CN1174081C - Prepn of side-chain liquid crystal polyimide film - Google Patents
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- CN1174081C CN1174081C CNB011072636A CN01107263A CN1174081C CN 1174081 C CN1174081 C CN 1174081C CN B011072636 A CNB011072636 A CN B011072636A CN 01107263 A CN01107263 A CN 01107263A CN 1174081 C CN1174081 C CN 1174081C
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Abstract
The present invention relates to a preparation method for side chain liquid crystal polyimide films. A side chain liquid crystal polyimide film is prepared by the condensation polymerization of aromatic diamine containing liquid crystal radical element side chains and aromatic teracarboxylic aic dianhydride containing flexible bridging groups. The side chain liquid crystal radical element is directly suspended on a polyimide main chain, and a side chain liquid crystal polyimide film with the effect of in-situ composite self-reinforcement can be obtained by controlling the content of the side chain liquid crystal radical element and the forming technology of liquid crystal phases. The method increases the kind of side chain liquid crystal polymers, and has larger theoretical value and social and economic benefits.
Description
The present invention relates to a kind of preparation method of side-chain liquid crystal polyimide film.Belong to the polymer molecule design and synthesize the field.
The later stage eighties, the backbone chain type liquid crystal polyimide has been launched research abroad, purpose is to utilize the self-assembly principle of liquid crystal unit to prepare high strength fibre, high modulus thermoplastic elastomerics and self-enhancement in-situ composite.European patent Eur.Pat 0 314 986 (1989) reported with aromatic diamine, dihydric phenol, aromatic tetracarboxylic acid's dianhydride be the condensation monomer prepare contain aromatic ester key liquid crystal polyimide, its rigidity is strong, the fusing point height can make the special engineering plastics of high temperature classification, but forming process is poor.Kricheldrof etc. is to containing fragrant acid amides of bonding (Kricheldrof. in addition, Makcromol.Chem.Rapid Commun, 1993,14:395～400), hour ans R etc. is to biphenyl type (hans R, Kricheldrof and half Pakull., Macromolecules, 1988,21 (3): 551～557) the main chain liquid crystal polyimide is studied.Their typical structure is as follows
The objective of the invention is to provide a kind of preparation method of side-chain liquid crystal polyimide film at the deficiencies in the prior art.It is to be prepared by copolycondensation with the aromatic diamine and the aromatic tetracarboxylic acid dianhydride that contain flexible bridge joint base by the aromatic diamine that contains liquid crystalline side-chain.Utilize content and the mesomorphic texture by control side chain liquid crystal unit of group of molecules packing technique-promptly to realize the compound self-strengthening of original position; Utilize the introducing of liquid crystalline side-chain and regularity that copolymerization changes main chain and symmetry to strengthen solvability, to improve moulding processability.
Purpose of the present invention is realized that by following technical measures wherein said raw material umber is molfraction except that specified otherwise.
