CN101007951A - Preparation method of polyimide liquid crystal vertical-tropism agent - Google Patents
Preparation method of polyimide liquid crystal vertical-tropism agent Download PDFInfo
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Abstract
The invention discloses a method for preparing medlin vetivcal orienting agent. It is characterized in that it comprises following steps: adding organic tetracarboxylic dianhydride 1- 100 unit by weight, special diamine 1- 100 unit by weight and organic diamine into three- necked bottle equipped with temperature gauge and stirring device, reacting for 24- 28 hours under nitrogen protection at normal temperature, gettingpolyamic acid vetivcal orienting agent, diluting said polyamic acid in organic solvent until the concentration being 2.5- 5%, rotary coating it on ITO glass board, pre- drying for 20- 40 minutes under nitrogen protection at 80- 120 Deg. C, curing at 200 Deg. C, 250 Deg. C and 300 Deg. C for 1-3 hours, then rubbing medlin film with rubbing machine or preparing liquid crystal box with it, the tilt angle of liquid crystal in liquid crystal box is near to 90 degrees.
Description
Technical field:
The present invention relates to a kind of preparation method of polyimide liquid crystal vertical-tropism agent, belong to the preparation field of various liquid-crystal displays in the electronic industry.
Background technology:
Liquid-crystal display will obtain the fine imaging results, necessarily requires liquid crystal molecule to have good stable initial arrangement, so the research that aligns of liquid crystal has become a key subject in the liquid-crystal display research and development.The orientation of liquid crystal mainly is that the substrate surface that has scribbled polymkeric substance by rubbing obtains, just so-called rubbing manipulation (rubbing method) (Ding Mengxian (Ding Meng-xian), He Tianbai (He Tian-bai). polyimide type material (Jvxianyaan Xinxing Cailiao). Beijing: Chemical Industry Press (Beijing:Chemical Industry Press), 1998:142.), the polyimide surface that is rubbed relies on it to adsorb a large amount of other liquid crystal molecules by short distance reactive force absorption one deck liquid crystal unimolecular layer then.The liquid-crystal display of traditional parallel-oriented technology of use has born chronic illness, as narrow angle of visibility.Because vertically aligned liquid crystal display (VA-LCDs) has excellent properties such as high-contrast, wide viewing angle and fast response time, so the research and development emphasis of liquid crystal molecular orientation technology has been transferred to vertical orientatedly to come up.Modern vertically aligned liquid crystal display all is as alignment films usually with the polyimide that has the alkane side chain or polyamic acid film.In order to control vertical orientated position angle of liquid crystal molecule and tilt angle, use traditional rubbing manipulation equally.Traditional rubbing manipulation has also been brought a series of detrimentally affects, the static charge of bringing such as friction, dust and wearing and tearing etc., even may damage thin film transistor in the Thin Film Transistor-LCD (TFT-LCD), therefore, non-friction techniques is widely studied (Ohe M and Hiroshi Y.Physical Review, 2004, E 69:051705.).By the chemical structure of particular design, polyimide film can obtain the liquid crystal vertical-tropism effect, and it is used in vertically aligned liquid crystal display (VA-LCD) and the multi-domain vertical alignment liquid-crystal display (MVA-LCD).MVA-LCDs is than early stage VA-LCDs, and the division on two farmlands even four farmlands has greatly improved liquid-crystal display at the angle of visibility of four direction up and down.MVA has possessed the ability with competitions such as other wide viewing angle technology such as film compensation TN box, plane switchable liquid crystal boxes (IPS).
Ball paddy English three, Li Shanjing are helped etc., Chinese patent, 200510064680.4, a series of liquid crystal vertical-tropism films that adopted the polymer manufacture that contains polyamic acid, polyimide component.In this polyamic acid or polyimide, at side chain all are alkyl chains of introducing carbon number 10～20, or the organic group of the carbon number 4～40 of fatty ring type bone, or be substituted with the organic group of the carbon number 6～20 of fluorine atom, or carbon number is 1～24 alkane group and halogenated alkane group.Substantially all be by introducing-O-,-CO-,-COO-,-OCO-,-NHCO-,-CONH-,-S-wait to link to each other with the main chain phenyl ring.Through checking, wherein major part can obtain good vertical at last
Orientation effect, voltage retention reaches more than 98%.The image retention cancellation time also can be controlled in the 50s.
Ogawa L et al WO, 042752, propose in polyimide, to have the dianhydride that 2 to 5 aliphatics rings constitute and have 5～20 long alkyl chain length or contain the fluoro-alkyl of length of 5～20 carbon or the diamines of the side-chain structure of cycloaliphatic ring family structure or aromatic ring structure is formed.The alignment films that evidence prepares thus has good coating and high voltage retention.
In sum, traditional parallel-oriented TN liquid crystal cell also exists many chronic illnesses because its displaying principle, and therefore for example slow time of response, narrow angle of visibility and not high contrast gradient have limited the development of liquid-crystal display industry; Though existing vertical orientated membrane technique has significant progress,, be unfavorable for the exploitation of the product for civilian use and the development of industrial chain because too numerous and diverse structure of chemical composition is difficult to realize the industrialization of this technology; Because quick development of modern science and technology, people increase the demand of liquid crystal technology, and are also more and more higher to the technical requirements of liquid-crystal display, as the raising in work-ing life etc., therefore, the thermostability for liquid crystal aligning and tilt angle thereof has all proposed new requirement.
Summary of the invention:
The objective of the invention is to provide a kind of preparation method of polyimide liquid crystal vertical-tropism agent at the deficiencies in the prior art, be characterized in this liquid crystal vertical-tropism agent can make liquid crystal molecule vertical orientated on substrate, have a polyamic acid liquid crystal orientation agent of good coated with glass simultaneously.Can overcome the chronic illness of many parallel-oriented liquid-crystal displays by the liquid-crystal display of liquid crystal vertical-tropism technology manufacturing, as high-contrast, wide visual angle and faster response time.
Purpose of the present invention is realized that by following technical measures wherein said raw material umber is parts by weight except that specifying.
The preparation method of polyimide liquid crystal vertical-tropism agent
(1) preparation of particular chemical structure diamines
The reaction formula of specific diamines is as follows:
Wherein, B is benzene, biphenyl or alicyclic ring; F is carboxylic acid or acid chloride functional groups; R is the alkyl group of 1～18 carbon atom; X is the chlorine or bromine atom.
