Photoaligning material
09765235 · 2017-09-19
Assignee
Inventors
Cpc classification
G02F1/133788
PHYSICS
Y10T428/31721
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
C09D179/08
CHEMISTRY; METALLURGY
International classification
B32B9/04
PERFORMING OPERATIONS; TRANSPORTING
C09D179/08
CHEMISTRY; METALLURGY
C08G73/10
CHEMISTRY; METALLURGY
Abstract
The present invention relates to a copolymer for the photoalignment of liquid crystals comprising a photoreactive group as given below in formula (I), compositions thereof, and its use for optical and electro optical devices, especially liquid crystal devices (LCDs).
Claims
1. Copolymer comprising a) a first monomer of formula (IV), ##STR00076## wherein B represents an unsubstituted or substituted benzene or phenylene, pyridine, triazine, pyrimidine, biphenylene, naphthalene, phenanthrene, triphenylene, tetraline; U is hydrogen, or with a polar group substituted or unsubstituted C.sub.1-C.sub.16alkyl group; or —CF.sub.3, —CF.sub.2H, —CH.sub.2F, -Q.sup.1-(C.sub.1-C.sub.6alkylen)-CF.sub.3, -Q.sup.1-(C.sub.1-C.sub.6 alkylen)-CF.sub.2H, -Q.sup.1-(C.sub.1-C.sub.6 alkylen)-CH.sub.2F, -Q.sup.1-(C.sub.1 -C.sub.6 alkylen)-CF.sub.2CF.sub.3, -Q.sup.1-(C.sub.1-C.sub.6 alkylen)-CF.sub.2CHF.sub.2 , -Q.sup.1-(C.sub.1-C.sub.6 alkylen)-CF.sub.2CH.sub.2F, -Q.sup.1-(C.sub.1-C.sub.6alkylen)-CFHCF.sub.3, -Q.sup.1-(C.sub.1-C.sub.6alkylen)-CFHCHF.sub.2, -Q.sup.1-(C.sub.1-C.sub.6 alkylen)-CFHCH.sub.2F, -Q.sup.1-(C.sub.1-C.sub.6alkylen)-CF.sub.2CH.sub.3, -Q.sup.1-(C.sub.1-C.sub.6 alkylen)-CFHCHF.sub.2,-Q.sup.1-(C.sub.1-C.sub.6 alkylen)-(CF.sub.2).sub.2CF.sub.3, -Q.sup.1-(C.sub.1-C.sub.6 alkylen)-(CF.sub.2).sub.2CHF.sub.2, -Q.sup.1-(C.sub.1-C.sub.6 alkylen)-(CF.sub.2).sub.2CH.sub.2F, -Q.sup.1-(C.sub.1-C.sub.6alkylen)-(CF.sub.2).sub.2CH.sub.3, -Q.sup.1-(C.sub.1-C.sub.6alkylen)-(CF.sub.2).sub.3CHF.sub.2, -Q.sup.1-(C.sub.1-C.sub.6alkylen)-(CF.sub.2).sub.3CH.sub.2F, -Q.sup.1-(C.sub.1-C.sub.6alkylen)-(CF.sub.2).sub.3CF.sub.3, -Q.sup.1-(C.sub.1-C.sub.6alkylen)-CF(CF.sub.3).sub.2, -Q.sup.1-(C.sub.1-C.sub.6alkylen)-CF.sub.2(CHF)CF.sub.3; wherein one or more C-atom, CH- or CH.sub.2-group is independently from each other not replaced or replaced by a linking group; and wherein Q.sup.1 represents a single bond or —NH—, —N(CH.sub.3)—, —NH—CO—, —CO—NH—, —NH—CO—O—, —O—CO—NH—, —NH—CONH—, —CON(CH.sub.3)—, —(CH.sub.3)NCO—, —O—, —CO—, —COO—, —OCO—, —OCF.sub.2—, —CF.sub.2—O—, —CF.sub.2S—, —SCF.sub.2—, —CF.sub.2NH—, —NHCF.sub.2—, —S—, —CS—, —SCS—, —SCO—, —CH═CH—, —C≡C—or —O—CO—O—; and Z is a bridging group selected from the group consisting of —O—, —CO—, —COO—, —OCO—, —OCOO—, —OCF.sub.2—, —CF.sub.2O—, —CON(CH.sub.3)—, —(CH.sub.3)NCO—, —CONH—, —NHCO—, —CO—S—, —S—CO—, —CSS—, —SOO—, —OSO—, —CSS—, —SOO—, —OSO—, —CH.sub.2(SO.sub.2)—, —CH.sub.2—CH.sub.2—, —OCH.sub.2—, —CH.sub.2O, —CH═CH—, —C≡C—, —CH═CH—COO—, —OCO—CH═CH—, or a single bond; S.sup.1 and S.sup.2 each independently from each other represents a single bond or a spacer unit, which is a cyclic, straight-chain or branched, substituted or unsubstituted C.sub.1-C.sub.24alkylen, in which one or more C-atom, CH- or CH.sub.2- group may be replaced by a linking group, and/or a non-aromatic, aromatic, unsubstituted or substituted carbocyclic or heterocyclic group of formula (V):