The preparation method of side-chain liquid crystal polyimide film provided by the invention
A. contain the preparation of end phenolic hydroxyl group liquid crystalline cpd
The starting raw material contraposition is contained 0.1～10.0 part of 0.1～10.0 part of the benzoyl halogen of polar substituent and dihydric phenols compound, 0.01～1.0 part of catalyzer, 5～100 parts of solvents, under 0～35 ℃ of temperature, reacted 8～10 hours, crude product is purified through separating, can prepare and contain liquid crystalline cpd I and the II that holds phenolic hydroxyl group, its structural formula is as follows:
M=-OR ,-COR ,-CN ,-X is R=C wherein
mH
2m+1, m=1～3, X=F, C
B. contain the preparation of the aromatic diamine compound of liquid crystalline side-chain
With 0.1～10.0 part of dinitrobenzene formyl halide with contain 0.1～10.0 part of liquid crystalline cpd holding phenolic hydroxyl group, 5～100 parts of solvents and 0.01～1.0 part of adding of catalyzer have in the reactor of agitator and thermometer, in-5～0 ℃ ice bath, reacted 8～10 hours, crude product is after separating purification, the dinitro compound that must contain liquid crystalline side-chain, again with 0.1～5.0 part of aforementioned dinitro compound with 1.0～10.0 parts of dissolvings of solvent, in the presence of 1% catalyzer, reduce with reductive agent, can prepare the aromatic diamine compound that contains liquid crystalline side-chain, its structural formula is as follows:
R=C wherein
mH
2m+1, m=1～3, X=
F,
Cl
C. the preparation of side-chain liquid crystal polyimide film
0.02～4.0 part of the aromatic diamine that will contain liquid crystalline side-chain, 0.08～6.0 part of the aromatic diamine that contains flexible bridge joint base, 0.1～10.1 part of aromatic tetracarboxylic acid dianhydride, 0.5～100.0 part of solvent, reaction is 12 hours in-5～0 ℃ ice bath, the intermediate polyamic acid solution, spin-coating on sol evenning machine then, under the negative pressure of 0.08～0.1atm in 110 ℃, 2 hours, 160 ℃, 2 hours, 200 ℃, 1 hour, 250 ℃, carried out imidization and handle the Kapton or the master that obtain having the compound self-enhancement feature of obvious side-chain liquid crystal original position in 1 hour, side chain all contains the combined liquid crystal polyimide film of liquid crystal unit; Again above-mentioned film is annealed or electric field polarization near second-order transition temperature, can obtain that side-chain liquid crystal primitive orientation degree is higher, the more tangible Kapton of the compound self-strengthening of original position.The structural formula of this side-chain liquid crystal polyimide is as follows:
R=C wherein
mH
2m+1, m=1～3, X=F, Cl
The benzoyl halogen that contraposition contains polar substituent is for to methoxybenzoyl halogen, to the phenetole formyl halide, to cyano group benzoyl halogen and/or at least a in the chlorobenzoyl halogen; The dinitrobenzene formyl halide is 3,5-dinitrobenzene formyl halide, 2,4-dinitrobenzene formyl halide and/or 2, at least a in the 5-dinitrobenzene formyl halide.
Catalyzer or acid-acceptor are pyridine, diacetyl oxide, N, and N-dimethyl benzylamine and/or imidazoles are at least a.
The aromatic diamine that contains flexible bridge joint group is 3,3 '-diamines yl diphenyl ether, and 4,4 '-diamines yl diphenyl ether, triphen two ether diamines, 4,4 '-two amido ditanes and/or 4,4 '-benzidine is at least a.
The aromatic tetracarboxylic acid dianhydride who contains flexible bridge joint group is the phenyl ether tetracarboxylic dianhydride, 3,3 ', 4, and 4 '-benzophenone tetracarboxylic dianhydride and/or 2, two (3, the 4-dicarboxyl phenyl) hexafluoropropane dianhydrides of 2-are at least a.
Solvent is a N-Methyl pyrrolidone, N,N-dimethylacetamide, N, and dinethylformamide, dimethyl sulfoxide (DMSO), ethylene dichloride, toluene, Glacial acetic acid, methyl alcohol and/or sherwood oil are at least a.
Reductive agent is that hydrogen, hydrazine hydrate and/or zinc-hydrochloric acid are at least a.
Experimental result shows, side-chain liquid crystal polyimide film presents nematic phase texture, combined liquid crystal polyimide film presents stratiform smectic phase texture, the two has all shown higher thermotolerance, liquid crystal thermostability and excellent mechanical property and good film moulding processability, detailed being shown in Table 1.
The present invention has following advantage:
1. when containing the diamine of liquid crystal unit side chain and containing the aromatic diamine copolymerization of flexible bridge joint group, as long as select different aromatic diamine that contains flexible bridge joint base or aromatic tetracarboxylic acid dianhydride, can prepare the multiple polyimide that contains liquid crystalline side-chain, by the content of control side chain liquid crystal unit and the formation technology of mesomorphic phase, can control the liquid crystal liquid crystal property and the mechanical property of side-chain liquid crystal polyimide film.
