbacidic acidic dianhydride.
Preferably R ' in logical formula I 1~ R ' 4separately represent hydrogen atom, and R 5~ R 8separately represent hydrogen atom.
Preferred in above-mentioned logical formula I further, R 1, R 4represent respectively carbonatoms be 1 ~ 4 straight or branched alkyl or carbonatoms be 1 ~ 4 straight or branched alkoxyl group, simultaneously R 2, R 3represent hydrogen atom respectively; Or R 2, R 3represent respectively carbonatoms be 1 ~ 4 straight or branched alkyl or carbonatoms be 1 ~ 4 straight or branched alkoxyl group, simultaneously R 1, R 4represent hydrogen atom respectively.
Further preferred in above-mentioned logical formula I, R 1, R 4represent methyl, sec.-propyl or methoxyl group respectively, simultaneously R 2, R 3represent hydrogen atom respectively; Or R 2, R 3represent methyl, sec.-propyl or methoxyl group respectively, simultaneously R 1, R 4represent hydrogen atom respectively.
The invention still further relates to a kind of polyimide, its structure as shown in following general formula (II),
In logical formula II, R 1~ R 4, R ' 1~ R ' 4separately represent hydrogen atom, carbonatoms be 1 ~ 4 straight or branched alkyl or carbonatoms be 1 ~ 4 straight or branched alkoxyl group, and R 1, R 2be asynchronously hydrogen atom, R 5~ R 8separately represent hydrogen atom, carbonatoms be 1 ~ 3 straight or branched alkyl or carbonatoms be 1 ~ 3 straight or branched alkoxyl group,
The number-average molecular weight of described polyamic acid is 4000 ~ 6000.
Described carbonatoms be 1 ~ 4 straight or branched alkyl can be methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl; Described carbonatoms be 1 ~ 4 straight or branched alkoxyl group can be methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, isobutoxy, tert.-butoxy.Work as R 1~ R 4, R ' 1~ R ' 4during for above-mentioned group, can provide on the one hand required sterically hindered, the naphthalenetetracarbacidic acidic dianhydride in structural formula is made to be in different planes from diaminodiphenylmethane, do not affect the polycondensation of naphthalenetetracarbacidic acidic dianhydride and diaminodiphenylmethane on the other hand, if the substituent carbochain of diaminodiphenylmethane is long, then likely hinder the polycondensation of naphthalenetetracarbacidic acidic dianhydride and diaminodiphenylmethane, such as, reduce condensation polymerization speed.Described carbonatoms be 1 ~ 3 straight or branched alkyl can be methyl, ethyl, n-propyl, sec.-propyl; Described carbonatoms be 1 ~ 3 straight or branched alkoxyl group can be methoxyl group, oxyethyl group, positive propoxy, isopropoxy.Work as R 5~ R 8during for above-mentioned group, because carbochain is shorter, so do not affect the two dimensional structure of naphthalenetetracarbacidic acidic dianhydride.
Preferably in logical formula II, R ' 1~ R ' 4separately represent hydrogen atom, and R 5~ R 8separately represent hydrogen atom.
Preferred in logical formula II further, R 1, R 4represent respectively carbonatoms be 1 ~ 4 straight or branched alkyl or carbonatoms be 1 ~ 4 straight or branched alkoxyl group, simultaneously R 2, R 3represent hydrogen atom respectively; Or R 2, R 3represent respectively carbonatoms be 1 ~ 4 straight or branched alkyl or carbonatoms be 1 ~ 4 straight or branched alkoxyl group, simultaneously R 1, R 4represent hydrogen atom respectively.
Further preferred in logical formula II, R 1, R 4represent methyl, sec.-propyl or methoxyl group respectively, simultaneously R 2, R 3represent hydrogen atom respectively; Or R 2, R 3represent methyl, sec.-propyl or methoxyl group respectively, simultaneously R 1, R 4represent hydrogen atom respectively.