—(Z.sup.1—C.sup.1).sub.a1—(Z.sup.2—C.sup.2) .sub.a2—(Z.sup.1a).sub.a3—(V) wherein: C.sup.1, C.sup.2 each independently represents an alicyclic or aromatic, optionally substituted carbocyclic or heterocyclic group, and Z.sup.1, Z.sup.2, Z.sup.1a each independently represents a bridging group within the above given meanings, and a1, a2 , a3 each independently represents an integer from 0 to 3, such that a1+a2+a3≦6; X is a bivalent aromatic group, or X is —CH.sub.2—, —CO—, —CS—, —O(CO)—, —(CO)O—, —NH(CO)—, —(CO)NH—, —OCF.sub.2—, —((C.sub.1- C.sub.6alkyl)- N)CO—, or —((CH.sub.3)N)CO—, or —S(CS)—, —O(CS)—, —S(CO)—; R.sup.2 and R.sup.3 are hydrogen and/or nitrile; y and z are each independently from each other 1, 2, 3 or 4; w is 1, 2, 3, or 4, and wherein D represents an unsubstituted or substituted aliphatic, aromatic or/and alicyclic polymerisable group, with the proviso that a 1,3-diamino phenyl group is excluded, and b) a second monomer having at least one monomer selected from the group of compounds having at least one not-photoreactive or at least one photoreactive group, with the proviso that the second monomer is different from that the first monomer and with the proviso that if Z of the first monomer is —OCF.sub.2— or —CF.sub.2O—, then Z of the second monomer is not —OCF.sub.2— or —CF.sub.2O—.
2. Copolymer according to claim 1, wherein the second monomer comprises a photoreactive group, which is selected from formula (II) ##STR00077## wherein A is selected from the group consisting of benzene, phenylene, pyridine, triazine, pyrimidine, biphenylene, naphthalene, phenanthrene, triphenylene, and tetraline which are uninterrupted or interrupted by at least a single heteroatom and/or at least a single bridging group; B is unsubstituted or substituted benzene or phenylene, pyridine, triazine, pyrimidine, biphenylene, naphthalene, phenanthrene, triphenylene, tetraline, cyclohexylene or a steroidal skeleton; U represents hydrogen or a straight-chain or branched, unsubstituted or at least once, with halogen, nitile, ether, ester, siloxane, amide or amine substituted C.sub.1-C.sub.16alkyl group, wherein one or more C-atom, CH—or CH.sub.2-group is independently from each other not replaced or replaced by a linking group which is selected from a single bond, —S—, —S(CS)—, —(CS)S—, —CO—S—, —S—CO—, —O—, —CO, —CO—O—, —O—CO—, ##STR00078## —NR.sup.2′—, —NR.sup.2′—CO—, —CO—NR.sup.2′—, —NR.sup.2′—CO—O—, —O—CO—NR.sup.2′—,—NR.sup.2′—CO—NR.sup.2′—,—CH═CH—, —C≡C—, O—,CO—O—, —Si(CH.sub.3).sub.2—O—Si(CH.sub.3).sub.2-, a cyclic, straight-chain or branched, substituted or unsubstituted C.sub.1-C.sub.24alkylen, wherein one or more C-atom, CH—or CH.sub.2-group may independently from each other be replaced by —O—; and unsubstituted or substituted cyclohexylen and unsubstituted or substituted phenylene and wherein: R.sup.2 ′ represents a hydrogen atom or C.sub.1-C.sub.6alkyl; with the proviso that oxygen atoms of linking groups are not directly linked to each other; Z is a bridging group selected from the group consisting of —O—, —CO—, —COO—, —OCO—, —OCOO—, —OCF.sub.2—, —CF.sub.2O—,—CON(CH.sub.3)—, —(CH.sub.3)NCO—, —CONH—, —NHCO—, —CO—S—, —S—CO—, —CSS—, —SOO—, —OSO—, —CSS—, —SOO——OSO——CH.sub.2(SO.sub.2)—, —CH.sub.2—CH.sub.2—, —OCH.sub.2—, —CH.sub.2O, —CH═CH—, —C≡C—,—CH═CH—COO—, —OCO—CH═CH—, or a single bond; X is a bivalent aromatic group, or X is —CH.sub.2—, —CO—, —CS—, —O(CO)—, —(CO)O—, —NH(CO)—, —(CO)NH—, —OCF.sub.2—, —((C.sub.1-C.sub.6alkyl)—N)CO—, or —((CH.sub.3)N)CO—, or —S(CS)—, —O(CS)—, —S(CO)—; R.sup.2 and R.sup.3 are hydrogen and/or nitrile; or coumarin group, chalcon group, stilben group and azobenzene group.