2. the introducing of side-chain liquid crystal primitive does not change the build-in attribute of polyimide main chain, (5% heat decomposition temperature is between 520～580 ℃ for the thermotolerance height of prepared side-chain liquid crystal polyimide, nitrogen atmosphere), the interval temperature wide (between 240～290 ℃) of mesomorphic phase.
Obtain high-strength, Gao Mo, high-dimensional stability can in, also improved the film forming processing characteristics.The tensile strength of film can increase by 40～170%, and modulus can increase by 60～170%, and film may be dissolved in conventional solvent such as N-Methyl pyrrolidone, N, in dinethylformamide, the N,N-dimethylacetamide.
Embodiment
Below by embodiment the present invention is specifically described.Be necessary to be pointed out that at this present embodiment only is used for the present invention is further detailed, can not be interpreted as limiting the scope of the invention, the person skilled in the art of this area can content according to the present invention make some nonessential improvement and adjustment.
1. with 0.5 mole 3,5-dinitrobenzene formyl halide splashes in the solution of being made up of the pyridine of equimolar 4-xenol, 2.0 moles of tetrahydrofuran (THF)s and 0.1 mole, and reaction is 10 hours in-5～0 ℃ ice bath, desolventizing under 0.08～0.1atm negative pressure, washing, the sodium hydroxide solution washing with 0.5% is washed to neutrality, suction filtration, drying is used the ethylene dichloride recrystallization, gets white needle-like crystals 3,5-dinitrobenzoic acid-4 '-biphenyl ester, 218～218.5 ℃ of fusing points.
With 0.5 mole 3,5-dinitrobenzoic acid-4 '-biphenyl ester is suspended in 2.5 moles the ethylene dichloride, adds 1% carbon-palladium catalyst, feeds H
2Reaction is 24～48 hours under 0～35 ℃, and filtered while hot is sloughed solvent, and with toluene, sherwood oil (1: 1 volume ratio) extraction, icy salt solution cooling recrystallization gets the white plates crystal 3,5-diamines yl benzoic acid-4 '-biphenyl ester, 170～172 ℃ of fusing points.
With 3,0.25 mole of 5-diamines yl benzoic acid-4 '-biphenyl ester, the phenyl ether diamines is dissolved in the N-Methyl pyrrolidone for 0.75 mole, the mass percent concentration of control solution is 6～8%, after treating dissolving fully, add 1.01 moles of phenyl ether tetracarboxylic dianhydrides, in-5～0 ℃ ice bath the reaction 12 hours after spin-coating on slide glass, under the negative pressure of 0.08～0.1atm, in 110 ℃ of temperature, 2 hours, 160 ℃, 2 hours, 200 ℃, 1 hour, 250 ℃, 1 hour imidization, obtain having the Kapton of the compound self-enhancement feature of obvious side-chain liquid crystal original position, the side-chain liquid crystal polyimide film of this method preparation is nematic phase texture, 241 ℃ of its second-order transition temperatures, 271 ℃ of clearing point transition temperatures, tensile strength is 226MPa, modulus is 5.06GPa, and 5% decomposition temperature is (nitrogen atmosphere) 553 ℃, and this film can be dissolved in conventional solvent such as N-Methyl pyrrolidone, N, dinethylformamide, in the N,N-dimethylacetamide.This film is being annealed a little more than under the second-order transition temperature, and its side-chain liquid crystal primitive orientation degree is higher, the compound self-strengthening of original position is more obvious, and the Kapton mechanical strength is increased to 235MPa, and modulus is increased to 5.36GPa.
2. 1.0 moles anisoyl chloride is slowly splashed under 0～5 ℃ by 1.2 moles of Resorcinol, 5.0 moles tetrahydrofuran (THF) and 0.5 mole N, in the solution that the N-dimethyl benzylamine is formed, react after 10 hours, under the negative pressure of 0.08～0.1atm, slough solvent, will precipitate in the crude product impouring water, with hot wash for several times, filter drying, recrystallization in the toluene, get white needle-like crystals 4-methoxyl group-4 '-hydroxy-benzoic acid first, 136～137 ℃ of fusing points.