The invention still further relates to the preparation method of above-mentioned polyamic acid, carry out polycondensation by making corresponding naphthalenetetracarbacidic acidic dianhydride and diaminodiphenylmethane and prepare polyamic acid of the present invention.Be specially, the diaminodiphenylmethane that the naphthalenetetracarbacidic acidic dianhydride represented by making following logical formula III and logical formula IV represent is carried out polycondensation and obtains polyamic acid,
Wherein, R 1~ R 4, R ' 1~ R ' 4, R 5~ R 8have and above-mentioned R 1~ R 4, R ' 1~ R ' 4, R 5~ R 8identical definition.
Preferably in above-mentioned preparation method, R 5~ R 8separately represent hydrogen atom, and the diaminodiphenylmethane that logical formula IV represents is 3,3 '-dimethyl-4,4 '-diaminodiphenylmethane, 3,3 '-di-isopropyl-4,4 '-diaminodiphenylmethane or 3,3 '-dimethoxy-4 ', 4 '-diaminodiphenylmethane.
The invention still further relates to the preparation method of polyimide, undertaken obtaining after shrink is reacted by polyamic acid of the present invention.
The invention still further relates to polyamic acid or the application in liquid crystal orientation film prepared by polyimide.
The present invention also provides a kind of liquid crystal orientation film, and it is prepared by polyimide of the present invention.
The present invention further provides a kind of display panels, it comprises above-mentioned liquid crystal orientation film.
Based on specific embodiment, the present invention is described below, but the present invention is not limited to these embodiments.
Embodiment 1
Under room temperature, by 3 shown in 0.05mol above formula, 3 '-dimethyl-4,4 '-diaminodiphenylmethane joins in N-Methyl pyrrolidone (NMP) solvent of 200ml drying, 1 shown in 0.05mol above formula is slowly added wherein under well-beaten state, 4,5,8-naphthalenetetracarbacidic acidic dianhydride, stir standing after 24 hours, filtration, obtain liquid polyamic acid, its number-average molecular weight is 4000 ~ 6000, its structural formula and IR spectroscopic data as follows.
IR（KBr）：1660cm -1，1720cm -1，3260-3270cm -1
Liquid polyamic acid is dissolved in N-Methyl pyrrolidone, obtains clear liquor, the clear liquor obtained is coated to transparent glass substrate surface equably, make its thickness be about 100nm.At 100 DEG C, heat 5min, remove solvent, then at 250 DEG C, heat 1hr, completely after solidification, obtain alignment film of polyimide.Structural formula and the IR spectroscopic data of described polyimide are as follows.And the number-average molecular weight of described polyimide is 4000 ~ 6000.
IR（KBr）：1360-1370cm -1
Owing to not observing the stretching vibration (1660cm of carbonyl in amide group in infrared spectra -1), the vibration (1720cm of the carbonyl of carboxyl in aromatic carboxylic acid -1) and the stretching vibration (3260-3270cm of secondary amine (-NH-) -1), and, observe the stretching vibration (1360-1370cm of imide (-CONCO-) -1), amide group and the carboxyl generation cyclization of polyamic acid are described thus, generate polyimide.
Embodiment 2
Under room temperature, by 3 shown in 0.05mol above formula, 3 '-di-isopropyl-4,4 '-diaminodiphenylmethane joins in N-Methyl pyrrolidone (NMP) solvent of 200ml drying, 1 shown in 0.05mol embodiment 1 is slowly added wherein under fully stirring, 4,5,8-naphthalenetetracarbacidic acidic dianhydride, stir standing after 24 hours, filtration, obtain liquid polyamic acid, the number-average molecular weight of described polyamic acid is 4000 ~ 6000, its structural formula and IR spectroscopic data as follows.