3. Copolymer according to claim 1, wherein the second monomer comprises a not-photoreactive group, which is a carbocyclic or heterocyclic aromatic and/or alicyclic or aliphatic group, which is unsubstituted or substituted by an acrylate group, vinyl group, allyl group, epoxy group, maleinimide group, straight-chain or branched C.sub.1-C.sub.16alkyl group, C.sub.1-C .sub.6alkylacrylate group, C.sub.1-C.sub.16 alkylvinyl group, C.sub.1-C.sub.16alkylallyl group, C.sub.1-C.sub.16alkylepoxy group, C.sub.1-C.sub.16alkylmaleinimide group.
4. Copolymer according to claim 1, wherein the second monomer comprises a not-photoreactive group, which is substituted or unsubstituted phenylen-(bridging group)-phenylene-, or (phenylene).sub.n1-(bridging group).sub.m1-(phenylene).sub.n2-(bridging group) .sub.m1-(cyclohexylen).sub.n3-, wherein n1, n2, n3 represent an integer of 0, 1, 2,3, 3 or 4 and m1, m2 an interger of 0 or 1, with proviso that at least one n1, n2, n3 or n4 is >1; or naphthylene or phenylene, which are unsubstituted or substituted by at least one, acrylate group, vinyl group, allyl group, epoxy group, maleinimide group, straight-chain or branched C.sub.1-C.sub.16alkyl group, C.sub.1-C.sub.16alkylacrylate group, C.sub.1-C.sub.16alkylvinyl group, C.sub.1-C.sub.16alkylallyl group, C.sub.1-C.sub.16alkylepoxy group, C.sub.1-C.sub.16alkylmaleinimide group; or a steroidal skeleton.
5. Copolymer according to claim 2, comprising a) a first monomer of formula (II) wherein U is a straight-chain or branched, with fluorine, in the terminal position of the alkyl group substituted C.sub.1-C.sub.16alkyl group, wherein one or more C-atom, CH—or CH.sub.2-group is independently from each other not replaced or replaced by a linking group, and b) a second monomer having at least one monomer selected from the group of compounds having at least one photoreactive group of formula (II) with the same meaning as described above, with the proviso that the U substituent is different from that of the first monomer.
6. Composition, comprising a copolymer as described in claims 1, 3, 4, or 5.
7. Method for the preparation of a copolymer as described in claim 1, which comprises bringing into contact the first and the second monomer.
8. Copolymer, which is obtainable by the method according to claim 7.
9. Copolymer layer comprising at least a copolymer as described in claim 1 or 8.
10. Optical and electro-optical unstructured or structured constructional elements, comprising a copolymer as described in claim 1.