The preparation of a.M1
1～40 part of HO-B-OH and 1～10 part of catalyzer adding are had in the three-necked bottle of thermometer, agitator, add 40～80 parts of solvents, making it dissolve the back fully in 50～70 ℃ of stirrings of temperature adds 1～10 part of halogenated alkane, continues reaction 12～24 hours, cold filtration under the room temperature behind the stopped reaction, filtrate is poured in a large amount of distilled water again, deposition, suction filtration is with diluted acid and distilled water repetitive scrubbing, dried overnight, recrystallization get product M1;
The preparation of b.M2
1～10 part of above-mentioned M1 and 0.01～1 part of catalyzer are added in the above-mentioned conversion unit, add 20～60 parts of solvents, add 1～10 part of dinitrobenzene compound again after stirring is dissolved it fully under the room temperature, react stopped reaction after 6～12 hours under the room temperature, pour in the big water gaging, deposition, suction filtration, thorough washing, vacuum-drying, recrystallization gets product M2;
The preparation of c.M3
Above-mentioned M2 1～10 and 0.1～1 part of adding of catalyzer are had in the three-necked bottle of agitator, add 20～60 parts of stirrings of solvent it is dissolved fully, be warming up to backflow, drip 0.1～1 part of proton donor, adopt the TLC monitoring reaction, vacuum is spin-dried for solvent, and recrystallization gets product M3 then;
(2) preparation of the vertical orientated agent solution of polyamic acid
With 1～100 part of tetracid acid dianhydride, 1～100 part of specific diamines and 1～100 part of organic diamine add and have in the three-necked bottle of thermometer, agitator; Make it to dissolve fully under room temperature with 50～200 parts of organic solvents, room temperature reaction is 24～48 hours under nitrogen protection, promptly obtains the vertical orientated agent solution of polyamic acid liquid crystal with solvent cut to 2.5%～5% again;
(3) preparation of liquid crystal cell
On ito glass substrate, use alkali lye, detergent solution, water and Virahol clean, after the drying above-mentioned polyamic acid solution is spun on the ito glass substrate, under nitrogen protection in 80～120 ℃ of preliminary drying 20～40min of temperature, then at 200 ℃, respectively solidify 1～3h under 250 ℃ and 300 ℃ of high temperature, polyimide film rubs or does not rub with rubbing machine, with the optic-solidified adhesive that contains 10～40um introns two ito glass substrates are bonded to box by the antiparallel frictional direction, utilize the liquid crystal of isotropic state the kapillary method to pour in the liquid crystal cell, seal with optic-solidified adhesive subsequently, the tilt angle that obtains liquid crystal vertical-tropism is near 90 °;
The chemical structural formula of polyimide is as follows:
Wherein, n=15～45, D1 is the quaternary organic group, promptly organic tetracarboxylic dianhydride removes the part of four carboxylic acids; D2 is organic divalent moiety that organic diamine is removed two amidos; B is benzene, biphenyl or alicyclic ring; R is the alkyl group of 1～18 carbon atom.
Organic diamine is Ursol D, mphenylenediamine, 4 ', 4 one diaminodiphenylmethane, 4 ', 4 one diamino benzophenone, 4,4 ' one diaminodiphenyl oxide, 3,4 ' one diaminodiphenyl oxide, 3,3 ' one diaminodiphenyl oxide, 4,4 '-two (4-amino-benzene oxygen) propane, 4,4 '-two (4-amino-benzene oxygen) HFC-236fa, 2, two [4-(4-amino-benzene oxygen) phenyl] propane, 2 of 2-, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 4 of 2-, any in 4 '-two (4-amino-benzene oxygen) benzene.They can be separately and 2 kinds or above being used in combination; Except that above-mentioned specific organic diamine,, also can and use other organic diamine as long as in the scope that does not hinder effect of the present invention.
The tetracarboxylic dianhydride is equal benzene tertacarbonic acid's dianhydride, biphenyl tetracarboxylic dianhydride, 3,3,4,4-phenyl ether tetracarboxylic dianhydride, 3,3,4,4-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-triphen diether tetracarboxylic dianhydride, 4,4 '-(hexafluoro sec.-propyl) two O-phthalic carboxylic acid dianhydride, 1,2,3,4-tetramethylene tetracarboxylic dianhydride, 3c-carboxymethyl pentamethylene-1r, 2c, 4c-tricarboxylic acid-1,4:2,3-dianhydride (TCAAH), 1,2,4, any among the 5-hexanaphthene tetracarboxylic dianhydride.They can be separately and 2 kinds or above being used in combination; Except that above-mentioned specific tetracid acid dianhydride,, also can and use other tetracarboxylic dianhydride as long as in the scope that does not hinder effect of the present invention.
Solvent is ethanol, propyl carbinol, methyl alcohol, tetrahydrofuran (THF), Virahol, N-Methyl pyrrolidone, N, any in dinethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), gamma-butyrolactone or its mixture.
Catalyzer is any among potassium hydroxide, sodium hydroxide, triethylamine, pyridine, iron, the Pd/C.
Proton donor is any in hydrazine hydrate, hydrochloric acid, the hydrogen.
The polyimide liquid crystal vertical-tropism agent that the preparation method of polyimide liquid crystal vertical-tropism agent prepares.
Polyimide liquid crystal vertical-tropism agent is used to make liquid crystal cell, and the tilt angle of liquid crystal is near 90 ° in the liquid crystal cell.
The performance test of polyimide liquid crystal vertical-tropism agent:
The effect of polyimide liquid crystal vertical-tropism agent is to observe by the microscope that has the cross-polarized light plate, if there is not light transmission, it then is liquid crystal vertical-tropism, rely on crystal rotation method to record the tilt angle of vertical orientated liquid crystal molecule near 90 °, under dark attitude, also can make assessment, see that whether to have bright spot or bright rays too much the homogeneity of liquid crystal molecular orientation;
The stability of liquid crystal cell is that the liquid crystal cell of having made is placed baking oven, toasts 12h under 120 ℃ of high temperature, observes with polarizing microscope in different time sections, measures its tilt angle simultaneously;
Whether the screening characteristics of liquid crystal is good, directly with the naked eye observes behind the spin coating polyamic acid solution, and assessment is detailed to be shown in Table 1.
The present invention has the following advantages:
1. adopt specific diamines synthesis of polyimides can obtain good vertical orientated effect;
Liquid crystal cell 120 ℃ down baking 12h vertical orientated destruction does not appear, illustrating that this product works long hours under higher temperature and is unlikely to lost efficacy;
3. the tilt angle of Huo Deing is near 90 °, and tilt angle is a stabilized uniform, even after stronger friction, significantly reducing does not appear in high tilt angle yet.
Embodiment:
Below by embodiment the present invention is carried out concrete description; Be necessary to be pointed out that at this present embodiment only is used for the present invention is further specified; but can not be interpreted as the restriction of protection domain of the present invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of the invention described above.
Embodiment 1:
1.1 the preparation of particular chemical structure diamines
A.4 '-preparation of Ding alkoxyl group-4-xenol
With 1 part 4,4 '-dihydroxybiphenyl and 1 part of potassium hydroxide add and have in the three-necked bottle of agitator, add 40 parts of methyl alcohol and in 50 ℃ of stirrings of temperature it are dissolved fully, 1 part of bromination of n-butane are added in the reaction mixture again, stirring reaction 12 hours, cold filtration under the room temperature behind the stopped reaction is poured filtrate in a large amount of distilled water into, deposits a large amount of solids crude products, suction filtration, with dilute hydrochloric acid and distilled water repetitive scrubbing, dried overnight, recrystallization promptly gets product;
B.4-fourth alkoxyl group xenol-3 ', the preparation of 5 '-dinitrobenzoic acid ester
1 part of above-mentioned product and 0.1 part of triethylamine adding are had in the three-necked bottle of agitator, add 20 parts of stirrings of tetrahydrofuran (THF) it is dissolved fully, again 1 part of 3,5 dinitrobenzoylchloride is added in the three-necked bottle, react stopped reaction after 6 hours under the room temperature, solution is poured in a large amount of cold water, and a large amount of solids are deposited suction filtration, behind the thorough washing, drying gets thick product, and recrystallization promptly gets product;
C.4-fourth alkoxyl group xenol-3 ', the preparation of 5 '-diamines yl benzoic acid ester
1 part of above-mentioned product and 20 parts of Virahols addings are had in the three-necked bottle of agitator, add 0.1 part of 5%Pd/C catalyzer again, stirring heating, be warming up to backflow, be added dropwise to 0.1 part of 80% hydrazine hydrate, the TLC monitoring reaction finishes the reaction after-filtration and falls catalyzer, vacuum is spin-dried for solvent, and recrystallization promptly gets product.