IR（KBr）：1660cm -1，1720cm -1，3260-3270cm -1
Liquid polyamic acid is dissolved in N-Methyl pyrrolidone, obtains clear liquor, the clear liquor obtained is coated to transparent glass substrate surface equably, make its thickness be about 100nm.At 100 DEG C, heat 5min, remove solvent, then at 250 DEG C, heat 1hr, completely after solidification, obtain alignment film of polyimide.Structural formula and the IR spectroscopic data of described polyimide are as follows.And the number-average molecular weight of described polyimide is 4000 ~ 6000.
IR（KBr）：1360-1370cm -1
Embodiment 3
Under room temperature, by 3 shown in 0.05mol above formula, 3 '-dimethoxy-4 ', 4 '-diaminodiphenylmethane joins in N-Methyl pyrrolidone (NMP) solvent of 200ml drying, 1 shown in 0.05mol embodiment 1 is slowly added wherein under fully stirring, 4,5,8-naphthalenetetracarbacidic acidic dianhydride, stir standing after 24 hours, filtration, obtain liquid polyamic acid, the number-average molecular weight of described polyamic acid is 4000 ~ 6000, its structural formula and IR spectroscopic data as follows.
IR（KBr）：1660cm -1，1720cm -1，3260-3270cm -1
Liquid polyamic acid is dissolved in N-Methyl pyrrolidone, obtains clear liquor, the clear liquor obtained is coated to transparent glass substrate surface equably, make its thickness be about 100nm.At 100 DEG C, heat 5min, remove solvent, then at 250 DEG C, heat 1hr, completely after solidification, obtain alignment film of polyimide.Structural formula and the IR spectroscopic data of described polyimide are as follows.And the number-average molecular weight of described polyimide is 4000 ~ 6000.
IR（KBr）：1360-1370cm -1
Comparative example 1
Under room temperature, by 0.05mol 4,4 '-diamino-diphenyl joins in N-Methyl pyrrolidone (NMP) solvent of 200ml drying, under fully stirring, slowly add Isosorbide-5-Nitrae wherein, 5,8-naphthalenetetracarbacidic acidic dianhydride 0.05mol, stirs standing after 24 hours, filtration, obtains liquid polyamic acid, the number-average molecular weight of described polyamic acid is 4000 ~ 6000, its structural formula and IR spectroscopic data as follows.
IR（KBr）：1660cm -1，1720cm -1，3260-3270cm -1
Liquid polyamic acid is dissolved in N-Methyl pyrrolidone, obtains clear liquor, the clear liquor obtained is coated to transparent glass substrate surface equably, make its thickness be about 100nm.At 100 DEG C, heat 5min, remove solvent, then at 250 DEG C, heat 1hr, completely after solidification, obtain alignment film of polyimide.Structural formula and the IR spectroscopic data of described polyimide are as follows.And the number-average molecular weight of described polyimide is 4000 ~ 6000.
IR（KBr）：1360-1370cm -1
Comparative example 2
Under room temperature, 2,2 '-dimethyl-4,4 '-diaminodiphenylmethane 0.05mol is joined in N-Methyl pyrrolidone (NMP) solvent of 200ml drying, slowly 1 is added wherein under fully stirring, 4,5,8-naphthalenetetracarbacidic acidic dianhydride 0.05mol, stir standing after 24 hours, filtration, obtain liquid polyamic acid, the number-average molecular weight of described polyamic acid is 4000 ~ 6000, its structural formula and IR spectroscopic data as follows.
IR（KBr）：1660cm -1，1720cm -1，3260-3270cm -1
Liquid polyamic acid is dissolved in N-Methyl pyrrolidone, obtains clear liquor, the clear liquor obtained is coated to transparent glass substrate surface equably, make its thickness be about 100nm.At 100 DEG C, heat 5min, remove solvent, then at 250 DEG C, heat 1hr, completely after solidification, obtain alignment film of polyimide.Structural formula and the IR spectroscopic data of described polyimide are as follows.And the number-average molecular weight of described polyimide is 4000 ~ 6000.