11. Optical and electro-optical unstructured or structured constructional elements according to claim 10, represented by multilayer systems, or devices for the preparation of a display waveguide, a security or brand protection element, a bar code, an optical grating, a filter, a retarder, a compensation film, a reflectively polarizing film, an absorptive polarizing film, an anisotropically scattering film compensator and retardation film, a twisted retarder film, a cholesteric liquid crystal film, a guest-host liquid crystal film, a monomer corrugated film, a smectic liquid crystal film, a polarizer, a piezoelectric cell, a thin film exhibiting non linear optical properties, a decorative optical element, a brightness enhancement film, a component for wavelength-band-selective compensation, a component for multi-domain compensation, a component of multiview liquid crystal displays, an achromatic retarder, a polarization state correction/adjustment film, a component of optical or electro-optical sensors, a component of brightness enhancement film, a component for light-based telecommunication devices, a G/H-polarizer with an anisotropic absorber, a reflective circular polarizer, a reflective linear polarizer, a MC (monomer corrugated film), twisted nematic (TN) liquid crystal displays, hybrid aligned nematic (HAN) liquid crystal displays, electrically controlled birefringence (ECB) liquid crystal displays, supertwisted nematic (STN) liquid crystal displays, optically compensated birefringence (OCB) liquid crystal displays, pi-cell liquid crystal displays, in-plane switching (IPS) liquid crystal displays, fringe field switching (FFS) liquid crystal displays; (PSVA) polymer stabilised vertically aligned; (FPA) field-induced photo-reactive alignment; hybrid FPA; vertically aligned (VA); VA-IPS mode liquid crystal displays, or displays using blue phase liquid crystals; all above display types are applied in either transmissive or reflective or transflective mode, comprising a copolymer as described in claim 1.
12. Orientation layer, comprising at least one composition as described in claim 6.
13. Copolymer according to claim 1, wherein y and z are each independently from each other 1 or 2, and w is 1 or 2.
Description
EXAMPLES
Definitions Used in the Examples
(1) Mass spectroscopy EI=EI (electron-impact) ES=electron spray [M+H]=MolecularMass plus proton .sup.1H NMR=.sup.1H nuclear magnetic resonance spectroscopy .sup.19F NMR=.sup.19F nuclear magnetic resonance spectroscopy DMSOd.sub.6=dimethylsulfoxid deutererd 300 MHz=300 Megaherz M.sup.+=MolecularMass of the cation m=multiplett d=douplet dd=double douplet t=triplett s=sigulett q=quintett br=broad δ□=chemical shift HCl=hydrogen chloride HCl solution (25%)=volume percent NaOH=sodium hydroxid NaOH (30%)=weight percent NMP=N-methyl-2-pyrrolidone THF=tetrahydrofuran TBME=tert. butyl methyl ether DMF=dimethylformamide Pd(OAc).sub.2=Palladiumacetat Pretilt=tilt of liquid crystal RT=room temperature Pd/C=palladium/carbon MLC-6610(Merck KGA)=Iicristal®, MLC-6610(Merck KGA), nematic liquid crystal
Accessibility of Starting Materials
(2) 4-(4,4,4-trifluorobutoxy)benzoic is prepared according to the process described in WO 2007/071091 A1 pages 76 which is herewith incorporated by reference.
(3) The 2,3,5-tricarboxycyclopentylacetic-1,2:3,4-dianhydride used in these examples comprises ≧99% in exo body content. The said exo body content is defined as ratio (%) of the whole content. 2,3,5-tricarboxycyclopentylacetic-1,2:3,4-dianhydride is accessible by processes as described in JP59-190945, JP60-13740 and JP58-109479, respectively DE 1078120 and JP58-109479, or GB 872,355, and JP04458299, which processes are herewith incorporated by reference.
Example 1
Preparation of (3(3)-cholest-5-en-3-yl 3,5-dinitrobenzoate
(4) ##STR00046##
(5) 20.00 g (51.7 mmol) of cholesterol, 2.88 g (25.75 mmol) of 4-dimethylaminopyridine, 6.27 g (62.04 mmol) of triethylamine are dissolved in 100 mL of dichloromethane. 11.92 g (51.7 mmol) of commercial 3,5-dinitrobenzoylchloride dissolved in 50 mL of dichloromethane are added at 0° C. The solution is stirred for 2 h at 0° C. and allowed to stir at room temperature overnight. After 22 hours at room temperature, the reaction mixture is partitioned between dichloromethane and water. The organic phase is washed repeatedly with water, dried over sodium sulfate, filtrated and concentrated under reduced pressure. Crystallization from ethyl acetate:hexane mixture yielded 16.94 g (56%) of (3(3)-cholest-5-en-3-yl 3,5-dinitrobenzoate as yellowish crystals.