1.2 the preparation of polymkeric substance
With 10 part 3,3,4,4-phenyl ether tetracarboxylic dianhydride, 3 parts of 4-fourth alkoxyl group xenols-3 ', 5 '-diamines yl benzoic acid ester and 7 parts of Ursol D are dissolved in 50 parts of N-Methyl pyrrolidone, at N
2Protection is diluted to 2.5% with N-Methyl pyrrolidone and can obtains the polyamic acid liquid crystal vertical-tropism agent down in room temperature reaction 24h.
1.3 the preparation of liquid crystal cell
On ito glass substrate, clean, after the drying above-mentioned polyamic acid solution is spun on the ito glass substrate, at N with alkali lye, detergent solution, water and Virahol
2Protection is down in 80 ℃ of preliminary drying 20min of temperature; respectively solidify 1h 200 ℃ of temperature, 250 ℃ and 300 ℃ then; polyimide film does not use rubbing machine to rub; with the optic-solidified adhesive that contains the 10um introns two ito glass substrates are bonded to box by the antiparallel frictional direction; utilize the liquid crystal of isotropic state the kapillary method to pour in the liquid crystal cell, seal with optic-solidified adhesive subsequently.
Embodiment 2:
2.1 the preparation of particular chemical structure diamines
A.4 '-preparation of Ding alkoxyl group-4-hydroxybenzene
With 20 part 4,4 '-dihydroxybiphenyl and 5 parts of sodium hydroxide add and have in the three-necked bottle of agitator, add 60 parts of ethanol and in 60 ℃ of stirrings of temperature it are dissolved fully, 5 parts of n-propylcarbinyl chlorides are added in the reaction mixtures again, stirring reaction 24 hours, cold filtration under the room temperature behind the stopped reaction is poured filtrate in a large amount of distilled water into, deposits a large amount of solids crude products, suction filtration, with dilute hydrochloric acid and distilled water repetitive scrubbing, dried overnight, recrystallization promptly gets product;
B.4-fourth alkoxy phenol-2 ', the preparation of 4 '-dinitrobenzoic acid ester
5 parts of above-mentioned products and 0.5 part of pyridine adding are had in the three-necked bottle of agitator, add 40 parts of stirrings of tetrahydrofuran (THF) it is dissolved fully, again with 5 part 2, the 4-dinitrobenzoyl chloride adds in the three-necked bottle, react stopped reaction after 12 hours under the room temperature, solution is poured in a large amount of cold water, and a large amount of solids are deposited suction filtration, behind the thorough washing, drying gets thick product, and recrystallization promptly gets product;
C.4-fourth alkoxy phenol-2 ', the preparation of 4 '-diamines yl benzoic acid ester
5 parts of above-mentioned products and 40 parts of ethanol addings are had in the three-necked bottle of agitator, add 0.5 part of 5%Pd/C catalyzer again, stirring heating, be warming up to backflow, feed 0.5 part of hydrogen, the TLC monitoring reaction, finish the reaction after-filtration and fall catalyzer, vacuum is spin-dried for solvent, and recrystallization promptly gets product.
2.2 the preparation of polymkeric substance
With 50 parts of biphenyl tetracarboxylic dianhydrides, 10 parts of 4-fourth alkoxy phenols-2 ', 4 '-diamines yl benzoic acid ester and 40 part 4,4 '-diamino benzophenone is dissolved in 100 parts of N, and dinethylformamide is at N
2Protection is used N down in room temperature reaction 36h, and dinethylformamide is diluted to 4% can obtain the polyamic acid liquid crystal vertical-tropism agent.
2.3 the preparation of liquid crystal cell
On ito glass substrate, clean, after the drying above-mentioned polyamic acid solution is spun on the ito glass substrate, at N with alkali lye, detergent solution, water and Virahol
2Protection is down in 100 ℃ of preliminary drying 30min of temperature; respectively solidify 2h 200 ℃ of temperature, 250 ℃ and 300 ℃ then; polyimide film uses rubbing machine to rub; the friction number of times is secondary (one way); with the optic-solidified adhesive that contains the 20um introns two ito glass substrates are bonded to box by the antiparallel frictional direction; utilize the liquid crystal of isotropic state the kapillary method to pour in the liquid crystal cell, seal with optic-solidified adhesive subsequently.
Embodiment 3:
3.1 the preparation of particular chemical structure diamines
A.4 '-preparation of Ding alkoxyl group-4-xenol
With 40 part 4,4 '-dihydroxybiphenyl and 10 parts of potassium hydroxide add and have in the three-necked bottle of agitator, add 80 parts of methyl alcohol and in 70 ℃ of stirrings it are dissolved fully; Again 10 parts of bromination of n-butane are added in the reaction mixture stirring reaction 24 hours, cold filtration under the room temperature behind the stopped reaction, filtrate is poured in a large amount of distilled water, deposit a large amount of solids crude products, suction filtration, with dilute hydrochloric acid and distilled water repetitive scrubbing, dried overnight, recrystallization promptly gets product;
B.4-fourth alkoxyl group xenol-3 ', the preparation of 5 '-dinitrobenzoic acid ester
10 parts of above-mentioned products and 1 part of triethylamine adding are had in the three-necked bottle of agitator, add 60 parts of stirrings of tetrahydrofuran (THF) it is dissolved fully, again 10 parts of 3,5 dinitrobenzoylchloride are added in the three-necked bottle, react stopped reaction after 24 hours under the room temperature, solution is poured in a large amount of cold water, and a large amount of solids are deposited suction filtration, behind the thorough washing, drying gets thick product, and recrystallization promptly gets product;
C.4-fourth alkoxyl group xenol-3 ', the preparation of 5 '-diamines yl benzoic acid ester
10 parts of above-mentioned products and 60 parts of propyl carbinols addings are had in the three-necked bottle of agitator, add 1 part of iron powder catalyzer again, stirring heating is warming up to backflow, is added dropwise to 1 part of concentrated hydrochloric acid, the TLC monitoring reaction.Finish the reaction after-filtration and fall catalyzer, vacuum is spin-dried for solvent, and recrystallization promptly gets product.
3.2 the preparation of polymkeric substance
With 100 part 3,3,4,4-benzophenone tetracarboxylic dianhydride, 25 parts of 4-fourth alkoxyl group xenols-3 ', 5 '-diamines yl benzoic acid ester and 75 part 3,4 '-diaminodiphenyl oxide be dissolved in 200 parts of dimethyl sulfoxide (DMSO) rare in, at N
2Protection is diluted to 5% with dimethyl sulfoxide (DMSO) and can obtains the polyamic acid liquid crystal vertical-tropism agent down in room temperature reaction 48h.