0.5 mole of above-mentioned 4-methoxyl group-4 '-hydroxy-benzoic acid methyl esters is dissolved in 4.0 moles the tetrahydrofuran solution, under 0～5 ℃, 0.5 mole 3,5 dinitrobenzoylchloride is splashed into wherein, reacted 8～10 hours, under the negative pressure of 0.08～0.1atm, slough solvent, precipitate washing, drying in the impouring water, use the tetrahydrofuran (THF) recrystallization, get 3,5-dinitrobenzoic acid-4 ' (to methoxyl group-phenylformic acid) phenyl ester white crystal, 170～172 ℃ of fusing points.
With above-mentioned 3,0.5 mole of 5-dinitrobenzoic acid-4 ' (to methoxyl group-phenylformic acid) phenyl ester is dissolved in 4.5 moles the tetrahydrofuran solution, makes catalyzer with 1% carbon-palladium, feeds H under 0～10 ℃ of temperature
2Reduced 48 hours, and filtered, concentrate, ethyl alcohol recrystallization gets white needle-like crystals 3,5-diamines yl benzoic acid-4 ' (to methoxyl group-phenylformic acid)-phenyl ester liquid crystalline cpd.
With above-mentioned 3,0.35 mole of 5-diamines yl benzoic acid-4 ' (to methoxyl group-phenylformic acid)-phenyl ester, 0.55 mole of benzophenone tetracarboxylic dianhydride, 0.55 mole of phenyl ether tetracarboxylic dianhydride and phenyl ether diamines are dissolved in an amount of N-Methyl pyrrolidone for 0.65 mole, the mass percent concentration of control solution is about 10%, reaction is 10 hours in-5～0 ℃ of ice bath, spin-coating is on slide glass then, under the negative pressure of 0.08～0.1atm, in 110 ℃ of temperature, 2 hours, 160 ℃, 2 hours, 200 ℃, 1 hour, 250 ℃, 1 hour imidization, obtain having the Kapton of the compound self-enhancement feature of obvious side-chain liquid crystal original position, the side-chain liquid crystal polyimide film of this method preparation is nematic phase texture, 246.4 ℃ of its second-order transition temperatures, 288 ℃ of clearing point transition temperatures, tensile strength are 194MPa, and modulus is 4.36GPa, 5% decomposition temperature is (nitrogen atmosphere) 549 ℃, can be dissolved in conventional solvent such as N-Methyl pyrrolidone, N, dinethylformamide, in the N,N-dimethylacetamide.A little more than electric field polarization under the second-order transition temperature, the mechanical strength of Kapton and modulus have improved 14.1MPa and 0.42GPa respectively with this film.
3. with 3,5-diamines yl benzoic acid-4 '-biphenyl ester 0.35 mole (preparation is with example 1), 4,0.4 mole of 4 '-diamines yl diphenyl ether, 4,0.25 mole of 4 '-benzidine and phenyl ether tetracarboxylic dianhydride add solvent N for 1.05 moles, dissolve in the N-N,N-DIMETHYLACETAMIDE, the mass percent concentration of control solution is 8～10%, at N
2Protection was reacted 10 hours in-5～0 ℃ of ice bath down, use the sol evenning machine spin-coating then, under the negative pressure of 0.08～0.1atm, in 110 ℃ of temperature, 2 hours, 160 ℃, 2 hours, 200 ℃, 1 hour, 250 ℃, 1 hour imidization, obtain having the compound self-enhancement combination of features of obvious liquid crystal original position type liquid crystal polyimide film, the combined liquid crystal polyimide film of this method preparation is smectic phase texture, 251 ℃ of its second-order transition temperatures, 284 ℃ of clearing point transition temperatures, tensile strength is 174MPa, modulus is 4.3GPa, and 5% decomposition temperature is (nitrogen atmosphere) 572 ℃, is dissolved in N-Methyl pyrrolidone, N, dinethylformamide, in the N,N-dimethylacetamide; This film is being annealed a little more than under the second-order transition temperature, and its side-chain liquid crystal primitive orientation degree is higher, the compound self-strengthening of original position is more obvious, and Kapton mechanical strength and modulus have improved 9.4% and 8.6% respectively.