Example 2
Preparation of (3β)-cholest-5-en-3-yl 3,5-diaminobenzoate
(6) ##STR00047##
(7) 11.42 g (19.66 mmol) of (3β)-cholest-5-en-3-yl-3,5-dinitrobenzoate are dissolved in a mixture of 54 mL of N,N-dimethylformamide and 6 mL water. 32.6 g (120 mmol) ferric chloride hexahydrate are added. 13.1 g (201 mmol) zinc powder is added portion wise within 60 minutes. The mixture is allowed to react for 2 hours. The reaction mixture is partitioned between ethyl acetate and water and filtrated. The organic phase is washed repeatedly with water, dried over sodium sulfate, filtrated and concentrated under reduced pressure. Filtration of the residue on 400 g silica gel using toluene:ethyl acetate 1:3 as eluent and crystallization from ethyl acetate:hexane mixture yielded 8.20 g of (3β)-cholest-5-en-3-yl-3,5-.sup.1H NMR DMSO d.sub.6 300 MHz
(8) 6.41 (d, 2H), 6.01 (t, 1H), 5.39 (m, 1H), 4.97 (s, 4H), 4.62 (m, 1H), 2.36 (m, 2H), 2.00-0.83 (m, 40H), 0.66 (s, 3H).
Example 3
Preparation of 5-(2,4-dinitrophenyl)pentan-1-ol
(9) ##STR00048##
(10) 50 g (304 mmol) of 5-phenylpentan-1-ol, 127 mL of NEt3 are dissolved in 50 mL of THF at 0° C. 46.5 g (456 mmol) of acetic anhydride is added to the mixture. The solution is stirred for 2 h at 0° C. and allowed to stir at room temperature overnight. After 22 hours at room temperature, the reaction mixture is partitioned between ethyl acetate and water. The organic phase is washed repeatedly with water, dried over sodium sulfate, filtrated and concentrated under reduced pressure. The crude product is added carefully to a mixture of 250 g sulphuric acid and 160 g nitric acid cooled at −5° C. The solution is stirred for 2 h at −5° C. The mixture is quenched with 500 g of ice and the product is extracted with toluene. The organic phase is washed repeatedly with water, dried over sodium sulfate, filtrated and concentrated under reduced pressure. The yellow oil is refluxed in 300 ml of methanol with 60 ml of HCl. After 22 hours under reflux, the reaction mixture is partitioned between ethyl acetate and water. The organic phase is washed repeatedly with water, dried over sodium sulfate, filtrated and concentrated under reduced pressure. Chromatography of the residue on 400 g silica gel using toluene:ethyl acetate 1:1 as eluant yielded 61 g (80%) of 5-(2,4-dinitrophenyl)pentan-1-ol as yellowish oil.
Example 4
Preparation of 7-{[5-(2,4-dinitrophenyl)pentyl]oxy}-2H-chromen-2-one
(11) ##STR00049##
(12) 5 g (30.8 mmol) of commercial available 7-hydroxy-2H-chromen-2-one, 7.84 (30.8 mmol) of 5-(2,4-dinitrophenyl)pentan-1-ol, 10.5 g (40.0 mmol) of triphenylphosphine are dissolved in 100 mL of THF at 0° C. 8.1 g (40.0 mmol) of DIAD is added to the mixture. The solution is stirred for 2 h at 0° C. and allowed to stir at room temperature overnight. After 22 hours at room temperature, the reaction mixture is partitioned between ethyl acetate and water. The organic phase is washed repeatedly with water, dried over sodium sulfate, filtrated and concentrated under reduced pressure. Chromatography of the residue on 200 g silica gel using toluene:ethyl acetate 9:1 as eluant yielded 7.9 g (65%) of 7-{[5-(2,4-dinitrophenyl)pentyl]oxy}-2H-chromen-2-one as yellowish crystals.
Example 5
Preparation of 7-[(3,5-dinitrobenzyl)oxy]-2H-chromen-2-one
(13) ##STR00050##
(14) 7-[(3,5-dinitrobenzyl)oxy]-2H-chromen-2-one is prepared analogous to 7-{[5-(2,4-dinitrophenyl)pentyl]oxy}-2H-chromen-2-one using 3,5-dinitrobenzyl alcohol.