3.3 the preparation of liquid crystal cell
On ito glass substrate, clean, after the drying above-mentioned polyamic acid solution is spun on the ito glass substrate, at N with alkali lye, detergent solution, water and Virahol
2Protection is down in 120 ℃ of preliminary drying 40min of temperature; respectively solidify 3h 200 ℃ of temperature, 250 ℃ and 300 ℃ then; polyimide film uses rubbing machine to rub; the friction number of times is four times (one way); with the optic-solidified adhesive that contains the 40um introns two ito glass substrates are bonded to box by the antiparallel frictional direction; utilize the liquid crystal of isotropic state the kapillary method to pour in the liquid crystal cell, seal with optic-solidified adhesive subsequently.
Embodiment 4:
4.1 the preparation of particular chemical structure diamines
A.4 '-preparation of own alkoxyl group-4-hydroxybenzene
With 1 part 4,4 '-dihydroxybiphenyl and 1 part of sodium hydroxide add and have in the three-necked bottle of agitator, add 40 parts of methyl alcohol and in 50 ℃ of stirrings of temperature it are dissolved fully, 1 part of chloro normal hexane are added in the reaction mixture again, stirring reaction 12 hours, cold filtration under the room temperature behind the stopped reaction is poured filtrate in a large amount of distilled water into, deposits a large amount of solids crude products, suction filtration, with dilute hydrochloric acid and distilled water repetitive scrubbing, dried overnight, recrystallization promptly gets product;
B.4-own alkoxy phenol-2 ', the preparation of 4 '-dinitrobenzoic acid ester
1 part of above-mentioned product and 0.1 part of pyridine adding are had in the three-necked bottle of agitator, add 20 parts of stirrings of tetrahydrofuran (THF) it is dissolved fully, again with 1 part 2, the 4-dinitrobenzoyl chloride adds in the three-necked bottle, react stopped reaction after 6 hours under the room temperature, solution is poured in a large amount of cold water, and a large amount of solids are deposited suction filtration, behind the thorough washing, drying gets thick product, and recrystallization promptly gets product;
C.4-own alkoxy phenol-2 ', the preparation of 4 '-diamines yl benzoic acid ester
1 part of above-mentioned product and 20 parts of Virahols addings are had in the three-necked bottle of agitator, add 0.1 part of 5%Pd/C catalyzer again, stirring heating, be warming up to backflow, be added dropwise to 0.1 part of 80% hydrazine hydrate, the TLC monitoring reaction finishes the reaction after-filtration and falls catalyzer, vacuum is spin-dried for solvent, and recrystallization promptly gets product.
4.2 the preparation of polymkeric substance
With 10 part 3,3 ', 4,4 '-triphen diether tetracarboxylic dianhydride, 3 parts of own alkoxy phenols-2 ' of 4-, 4 '-diamines yl benzoic acid ester and 7 part 4,4 '-two (4-amino-benzene oxygen) propane is dissolved in 50 parts of N, in the dinethylformamide, at N
2Protection is used N down in room temperature reaction 24h, and dinethylformamide is diluted to 2.5% can obtain the polyamic acid liquid crystal vertical-tropism agent.
4.3 the preparation of liquid crystal cell
On ito glass substrate, clean, after the drying above-mentioned polyamic acid solution is spun on the ito glass substrate, at N with alkali lye, detergent solution, water and Virahol
2Protection is down in 80 ℃ of preliminary drying 20min of temperature; respectively solidify 1h 200 ℃ of temperature, 250 ℃ and 300 ℃ then; polyimide film does not use rubbing machine to rub; with the optic-solidified adhesive that contains the 10um introns two ito glass substrates are bonded to box by the antiparallel frictional direction; utilize the liquid crystal of isotropic state the kapillary method to pour in the liquid crystal cell, seal with optic-solidified adhesive subsequently.
Embodiment 5:
5.1 the preparation of particular chemical structure diamines
A.4 '-preparation of own alkoxyl group-4-xenol
With 20 part 4,4 '-dihydroxybiphenyl and 5 parts of potassium hydroxide add and have in the three-necked bottle of agitator, add 60 parts of ethanol and in 60 ℃ of stirrings of temperature it are dissolved fully, 5 parts of bromo normal hexanes are added in the reaction mixtures again, stirring reaction 24 hours, cold filtration under the room temperature behind the stopped reaction is poured filtrate in a large amount of distilled water into, deposits a large amount of solids crude products, suction filtration, with dilute hydrochloric acid and distilled water repetitive scrubbing, dried overnight, recrystallization promptly gets product;
B.4-own alkoxyl group xenol-3 ', the preparation of 5 '-dinitrobenzoic acid ester
5 parts of above-mentioned products and 0.5 part of triethylamine adding are had in the three-necked bottle of agitator, add 40 parts of stirrings of tetrahydrofuran (THF) it is dissolved fully, again 5 parts of 3,5 dinitrobenzoylchloride are added in the three-necked bottle, react stopped reaction after 12 hours under the room temperature, solution is poured in a large amount of cold water, and a large amount of solids are deposited suction filtration, behind the thorough washing, drying gets thick product, and recrystallization promptly gets product;
C.4-own alkoxyl group xenol-3 ', the preparation of 5 '-diamines yl benzoic acid ester
5 parts of above-mentioned products and 40 parts of ethanol addings are had in the three-necked bottle of agitator, add 0.5 part of 5%Pd/C catalyzer again, stirring heating, be warming up to backflow, feed 0.5 part of hydrogen, the TLC monitoring reaction, finish the reaction after-filtration and fall catalyzer, vacuum is spin-dried for solvent, and recrystallization promptly gets product.
5.2 the preparation of polymkeric substance
With 50 part 4,4 '-(hexafluoro sec.-propyl) two O-phthalic carboxylic acid dianhydride, 10 parts of own alkoxyl group xenols-3 ' of 4-, 5 '-diamines yl benzoic acid ester and 40 part 4,4 '-two (4-amino-benzene oxygen) HFC-236fa is dissolved in 100 parts of N,N-dimethylacetamide, at N
2Protection is diluted to 4% with N,N-dimethylacetamide and can obtains the polyamic acid liquid crystal vertical-tropism agent down in room temperature reaction 36h.
5.3 the preparation of liquid crystal cell
On ito glass substrate, clean, after the drying above-mentioned polyamic acid solution is spun on the ito glass substrate, at N with alkali lye, detergent solution, water and Virahol
2Protection is down in 100 ℃ of preliminary drying 30min of temperature; respectively solidify 2h 200 ℃ of temperature, 250 ℃ and 300 ℃ then; polyimide film uses rubbing machine to rub; the friction number of times is secondary (one way); with the optic-solidified adhesive that contains the 20um introns two ito glass substrates are bonded to box by the antiparallel frictional direction; utilize the liquid crystal of isotropic state the kapillary method to pour in the liquid crystal cell, seal with optic-solidified adhesive subsequently.