IR（KBr）：1360-1370cm -1
Comparative example 3
Under room temperature, by 2,2 '-dimethoxy-4 ', 4 '-diaminodiphenylmethane 0.05mol joins in N-Methyl pyrrolidone (NMP) solvent of 200ml drying, slowly 1 is added wherein under fully stirring, 4,5,8-naphthalenetetracarbacidic acidic dianhydride 0.05mol, stir standing after 24 hours, filtration, obtain liquid polyamic acid, the number-average molecular weight of described polyamic acid is 4000 ~ 6000, its structural formula and IR spectroscopic data as follows.
IR（KBr）：1660cm -1，1720cm -1，3260-3270cm -1
Liquid polyamic acid is dissolved in N-Methyl pyrrolidone, obtains clear liquor, the clear liquor obtained is coated to transparent glass substrate surface equably, make its thickness be about 100nm.At 100 DEG C, heat 5min, remove solvent, then at 250 DEG C, heat 1hr, completely after solidification, obtain alignment film of polyimide.Structural formula and the IR spectroscopic data of described polyimide are as follows.And the number-average molecular weight of described polyimide is 4000 ~ 6000.
IR（KBr）：1360-1370cm -1
The solvability evaluation of polyamic acid
At room temperature mixed with mass ratio 1:1 with the industrial solvent shown in table 1 by the polyamic acid that embodiment 1 ~ 3 and comparative example 1 ~ 3 prepare respectively, vibration, observes each mixed solution after static 5min, evaluates the solvability of polyamic acid.When mixed solution clarification, then represent that polyamic acid dissolves in this industrial solvent; When mixed solution presents muddy state, then represent that polyamic acid is not soluble in this industrial solvent.Solvability evaluation result is shown in table 1.
Table 1
"+" represents solvable; "-" represents not easily molten
As shown in Table 1, all there is good solubility in the polyamic acid of embodiments of the invention 1 ~ 3 all industrial solvents shown in table 1, and the solvability of the polyamic acid of comparative example 1 ~ 3 is poor.
The transmissivity evaluation of alignment film of polyimide
Next, the alignment film of polyimide optical transmittance at different wavelengths prepared by EZ-COM optical measuring system measurement embodiment 1 ~ 3 and comparative example 1 ~ 3, measuring result is as shown in table 2.
Table 2
As shown in Table 2, the transmissivity of the alignment film of polyimide of comparative example 1 ~ 3 is lower, and the transmissivity of alignment film of polyimide under each wavelength of embodiments of the invention 1 ~ 3 is all higher.
Obviously, those skilled in the art can carry out various change and modification to the present invention and not depart from the spirit and scope of the present invention.Like this, if these amendments of the present invention and modification belong within the scope of the claims in the present invention and equivalent technologies thereof, then the present invention is also intended to comprise these change and modification.

Claims (15)

1. a polyamic acid, is characterized in that, structure as shown in following general formula (I),
In logical formula I, R 1~ R 4, R ' 1~ R ' 4separately represent hydrogen atom, carbonatoms be 1 ~ 4 straight or branched alkyl or carbonatoms be 1 ~ 4 straight or branched alkoxyl group, and R 1, R 2be asynchronously hydrogen atom, R 5~ R 8separately represent hydrogen atom, carbonatoms be 1 ~ 3 straight or branched alkyl or carbonatoms be 1 ~ 3 straight or branched alkoxyl group,
The number-average molecular weight of described polyamic acid is 4000 ~ 6000.
2. polyamic acid according to claim 1, is characterized in that, R ' 1~ R ' 4separately represent hydrogen atom, and R 5~ R 8separately represent hydrogen atom.
3. polyamic acid according to claim 2, is characterized in that, R 1, R 4represent respectively carbonatoms be 1 ~ 4 straight or branched alkyl or carbonatoms be 1 ~ 4 straight or branched alkoxyl group, simultaneously R 2, R 3represent hydrogen atom respectively; Or R 2, R 3represent respectively carbonatoms be 1 ~ 4 straight or branched alkyl or carbonatoms be 1 ~ 4 straight or branched alkoxyl group, simultaneously R 1, R 4represent hydrogen atom respectively.