Example 6
Preparation of 7-{[5-(2,4-diaminophenyl)pentyl]oxy}-2H-chromen-2-one
(15) ##STR00051##
(16) 2.90 g (7.28 mmol) of 7-{[5-(2,4-dinitrophenyl)pentyl]oxy}-2H-chromen-2-on are dissolved in a mixture of 63 ml of N,N-dimethylformamide and 7 ml water. 11.8 g (43.6 mmol) ferric chloride hexahydrate are added. 4.75 g (72.8 mmol) Zinc powder are added portionwise within 60 min. The mixture is allowed to react for 2 hours. The reaction mixture is then partitioned between ethyl acetate and water and filtered. The organic phase is washed repeatedly with water, dried over sodium sulfate, filtered and concentrated by rotary evaporation. Filtration of the residue on 200 g silica gel using toluene:ethyl acetate(1:3) as eluant and crystallization form ethylacetate:hexane mixture yielded 1.53 g of 7-{[5-(2,4-diaminophenyl)pentyl]oxy}-2H-chromen-2-one as yellowish crystals.
(17) .sup.1H NMR DMSO d.sub.6 300 MHz
(18) 8.00 (d, 1H), 7.63 (d, 1H), 6.98 (d, 1H), 6.95 (dd, 1H), 6.56 (d, 1H), 6.29 (d, 1H), 5.87 (d, 1H), 5.76 (dd, 1H), 4.46 (d, 4H), 4.08 (t, 2H), 2.29 (m, 2H), 1.75 (m, 2H), 1.46 (m, 4H).
Example 7
7-[(3,5-diaminobenzyl)oxy]-2H-chromen-2-one is prepared analogous to 7-{[5-(2,4-diaminophenyl)pentyl]oxy}-2H-chromen-2-one using 7-[(3,5-dinitrobenzyl)oxy]-2H-chromen-2-one.
(19) ##STR00052##
(20) Mass spectroscopy EI: 283 (MH.sup.+).
Example 8
Preparation of 4,4′-Dinitro-1,1′-biphenyl-2,2′-dicarboxylic acid
(21) ##STR00053##
(22) 30.0 g (120.13 mmol) Diphenic acid are dissolved at room temperature in 469 g (4.59 mol) concentrated sulfuric acid (96%). The solution is cooled to −15° C. and a mixture of 92.4 g (1.011 mol) concentrated nitric acid (69%) and 12.0 g (0.117 mol) concentrated sulfuric acid (96%) is added slowly so that the mixture temperature is maintained below 0° C. After the addition the solution is allowed to react at room temperature for 24 h. After the mixture is poured onto crushed ice, the precipitate that formed i collected by filtration, washed with water and dried at room temperature under vacuum for 10 h.
Example 9
Preparation of 4,4′-Dinitro-1,1′-biphenyl-2,2′-dimethanol
(23) ##STR00054##
(24) 3.6 g (10.83 mmol) 4,4′-Dinitro-1,1′-biphenyl-2,2′-dicarboxylic acid are dissolved in 25 ml tetrahydrofuran and added dropwise in a the course of 1 hours to 65 ml (65.02 mmol) of a borane-tetrahydrofuran complex 1.0 M solution in tetrahydrofuran. After 19 hours at 25° C., 50 ml water are carefully added. After 1 h the solution is acidified to pH=1-2 with 10 ml 1N HCl solution and allowed to stirred for 30 min. The reaction mixture is then partitioned between ethyl acetate and water; the organic phase is washed repeatedly with water, dried over sodium sulfate, filtered and concentrated by rotary evaporation. The residue, 4.2 g of 4,4′-Dinitro-1,1′-biphenyl-2,2′-dimethanol as white powder is used without further purification.
Example 10
Preparation of {2′-[(acryloyloxy)methyl]-4′,4-dinitro-1,1′-biphenyl-2-yl}methyl acrylate
(25) ##STR00055##
(26) 10 g (32.8 mmol) of 4,4′-Dinitro-1,1′-biphenyl-2,2′-dimethanol, 13.5 g (111 mmol) of N,N-dimethylaniline are dissolved in 100 ml of THF at 0° C. 8.92 g (98.5 mmol) of acryloyl chlorid is added dropwise. The solution is stirred for 2 h at 0° C. and allowed to stir at room temperature overnight. After 22 hours at room temperature, the reaction mixture is partitioned between ethyl acetate and water. The organic phase is washed repeatedly with water, dried over sodium sulfate, filtrated and concentrated under reduced pressure. Filtration of the residue on 400 g silica gel using toluene:ethyl acetate(1:1) as eluant yielded 8.9 g of {2′-[(acryloyloxy)methyl]-4′,4-dinitro-1,1′-biphenyl-2-yl}methyl acrylate as a yellowish oil.