Embodiment 6:
6.1 the preparation of particular chemical structure diamines
A.4 '-preparation of own alkoxyl group-4-xenol
With 40 part 4,4 '-dihydroxybiphenyl and 10 parts of sodium hydroxide add and have in the three-necked bottle of agitator, add 80 parts of methyl alcohol and in 70 ℃ of stirrings it are dissolved fully; Again 10 parts of chloro normal hexanes are added in the reaction mixture stirring reaction 24 hours, cold filtration under the room temperature behind the stopped reaction, filtrate is poured in a large amount of distilled water, deposit a large amount of solids crude products, suction filtration, with dilute hydrochloric acid and distilled water repetitive scrubbing, dried overnight, recrystallization promptly gets product;
B.4-own alkoxyl group xenol-2 ', the preparation of 4 '-dinitrobenzoic acid ester
10 parts of above-mentioned products and 1 part of pyridine adding are had in the three-necked bottle of agitator, add 60 parts of stirrings of tetrahydrofuran (THF) it is dissolved fully, again with 10 part 2, the 4-dinitrobenzoyl chloride adds in the three-necked bottle, react stopped reaction after 24 hours under the room temperature, solution is poured in a large amount of cold water, and a large amount of solids are deposited suction filtration, behind the thorough washing, drying gets thick product, and recrystallization promptly gets product;
C.4-own alkoxyl group xenol-2 ', the preparation of 4 '-diamines yl benzoic acid ester
10 parts of above-mentioned products and 60 parts of propyl carbinols addings are had in the three-necked bottle of agitator, add 1 part of iron powder catalyzer again, stirring heating is warming up to backflow, is added dropwise to 1 part of concentrated hydrochloric acid, the TLC monitoring reaction.Finish the reaction after-filtration and fall catalyzer, vacuum is spin-dried for solvent, and recrystallization promptly gets product.
6.2 the preparation of polymkeric substance
With 100 part 1,2,3,4-tetramethylene tetracarboxylic dianhydride, 25 parts of own alkoxyl group xenols-2 ' of 4-, 4 '-diamines yl benzoic acid ester and 75 part 2, two [4-(4-amino-benzene oxygen) phenyl] propane of 2-are dissolved in 200 parts of gamma-butyrolactones, at N
2Protection is diluted to 5% with gamma-butyrolactone and can obtains the polyamic acid liquid crystal vertical-tropism agent down in room temperature reaction 48h.
6.3 the preparation of liquid crystal cell
On ito glass substrate, clean, after the drying above-mentioned polyamic acid solution is spun on the ito glass substrate, at N with alkali lye, detergent solution, water and Virahol
2Protection is down in 120 ℃ of preliminary drying 40min of temperature; respectively solidify 3h 200 ℃ of temperature, 250 ℃ and 300 ℃ then; polyimide film uses rubbing machine to rub; the friction number of times is four times (one way); with the optic-solidified adhesive that contains the 40um introns two ito glass substrates are bonded to box by the antiparallel frictional direction; utilize the liquid crystal of isotropic state the kapillary method to pour in the liquid crystal cell, seal with optic-solidified adhesive subsequently.
Embodiment 7:
7.1 the preparation of particular chemical structure diamines
A.4 '-preparation of dodecyloxy-4-hydroxybenzene
With 1 part 4,4 '-dihydroxybiphenyl and 1 part of potassium hydroxide add and have in the three-necked bottle of agitator, add 40 parts of ethanol and in 50 ℃ of stirrings of temperature it are dissolved fully, 1 part of bromo n-dodecane are added in the reaction mixture again, stirring reaction 12 hours, cold filtration under the room temperature behind the stopped reaction is poured filtrate in a large amount of distilled water into, deposits a large amount of solids crude products, suction filtration, with dilute hydrochloric acid and distilled water repetitive scrubbing, dried overnight, recrystallization promptly gets product;
B.4-dodecyloxy phenol-3 ', the preparation of 5 '-dinitrobenzoic acid ester
1 part of above-mentioned product and 0.1 part of triethylamine adding are had in the three-necked bottle of agitator, add 20 parts of stirrings of tetrahydrofuran (THF) it is dissolved fully, again 1 part of 3,5 dinitrobenzoylchloride is added in the three-necked bottle, react stopped reaction after 6 hours under the room temperature, solution is poured in a large amount of cold water, and a large amount of solids are deposited suction filtration, behind the thorough washing, drying gets thick product, and recrystallization promptly gets product;
C.4-dodecyloxy phenol-3 ', the preparation of 5 '-diamines yl benzoic acid ester
1 part of above-mentioned product and 20 parts of Virahols addings are had in the three-necked bottle of agitator, add 0.1 part of 5%Pd/C catalyzer again, stirring heating, be warming up to backflow, be added dropwise to 0.1 part of 80% hydrazine hydrate, the TLC monitoring reaction finishes the reaction after-filtration and falls catalyzer, vacuum is spin-dried for solvent, and recrystallization promptly gets product.
7.2 the preparation of polymkeric substance
With 10 parts of 3c-carboxymethyl pentamethylene-1r, 2c, 4c-tricarboxylic acid-1,4:2,3-dianhydride, 3 parts of 4-dodecyloxy phenol-3 ', 5 '-diamines yl benzoic acid ester and 7 part 2, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa of 2-are dissolved in 50 parts of N-Methyl pyrrolidone, at N
2Protection is diluted to 2.5% with N-Methyl pyrrolidone and can obtains the polyamic acid liquid crystal vertical-tropism agent down in room temperature reaction 24h.
7.3 the preparation of liquid crystal cell
On ito glass substrate, clean, after the drying above-mentioned polyamic acid solution is spun on the ito glass substrate, at N with alkali lye, detergent solution, water and Virahol
2Protection is down in 80 ℃ of preliminary drying 20min of temperature; respectively solidify 1h 200 ℃ of temperature, 250 ℃ and 300 ℃ then; polyimide film does not use rubbing machine to rub; with the optic-solidified adhesive that contains the 10um introns two ito glass substrates are bonded to box by the antiparallel frictional direction; utilize the liquid crystal of isotropic state the kapillary method to pour in the liquid crystal cell, seal with optic-solidified adhesive subsequently.
Embodiment 8:
8.1 the preparation of particular chemical structure diamines
A.4 '-preparation of dodecyloxy-4-xenol
With 20 part 4,4 '-dihydroxybiphenyl and 5 parts of sodium hydroxide add and have in the three-necked bottle of agitator, add 60 parts of methyl alcohol and in 60 ℃ of stirrings of temperature it are dissolved fully, 5 parts of chloro n-dodecanes are added in the reaction mixtures again, stirring reaction 24 hours, cold filtration under the room temperature behind the stopped reaction is poured filtrate in a large amount of distilled water into, deposits a large amount of solids crude products, suction filtration, with dilute hydrochloric acid and distilled water repetitive scrubbing, dried overnight, recrystallization promptly gets product;
B.4-dodecyloxy xenol-2 ', the preparation of 4 '-dinitrobenzoic acid ester
5 parts of above-mentioned products and 0.5 part of pyridine adding are had in the three-necked bottle of agitator, add 40 parts of stirrings of tetrahydrofuran (THF) it is dissolved fully, again with 5 part 2, the 4-dinitrobenzoyl chloride adds in the three-necked bottle, react stopped reaction after 12 hours under the room temperature, solution is poured in a large amount of cold water, and a large amount of solids are deposited suction filtration, behind the thorough washing, drying gets thick product, and recrystallization promptly gets product;
C.4-dodecyloxy xenol-2 ', the preparation of 4 '-diamines yl benzoic acid ester
5 parts of above-mentioned products and 40 parts of ethanol addings are had in the three-necked bottle of agitator, add 0.5 part of 5%Pd/C catalyzer again, stirring heating, be warming up to backflow, feed 0.5 part of hydrogen, the TLC monitoring reaction, finish the reaction after-filtration and fall catalyzer, vacuum is spin-dried for solvent, and recrystallization promptly gets product.