4. with 3,5-diamines yl benzoic acid-4 '-biphenyl ester 0.025 mole (preparation is with example 1), 4,0.05 mole of 4 '-diamines yl diphenyl ether, 4,0.025 mole of 4 '-benzidine and 2,2-two (3,4-dicarboxyl phenyl) dissolve in 0.105 mole of adding of hexafluoropropane dianhydride solvent N-Methyl pyrrolidone, the mass percent concentration of control solution is 8～10%, at N
2Protection was reacted 10 hours in-5～0 ℃ of ice bath down; use the sol evenning machine spin-coating then; under the negative pressure of 0.08～0.1atm; in 140 ℃ of temperature; 2 hours, 160 ℃, 2 hours; 200 ℃; 1 hour, 250 ℃, 1 hour imidization; obtain having the compound self-enhancement combination of features of obvious liquid crystal original position type liquid crystal polyimide film; the combined liquid crystal polyimide film of this method preparation is smectic phase texture, 236 ℃ of its second-order transition temperatures, 280 ℃ of clearing point transition temperatures; tensile strength is 164MPa; modulus is 3.76GPa, and 5% decomposition temperature is (nitrogen atmosphere) 552 ℃, is soluble in N-Methyl pyrrolidone; N; dinethylformamide; in the N,N-dimethylacetamide equal solvent.
The performance of table 1 side-chain liquid crystal polyimide film
*
The interval temperature strength modulus of liquid crystal polyamides 5% decomposition temperature crystalline phase solubility property
*
Imines (℃, N
2) (℃) (MPa) (GPa) NMP DMF DMAc DMSO
Side chain type 520～560 240～290 140～235 2.7～5.3 are broad
Combined 540～590 235～290 130～180 3.3～4.3 is broad
*In the diamine, the molfraction of side-chain liquid crystal primitive diamine is 10～40%
*The NMP:N-methyl-2-pyrrolidone; DMF:N, dinethylformamide; DMAc:N, the N-N,N-DIMETHYLACETAMIDE; DMSO: dimethyl sulfoxide (DMSO)
Claims (7)
1. the preparation method of side-chain liquid crystal polyimide film is characterized in that:
A. contain the preparation of end phenolic hydroxyl group liquid crystalline cpd
(wherein said raw material umber is except that specified otherwise with starting raw material, being molfraction) contraposition contains 0.1～10.0 part of the benzoyl halogen of polar substituent, 0.1～10.0 part of dihydric phenols compound, and 0.01～1.0 part of catalyzer, 5～100 parts of solvents, in 0～35 ℃ of reaction 8～10 hours, crude product was purified through separating, can prepare and contain aromatic ester liquid crystalline cpd I and the II that holds phenolic hydroxyl group, its structural formula is as follows:
M＝-OR，-COR，-CN，-X
R=G wherein
mH
2m+1, m=1～3, X=F, Cl
B, contain the preparation of the aromatic diamine compound of liquid crystalline side-chain
With 0.1～10.0 part of dinitrobenzene formyl halide, contain 0.1～10.0 part of liquid crystalline cpd holding phenolic hydroxyl group, 5～100 parts of solvents and 0.01～1.0 part of adding of catalyzer have in the reactor of agitator and thermometer, in-5～0 ℃ ice bath, reacted 8～10 hours, crude product is after separating purification, the dinitro compound that must contain liquid crystalline side-chain, again with the dissolution with solvents of 1～10.0 part of 0.1～5.0 part of usefulness of aforementioned dinitro compound, in the presence of 1% catalyzer, reduce with reductive agent, can prepare the aromatic diamine compound that contains liquid crystalline side-chain, its structural formula is as follows:
F＝H，CN M＝-OR，-COR，-CN，-X
R=C wherein
mH
2m+1, m=1～3, X=F, Cl
The preparation method of c, side-chain liquid crystal polyimide film