Example 11
Preparation of {2′-[(acryloyloxy)methyl]-4′,4-diamino-1,1′-biphenyl-2-yl}methyl acrylate
(27) ##STR00056##
(28) {2′-[(acryloyloxy)methyl]-4′,4-diamino-1,1′-biphenyl-2-yl}methyl acrylate is prepared analogous to 7-{[5-(2,4-diaminophenyl)pentyl]oxy}-2H-chromen-2-one starting from {2′-[(acryloyloxy)methyl]-4′,4-dinitro-1,1′-biphenyl-2-yl}methyl acrylate.
(29) .sup.1H NMR DMSO d.sub.6 300 MHz
(30) 6.78 (d, 2H), 6.64 (d, 2H), 6.53 (d, 2H), 6.31 (m, 2H), 6.17 (m, 2H), 5.94 (d, 2H), 5.14 (s, 4H), 4.73 (s, 4H).
Example 12
Preparation of (2E)-3-{4-[(4-benzoylbenzoyl)oxy]phenyl}prop-2-enoic acid
(31) ##STR00057##
(32) 6.89 g (56.4 mmol) of 4-hydroxybenzaldehyd, 12.7 g (56.4 mmol) of 4-benzoylbenzoic acid, 0.69 g (5.6 mmol) of 4-Dimethylaminopyridine are dissolved in 100 ml of dichloromethane. 11.89 g (62.0 mmol) of N-(3-Dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride (EDC hydrochloride) are added at 0° C. The solution is stirred for 1 h at 0° C. and allowed to stir at room temperature overnight. After 22 hours at room temperature the reaction mixture was partitioned between dichloromethane and water; the organic phase is washed repeatedly with water, dried over sodium sulphate, filtered and concentrated by rotary evaporation. 4.69 g (14.2 mMol) of the intermediate 4-formylphenyl 4-benzoylbenzoate and 3.00 g (28.4 mMol) of Malonic acid are dissolved in 18 ml (227.1 mMol) of Pyridin.1.21 g (14.2 mMol) of Piperidin are added to the suspension which is allowed to react at 100° C. under argon for 1.5 h. The yellow solution is then thrown on ice. The solution is carefully acidified to pH=1-2 with a 25% HCl solution and is stirred for 15 min. The product is filtrated off and dried at room temperature under vacuum for 10 h to give 5.2 g of (2E)-3-{4-[(4-benzoylbenzoyl)oxy]phenyl}prop-2-enoic acid as white powder.
Example 13
Preparation of 4-{(1E)-3-[2-(2,4-dinitrophenyl)ethoxy]-3-oxoprop-1-enyl}phenyl 4-benzoylbenzoate
(33) ##STR00058##
(34) 2.50 g (11.8 mmol) of 2-(2,4-dinitrophenyl)ethanol, 4.39 g (11.8 mmol) of (2E)-3-{4-[(4-benzoylbenzoyl)oxy]phenyl}prop-2-enoic acid, 144 mg (1.2 mmol) of 4-Dimethylaminopyridine are dissolved in 30 ml of dichloromethane. 2.48 g (13.0 mmol) of N-(3-Dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride (EDC hydrochloride) are added at 0° C. The solution is stirred for 1 h at 0° C. and allowed to stir at room temperature overnight. After 22 hours at room temperature the reaction mixture is partitioned between dichloromethane and water. The organic phase is washed repeatedly with water, dried over sodium sulphate, filtered and concentrated by rotary evaporation. Chromatography of the residue on 200 g silica gel using toluene:ethyl acetate 95:5 as eluant and crystallization form ethylacetate:hexane mixture to yield 5.35 g of 4-{(1E)-3-[2-(2,4-dinitrophenyl)ethoxy]-3-oxoprop-1-enyl}phenyl 4-benzoylbenzoate as colorless crystals.