8.2 the preparation of polymkeric substance
With 50 parts of equal benzene tertacarbonic acid's dianhydrides, 10 parts of 4-dodecyloxy xenols-2 ', 4 '-diamines yl benzoic acid ester and 40 part 4,4 ' one diaminodiphenylmethane is dissolved in 100 parts of N, in the dinethylformamide, at N
2Protection is used N down in room temperature reaction 48h, and dinethylformamide is diluted to 5% can obtain the polyamic acid liquid crystal vertical-tropism agent.
8.3 the preparation of liquid crystal cell
On ito glass substrate, clean, after the drying above-mentioned polyamic acid solution is spun on the ito glass substrate, at N with alkali lye, detergent solution, water and Virahol
2Protection is down in 100 ℃ of preliminary drying 30min of temperature; respectively solidify 2h 200 ℃ of temperature, 250 ℃ and 300 ℃ then; polyimide film uses rubbing machine to rub; the friction number of times is secondary (one way); with the optic-solidified adhesive that contains the 20um introns two ito glass substrates are bonded to box by the antiparallel frictional direction; utilize the liquid crystal of isotropic state the kapillary method to pour in the liquid crystal cell, seal with optic-solidified adhesive subsequently.
Embodiment 9:
9.1 the preparation of particular chemical structure diamines
A.4 '-preparation of dodecyloxy-4-xenol
With 40 part 4,4 '-dihydroxybiphenyl and 10 parts of potassium hydroxide add and have in the three-necked bottle of agitator, add 80 parts of ethanol and in 70 ℃ of stirrings it are dissolved fully; Again 10 parts of bromo n-dodecanes are added in the reaction mixture stirring reaction 24 hours, cold filtration under the room temperature behind the stopped reaction, filtrate is poured in a large amount of distilled water, deposit a large amount of solids crude products, suction filtration, with dilute hydrochloric acid and distilled water repetitive scrubbing, dried overnight, recrystallization promptly gets product;
B.4-dodecyloxy xenol-3 ', the preparation of 5 '-dinitrobenzoic acid ester
10 parts of above-mentioned products and 1 part of triethylamine adding are had in the three-necked bottle of agitator, add 60 parts of stirrings of tetrahydrofuran (THF) it is dissolved fully, again 10 parts of 3,5 dinitrobenzoylchloride are added in the three-necked bottle, react stopped reaction after 24 hours under the room temperature, solution is poured in a large amount of cold water, and a large amount of solids are deposited suction filtration, behind the thorough washing, drying gets thick product, and recrystallization promptly gets product;
C.4-dodecyloxy xenol-3 ', the preparation of 5 '-diamines yl benzoic acid ester
10 parts of above-mentioned products and 60 parts of propyl carbinols addings are had in the three-necked bottle of agitator, add 1 part of iron powder catalyzer again, stirring heating is warming up to backflow, is added dropwise to 1 part of concentrated hydrochloric acid, the TLC monitoring reaction.Finish the reaction after-filtration and fall catalyzer, vacuum is spin-dried for solvent, and recrystallization promptly gets product.
9.2 the preparation of polymkeric substance
With 100 part 1,2,4,5-hexanaphthene tetracarboxylic dianhydride, 25 parts of 4-dodecyloxy xenols-3 ', 5 '-diamines yl benzoic acid ester and 75 part 4,4 '-two (4-amino-benzene oxygen) benzene is dissolved in 200 parts of N-Methyl pyrrolidone, at N
2Protection is diluted to 4% with N-Methyl pyrrolidone and can obtains the polyamic acid liquid crystal vertical-tropism agent down in room temperature reaction 36h.
9.3 the preparation of liquid crystal cell
On ito glass substrate, clean, after the drying above-mentioned polyamic acid solution is spun on the ito glass substrate, at N with alkali lye, detergent solution, water and Virahol
2Protection is down in 120 ℃ of preliminary drying 40min of temperature; respectively solidify 3h 200 ℃ of temperature, 250 ℃ and 300 ℃ then; polyimide film uses rubbing machine to rub; the friction number of times is four times (one way); with the optic-solidified adhesive that contains the 40um introns two ito glass substrates are bonded to box by the antiparallel frictional direction; utilize the liquid crystal of isotropic state the kapillary method to pour in the liquid crystal cell, seal with optic-solidified adhesive subsequently.
Embodiment 10:
10.1 the preparation of particular chemical structure diamines
A.4 '-preparation of dodecyloxy-4-hydroxyl hexanaphthene
With 40 part 4,4 '-dihydroxyl hexanaphthene and 10 parts of sodium hydroxide add and have in the three-necked bottle of agitator, add 70 ℃ of stirrings of ethanol 80 one's shares of expenses for a joint undertaking it is dissolved fully; Again 10 parts of bromo n-dodecanes are added in the reaction mixture stirring reaction 24 hours, cold filtration under the room temperature behind the stopped reaction, filtrate is poured in a large amount of distilled water, deposit a large amount of solids crude products, suction filtration, with dilute hydrochloric acid and distilled water repetitive scrubbing, dried overnight, recrystallization promptly gets product;
B.4-dodecyloxy hexamethylene phenol-3 ', the preparation of 5 '-dinitrobenzoic acid ester
10 parts of above-mentioned products and 1 part of pyridine adding are had in the three-necked bottle of agitator, add 60 parts of stirrings of tetrahydrofuran (THF) it is dissolved fully, again with 10 part 3, the 5-dinitrobenzoic acid adds in the three-necked bottle, react stopped reaction after 24 hours under the room temperature, solution is poured in a large amount of cold water, and a large amount of solids are deposited suction filtration, behind the thorough washing, drying gets thick product, and recrystallization promptly gets product;
C.4-dodecyloxy hexamethylene phenol-3 ', the preparation of 5 '-diamines yl benzoic acid ester
10 parts of above-mentioned products and 60 parts of propyl carbinols addings are had in the three-necked bottle of agitator, add 1 part of 5%Pd/C catalyzer again, stirring heating is warming up to backflow, is added dropwise to 1 part of 80% hydrazine hydrate, the TLC monitoring reaction.Finish the reaction after-filtration and fall catalyzer, vacuum is spin-dried for solvent, and recrystallization promptly gets product.
10.2 the preparation of polymkeric substance
With 100 part 1,2,4,5-hexanaphthene tetracarboxylic dianhydride, 25 parts of 4-dodecyloxy hexamethylene phenol-3 ', 5 '-diamines yl benzoic acid ester and 75 part 3,4 ' one diaminodiphenyl oxide is dissolved in 150 parts of N-Methyl pyrrolidone, at N
2Protection is diluted to 4% with N-Methyl pyrrolidone and can obtains the polyamic acid liquid crystal vertical-tropism agent down in room temperature reaction 36h.
10.3 the preparation of liquid crystal cell
On ito glass substrate, clean, after the drying above-mentioned polyamic acid solution is spun on the ito glass substrate, at N with alkali lye, detergent solution, water and Virahol
2Protection is down in 120 ℃ of preliminary drying 40min of temperature; respectively solidify 3h 200 ℃ of temperature, 250 ℃ and 300 ℃ then; polyimide film uses rubbing machine to rub; the friction number of times is four times (one way); with the optic-solidified adhesive that contains the 40um introns two ito glass substrates are bonded to box by the antiparallel frictional direction; utilize the liquid crystal of isotropic state the kapillary method to pour in the liquid crystal cell, seal with optic-solidified adhesive subsequently.