4. polyamic acid according to claim 3, is characterized in that, R 1, R 4represent methyl, sec.-propyl or methoxyl group respectively, simultaneously R 2, R 3represent hydrogen atom respectively; Or R 2, R 3represent methyl, sec.-propyl or methoxyl group respectively, simultaneously R 1, R 4represent hydrogen atom respectively.
5. a polyimide, is characterized in that, structure as shown in following general formula (II),
In logical formula II, R 1~ R 4, R ' 1~ R ' 4separately represent hydrogen atom, carbonatoms be 1 ~ 4 straight or branched alkyl or carbonatoms be 1 ~ 4 straight or branched alkoxyl group, and R 1, R 2be asynchronously hydrogen atom, R 5~ R 8separately represent hydrogen atom, carbonatoms be 1 ~ 3 straight or branched alkyl or carbonatoms be 1 ~ 3 straight or branched alkoxyl group,
The number-average molecular weight of described polyimide is 4000 ~ 6000.
6. polyimide according to claim 5, is characterized in that, in logical formula II, and R ' 1~ R ' 4separately represent hydrogen atom, and R 5~ R 8separately represent hydrogen atom.
7. polyimide according to claim 6, is characterized in that, in logical formula II, and R 1, R 4represent respectively carbonatoms be 1 ~ 4 straight or branched alkyl or carbonatoms be 1 ~ 4 straight or branched alkoxyl group, simultaneously R 2, R 3represent hydrogen atom respectively; Or R 2, R 3represent respectively carbonatoms be 1 ~ 4 straight or branched alkyl or carbonatoms be 1 ~ 4 straight or branched alkoxyl group, simultaneously R 1, R 4represent hydrogen atom respectively.
8. polyimide according to claim 7, is characterized in that, in logical formula II, and R 1, R 4represent methyl, sec.-propyl or methoxyl group respectively, simultaneously R 2, R 3represent hydrogen atom respectively; Or R 2, R 3represent methyl, sec.-propyl or methoxyl group respectively, simultaneously R 1, R 4represent hydrogen atom respectively.
9. prepare a method for polyamic acid according to claim 1, it is characterized in that, the diaminodiphenylmethane that the naphthalenetetracarbacidic acidic dianhydride represented by making logical formula III and logical formula IV represent is carried out polycondensation and obtains,
Wherein, R 1~ R 4, R ' 1~ R ' 4, R 5~ R 8have and R in claim 1 1~ R 4, R ' 1~ R ' 4, R 5~ R 8identical definition.
10. method according to claim 9, is characterized in that, in logical formula III, and R 5~ R 8separately represent hydrogen atom, the diaminodiphenylmethane that logical formula IV represents is 3,3 '-dimethyl-4,4 '-diaminodiphenylmethane, 3,3 '-di-isopropyl-4,4 '-diaminodiphenylmethane or 3,3 '-dimethoxy-4 ', 4 '-diaminodiphenylmethane.
11. 1 kinds of methods preparing polyimide according to claim 5, is characterized in that, carry out shrink react and obtain by polyamic acid according to claim 1.
12. methods according to claim 11, is characterized in that, described polyamic acid is prepared by the method described in claim 9 or 10.
The application in liquid crystal orientation film prepared by polyamic acid according to any one of 13. Claims 1 to 4 or the polyimide according to any one of claim 5 ~ 8.
14. 1 kinds of liquid crystal orientation films, is characterized in that, the polyimide according to any one of claim 5 ~ 8 prepares.
15. 1 kinds of display panels, is characterized in that, comprise liquid crystal orientation film according to claim 14.
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WO2016015408A1 (en) 2014-07-29 2016-02-04 京东方科技集团股份有限公司 Functional material, preparation method therefor, organic light-emitting diode display panel
WO2018126141A1 (en) * 2016-12-31 2018-07-05 Sabic Global Technologies B.V. Branched polyimide compositions, method of manufacture, and uses thereof

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