0.02～4.0 part of the aromatic diamine that will contain liquid crystalline side-chain, 0.08～6.0 part of the aromatic diamine that contains flexible bridge joint base, 0.1～10.1 part of aromatic tetracarboxylic acid dianhydride, 0.5～100.0 part of solvent, reaction is 12 hours in-5～0 ℃ ice bath, gets intermediate polyamic acid solution, spin-coating on sol evenning machine then, under the negative pressure of 0.08～0.1atm, in 110 ℃ of temperature, 2 hours, 160 ℃, 2 hours, 200 ℃, 1 hour, 250 ℃, imidization was handled in 1 hour, the Kapton or the master that obtain having the compound self-enhancement feature of obvious side-chain liquid crystal original position, side chain all contains the combined liquid crystal polyimide film of liquid crystal unit; Above-mentioned film is annealed or electric field polarization near second-order transition temperature, can obtain that side-chain liquid crystal primitive orientation degree is higher, the more tangible Kapton of the compound self-strengthening of original position, the structural formula of side-chain liquid crystal polyimide is as follows:
M＝-OR，-COR，-CN，-X
R=C wherein
mH
2m+1, m=1～3, X=F, Cl
2. according to the preparation method of the described side-chain liquid crystal polyimide film of claim 1, it is characterized in that benzoyl halogen that described contraposition contains polar substituent is for to methoxybenzoyl halogen, to the phenetole formyl halide, to cyano group benzoyl halogen and/or at least a to chlorobenzoyl halogen; The dinitrobenzene formyl halide is 3,5-dinitrobenzene formyl halide, and 2,4-dinitrobenzene formyl halide and/or 2,5-dinitrobenzene formyl halide is at least a.
3. according to the preparation method of the described side-chain liquid crystal polyimide film of claim 1, it is characterized in that catalyzer or acid-acceptor are carbon-palladium, pyridine, diacetyl oxide, N, N-dimethyl benzylamine and/or imidazoles are at least a.
4. according to the preparation method of the described side-chain liquid crystal polyimide film of claim 1, the aromatic diamine that it is characterized in that containing flexible bridge joint group is 3,3 '-diamines yl diphenyl ether, 4,4 '-diamines yl diphenyl ether, triphen two ether diamines, 4,4 '-two amido ditanes and/or 4,4 '-benzidine is at least a.
5. according to the preparation method of the described side-chain liquid crystal polyimide film of claim 1, the aromatic tetracarboxylic acid dianhydride who it is characterized in that containing flexible bridge joint group is the phenyl ether tetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride and/or 2, two (3, the 4-dicarboxyl phenyl) hexafluoropropane dianhydrides of 2-are at least a.
6. according to the preparation method of the described side-chain liquid crystal polyimide film of claim 1, it is characterized in that solvent is a N-Methyl pyrrolidone, N,N-dimethylacetamide, N, dinethylformamide, dimethyl sulfoxide (DMSO), toluene, Glacial acetic acid, methyl alcohol, ethylene dichloride and/or sherwood oil are at least a.
7. according to the preparation method of the described side-chain liquid crystal polyimide film of claim 1, it is characterized in that reductive agent is that hydrogen, hydrazine hydrate and/or zinc-hydrochloric acid are at least a.
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| JP5239231B2 (en) | 2007-07-06 | 2013-07-17 | 株式会社リコー | Diamine compound, polyamic acid and soluble polyimide, and wettability changing film and electrode obtained therefrom |
| JP5569441B2 (en) * | 2010-08-27 | 2014-08-13 | Ｊｓｒ株式会社 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element |
| JP5673869B2 (en) * | 2014-01-15 | 2015-02-18 | Jnc株式会社 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element |
| CN109694574A (en) * | 2018-12-17 | 2019-04-30 | 无锡创彩光学材料有限公司 | A kind of high adhesiveness Kapton, preparation method and flexible copper-clad plate |
| CN112062953B (en) * | 2020-09-07 | 2022-05-31 | 陕西师范大学 | Oxazole group-containing quaternary ammonium salt side chain liquid crystal ionomer and preparation method thereof |
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