Embodiment 11:
11.1 the preparation of particular chemical structure diamines
A.4 '-preparation of own alkoxyl group-4-hydroxyl hexanaphthene
With 40 part 4,4 '-dihydroxyl hexanaphthene and 10 parts of sodium hydroxide add and have in the three-necked bottle of agitator, add 60 parts of ethanol and in 60 ℃ of stirrings it are dissolved fully; Again 10 parts of bromo normal hexanes are added in the reaction mixture stirring reaction 12 hours, cold filtration under the room temperature behind the stopped reaction, filtrate is poured in a large amount of distilled water, deposit a large amount of solids crude products, suction filtration, with dilute hydrochloric acid and distilled water repetitive scrubbing, dried overnight, recrystallization promptly gets product;
B.4-the own phenol-3 ' of hexane oxygen basic ring, the preparation of 5 '-dinitrobenzoic acid ester
10 parts of above-mentioned products and 1 part of pyridine adding are had in the three-necked bottle of agitator, add 50 parts of stirrings of tetrahydrofuran (THF) it is dissolved fully, again with 10 part 3, the 5-dinitrobenzoic acid adds in the three-necked bottle, react stopped reaction after 12 hours under the room temperature, solution is poured in a large amount of cold water, and a large amount of solids are deposited suction filtration, behind the thorough washing, drying gets thick product, and recrystallization promptly gets product;
C.4-the own phenol-3 ' of hexane oxygen basic ring, the preparation of 5 '-diamines yl benzoic acid ester
10 parts of above-mentioned products and 60 parts of propyl carbinols addings are had in the three-necked bottle of agitator, add 1 part of 5%Pd/C catalyzer again, stirring heating is warming up to backflow, feeds 1 part of hydrogen, the TLC monitoring reaction.Finish the reaction after-filtration and fall catalyzer, vacuum is spin-dried for solvent, and recrystallization promptly gets product.
11.2 the preparation of polymkeric substance
With 100 parts of equal benzene tertacarbonic acid's dianhydrides, 40 parts of 4-dodecyloxy hexamethylene phenol-3 ', 5 '-diamines yl benzoic acid ester and 60 parts of mphenylenediamines are dissolved in 150 parts of N,N-dimethylacetamide, at N
2Protection is diluted to 2.5% with N,N-dimethylacetamide and can obtains the polyamic acid liquid crystal vertical-tropism agent down in room temperature reaction 24h.
11.3 the preparation of liquid crystal cell
On ito glass substrate, clean, after the drying above-mentioned polyamic acid solution is spun on the ito glass substrate, at N with alkali lye, detergent solution, water and Virahol
2Protection is down in 100 ℃ of preliminary drying 30min of temperature; respectively solidify 1h 200 ℃ of temperature, 250 ℃ and 300 ℃ then; polyimide film uses rubbing machine to rub; the friction number of times is secondary (one way); with the optic-solidified adhesive that contains the 30um introns two ito glass substrates are bonded to box by the antiparallel frictional direction; utilize the liquid crystal of isotropic state the kapillary method to pour in the liquid crystal cell, seal with optic-solidified adhesive subsequently.
Embodiment 12:
12.1 the preparation of particular chemical structure diamines
A.4 '-preparation of octadecane oxygen base-4-xenol
With 20 part 4,4 '-dihydroxybiphenyl and 5 parts of sodium hydroxide add and have in the three-necked bottle of agitator, add 60 parts of methyl alcohol and in 60 ℃ of stirrings of temperature it are dissolved fully, 5 parts of chloro Octadecanes are added in the reaction mixtures again, stirring reaction 24 hours, cold filtration under the room temperature behind the stopped reaction is poured filtrate in a large amount of distilled water into, deposits a large amount of solids crude products, suction filtration, with dilute hydrochloric acid and distilled water repetitive scrubbing, dried overnight, recrystallization promptly gets product;
B.4-octadecane oxygen base xenol-2 ', the preparation of 4 '-dinitrobenzoic acid ester
5 parts of above-mentioned products and 0.5 part of pyridine adding are had in the three-necked bottle of agitator, add 40 parts of stirrings of tetrahydrofuran (THF) it is dissolved fully, again with 5 part 2, the 4-dinitrobenzoyl chloride adds in the three-necked bottle, react stopped reaction after 12 hours under the room temperature, solution is poured in a large amount of cold water, and a large amount of solids are deposited suction filtration, behind the thorough washing, drying gets thick product, and recrystallization promptly gets product;
C.4-octadecane oxygen base xenol-2 ', the preparation of 4 '-diamines yl benzoic acid ester
5 parts of above-mentioned products and 40 parts of ethanol addings are had in the three-necked bottle of agitator, add 0.5 part of 5%Pd/C catalyzer again, stirring heating, be warming up to backflow, feed 0.5 part of hydrogen, the TLC monitoring reaction, finish the reaction after-filtration and fall catalyzer, vacuum is spin-dried for solvent, and recrystallization promptly gets product.
12.2 the preparation of polymkeric substance
With 50 part 3,3,4,4-phenyl ether tetracarboxylic dianhydride, 10 parts of 4-octadecane oxygen base xenols-2 ', 4 '-diamines yl benzoic acid ester and 40 part 3,4 '-diaminodiphenyl oxide is dissolved in 100 parts of N, in the dinethylformamide, at N
2Protection is used N down in room temperature reaction 48h, and dinethylformamide is diluted to 5% can obtain the polyamic acid liquid crystal vertical-tropism agent.
12.3 the preparation of liquid crystal cell
On ito glass substrate, clean, after the drying above-mentioned polyamic acid solution is spun on the ito glass substrate, at N with alkali lye, detergent solution, water and Virahol
2Protection is down in 100 ℃ of preliminary drying 30min of temperature; respectively solidify 2h 200 ℃ of temperature, 250 ℃ and 300 ℃ then; polyimide film uses rubbing machine to rub; the friction number of times is secondary (one way); with the optic-solidified adhesive that contains the 20um introns two ito glass substrates are bonded to box by the antiparallel frictional direction; utilize the liquid crystal of isotropic state the kapillary method to pour in the liquid crystal cell, seal with optic-solidified adhesive subsequently.
Table 1 is polyamic acid solution orientation effect, thermostability and screening characteristics
| Embodiment | Vertical orientated property | The tilt angle thermostability | The orientation homogeneity | Screening characteristics |
| Embodiment 1 | Well | Well | Well | Well |
| Embodiment 2 | Well | Well | Well | Well |
| Embodiment 3 | Well | Well | Well | Well |
| Embodiment 4 | Well | Well | Well | Well |
| Embodiment 5 | Well | Well | Well | Well |
| Embodiment 6 | Well | Well | Well | Well |
| Embodiment 7 | Well | Well | Well | Well |
| Embodiment 8 | Well | Well | Well | Well |
| Embodiment 9 | Well | Well | Well | Well |
| Embodiment 10 | Well | Well | Well | Well |
| Embodiment 11 | Well | Well | Well | Well |
| Embodiment 12 | Well | Well | Well | Well |
Claims (8)
1. the preparation method of a polyimide liquid crystal vertical-tropism agent is characterized in that this method may further comprise the steps, and wherein said raw material umber is parts by weight except that specified otherwise;
(1) preparation of particular chemical structure diamines
The reaction formula of specific diamines is as follows:
Wherein, B is benzene, biphenyl or alicyclic ring, and F is carboxylic acid or acid chloride functional groups, and R is the alkyl group of 1～18 carbon atom, and X is the chlorine or bromine atom;
The preparation of a.M1
1～40 part of HO-B-OH and 1～10 part of catalyzer adding are had in the three-necked bottle of thermometer, agitator, add 40～80 parts of solvents, making it dissolve the back fully in 50～70 ℃ of stirrings of temperature adds 1～10 part of halogenated alkane, continues reaction 12～24 hours, cold filtration under the room temperature behind the stopped reaction, filtrate is poured in a large amount of distilled water again, deposition, suction filtration is with diluted acid and distilled water repetitive scrubbing, dried overnight, recrystallization get product M1;
The preparation of b.M2
1～10 part of above-mentioned M1 and 0.01～1 part of catalyzer are added in the above-mentioned conversion unit, add 20～60 parts of solvents, add 1～10 part of dinitrobenzene compound again after stirring is dissolved it fully under the room temperature, under the room temperature
React stopped reaction after 6～12 hours, pour in the big water gaging, deposition, suction filtration, thorough washing, vacuum-drying, recrystallization gets product M2;
The preparation of c.M3
Above-mentioned M2 1～10 and 0.1～1 part of adding of catalyzer are had in the three-necked bottle of agitator, add 20～60 parts of stirrings of solvent it is dissolved fully, be warming up to backflow, drip 0.1～1 part of proton donor, adopt the TLC monitoring reaction, vacuum is spin-dried for solvent, and recrystallization gets product M3 then;
(2) preparation of the vertical orientated agent solution of polyamic acid
With 1～100 part of tetracid acid dianhydride, 1～100 part of specific diamines and 1～100 part of organic diamine add and have in the three-necked bottle of thermometer, agitator; Make it to dissolve fully under room temperature with 50～200 parts of organic solvents, room temperature reaction is 24～48 hours under nitrogen protection, is 2.5%～5% with solvent cut to concentration again, obtains the vertical orientated agent solution of polyamic acid liquid crystal;
(3) preparation of liquid crystal cell
On ito glass substrate, use alkali lye, detergent solution, water and Virahol clean, after the drying above-mentioned polyamic acid solution is spun on the ito glass substrate, under nitrogen protection in 80～120 ℃ of preliminary drying 20～40min of temperature, then at 200 ℃, respectively solidify 1～3h under 250 ℃ and 300 ℃ of high temperature, polyimide film rubs or does not rub with rubbing machine, with the optic-solidified adhesive that contains 10～40um introns two ito glass substrates are bonded to box by the antiparallel frictional direction, utilize the liquid crystal of isotropic state the kapillary method to pour in the liquid crystal cell, seal with optic-solidified adhesive subsequently, the tilt angle that obtains liquid crystal vertical-tropism is near 90 °;
The chemical structural formula of polyimide is as follows:
Wherein, n=15～45, D1 is the quaternary organic group, promptly organic tetracarboxylic dianhydride removes the part of four carboxylic acids; D2 is the divalent organic group that organic diamine is removed two amidos; B is benzene, biphenyl or alicyclic ring; R is the alkyl group of 1～18 carbon atom.
2. the preparation method of polyimide liquid crystal vertical-tropism agent according to claim 1, it is characterized in that organic diamine is a Ursol D, mphenylenediamine, 4,4 ' one diaminodiphenylmethane, 4,4 ' one diamino benzophenone, 4,4 ' one diaminodiphenyl oxide, 3,4 ' one diaminodiphenyl oxide, 3,3 ' one diaminodiphenyl oxide, 4,4 '-two (4-amino-benzene oxygen) propane, 4,4 '-two (4-amino-benzene oxygen) HFC-236fa, 2, two [4-(4-amino-benzene oxygen) phenyl] propane of 2-, 2, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa of 2-, in 4,4 '-two (4-amino-benzene oxygen) benzene any.
3. the preparation method of polyimide liquid crystal vertical-tropism agent according to claim 1 is characterized in that the tetracarboxylic dianhydride is equal benzene tertacarbonic acid's dianhydride, biphenyl tetracarboxylic dianhydride, 3,3,4,4-phenyl ether tetracarboxylic dianhydride, 3,3,4,4-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-triphen diether tetracarboxylic dianhydride, 4,4 '-(hexafluoro sec.-propyl) two O-phthalic carboxylic acid dianhydride, 1,2,3,4-tetramethylene tetracarboxylic dianhydride, 3c-carboxymethyl pentamethylene-1r, 2c, 4c-tricarboxylic acid-1,4: 2,3-dianhydride, 1,2,4, any among the 5-hexanaphthene tetracarboxylic dianhydride.
4. the preparation method of polyimide liquid crystal vertical-tropism agent according to claim 1, it is characterized in that solvent is ethanol, propyl carbinol, methyl alcohol, tetrahydrofuran (THF), Virahol, N-Methyl pyrrolidone, N, in dinethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), gamma-butyrolactone or its mixture any.
5. the preparation method of polyimide liquid crystal vertical-tropism agent according to claim 1 is characterized in that catalyzer is any among potassium hydroxide, sodium hydroxide, triethylamine, pyridine, iron, the Pd/C.
6. the preparation method of polyimide liquid crystal vertical-tropism agent according to claim 1 is characterized in that proton donor is any in hydrazine hydrate, hydrochloric acid, the hydrogen.
7. the polyimide liquid crystal vertical-tropism agent for preparing of method according to claim 1.
8. the polyimide liquid crystal vertical-tropism agent for preparing as method as described in the claim 7 is used to make liquid crystal cell, and the tilt angle of liquid crystal is near 90 ° in the liquid crystal cell.
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| TWI480313B (en) * | 2009-06-11 | 2015-04-11 | Jsr Corp | Liquid crystal aligning agent and liquid crystal display element |
| CN101717648A (en) * | 2009-11-13 | 2010-06-02 | 四川大学 | Soluble polyimide liquid crystal vertical alignment agent, prepration method and liquid crystal box prepared thereby |
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| CN102382661B (en) * | 2010-08-27 | 2014-08-06 | Jsr株式会社 | Liquid crystal orientation agent, liquid crystal orientation film, liquid crystal orientation display element, polyamic acid and polyimide |
| CN102504254A (en) * | 2011-10-25 | 2012-06-20 | 珠海彩珠实业有限公司 | Method for preparing efficient liquid crystal alignment agent and equipment therefor |
| CN102585222A (en) * | 2012-02-25 | 2012-07-18 | 舟山维特新材料科技有限公司 | Thermoplastic polyimide material and method for preparing flexible copper clad laminate through using material |
| CN102585222B (en) * | 2012-02-25 | 2014-05-07 | 舟山维特新材料科技有限公司 | Thermoplastic polyimide material and method for preparing flexible copper clad laminate through using material |
| CN104211637A (en) * | 2013-06-25 | 2014-12-17 | 四川大学 | Aromatic diamine containing triphenylpyridine and tert-butyl group, and preparation method thereof |
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| CN107942004A (en) * | 2017-11-24 | 2018-04-20 | 深圳市华星光电技术有限公司 | For dissolving the double solvents and liquid crystal test method of liquid crystal |
| CN108919565A (en) * | 2018-06-29 | 2018-11-30 | 张家港康得新光电材料有限公司 | A kind of cleaning method of electro-conductive glass |
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