Example 14
Preparation of 4-{(1E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxoprop-1-enyl}phenyl 4-benzoylbenzoate
(35) ##STR00059##
(36) 4.74 g (8.38 mmol) of (4-{(1E)-3-[2-(2,4-dinitrophenyl)ethoxy]-3-oxoprop-1-enyl}phenyl 4-benzoylbenzoate are dissolved in a mixture of 54 ml of N,N-dimethylformamide and 6 ml water. 13.9 g (51.4 mmol) ferric chloride hexahydrate are added. 5.60 g (85.7 mmol) Zinc powder are added portionwise within 60 min. The mixture is allowed to react for 2 hours. The reaction mixture is then partitioned between ethyl acetate and water and filtered. The organic phase is washed repeatedly with water, dried over sodium sulfate, filtered and concentrated by rotary evaporation. Filtration of the residue on 200 g silica gel using toluene:ethyl acetate(1:3) as eluant and crystallization form ethylacetate:hexane mixture yielded 3.30 g of 4-{(1E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxoprop-1-enyl}phenyl 4-benzoylbenzoate as yellowish crystals
(37) .sup.1H NMR DMSO d.sub.6 300 MHz
(38) 8.82 (d, 2H), 8.56-7.60 (m, 10H), 7.63 (d, 2H), 6.69 (m, 2H), 5.89 (d, 1H), 5.81 (m, 1H), 4.66 (s, 2H), 4.59 (s, 2H), 4.16 (t, 2H), 2.72 (t, 2H)
(39) List of the Diamines Used for the Polymer Preparation
(40) TABLE-US-00001
(41) A polymer backbone which can be referred as polymer main chain is a polyimide or polyamic acid material. Polyamic acids are precursor materials of polyimides.
(42) General Procedure for Polymerisation Step a (Formation of Polyamic Acid)
(43) 0.820 g (3.66 mmol) of 2,3,5-tricarboxycyclopentylacetic-1,2:3,4-dianhydride is added to a solution of 0.549 g (1.09 mmol) of 4-{(1E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-1-propenyl}phenyl 4-(2,2,2-trifluoroethoxy)benzoate and 2.55 g (2.56 mmol) of [4,4′-diamino-2′-({[(2E)-3-(4-{[4-(4,4,4-trifluorobutoxy)benzoyl]oxy}phenyl)prop-2-enoyl]oxy}methyl)-1,1′-biphenyl-2-yl]methyl (2E)-3-(4-{[4-(4,4,4-trifluorobutoxy)benzoyl]oxy}phenyl)prop-2-enoate in 6.56 mL of NMP. Stirring is then carried out at 0° C. for 2 hours. The mixture is subsequently allowed to react for 21 hours at room temperature. The polymer mixture is diluted with 18 mL of THF, precipitated into 800 mL of water to yield, after drying at room temperature under vacum, 3.76 g of polyamic acid P1 in the form of a white powder.
(44) General Procedure for Imidization Step B (Formation of the Polyimide)
(45) 1.00 g of polyamic acid P1 obtained in above is dissolved in 9 ml of NMP. Thereto are added 0.753 mL of pyridine and 883 mL of acetic acid anhydride, and the dehydration and ring closure is carried out at 80° C. for 6 h. The polymer mixture is diluted with 10 ml NMP, precipitated into 100 ml diethyl ether and collected by filtration. The polymer is reprecipitated from THF (10 ml) into 200 ml water to yield, after drying at room temperature under vacuum, 0.950 g polyimide P29.
(46) Polymer formed was characterized through its intrinsec viscosity and NMR data. In NMR, some representative signals could be seen. The integration are given as relative values. Molecular weight of the polymers formed is preferably in the range of 20000 to 200000.
(47) List of the Polymers
(48) TABLE-US-00002 Diamines (in Dianhydrides (in Viscosity Imidization Polymer % mol ratio) % mol ratio) dL/g degree (%) P1 4 (30) 5 (70) TCA (100) 0.34 0 Analytical data of polymer P1: .sup.1H NMR/DMSO d6 300 MHz
(49) 12.38 (s, 1.0H), 10.33-9.52 (m, 0.8H), 8.04-8.01 (m, 1.9H), 7.82-7.58 (m, 4.5H), 7.24-7.06 (m, 4.6H), 6.56 (m, 0.9H), 4.90 (s, 1.7H), 4.25 (s, 0.3H), 4.10 (s, 1.5H), 3.33-2.70 (m, 8H), 2.49 (m, 2.7H), 1.90 (m, 2.7H)
(50) TABLE-US-00003 Diamines (in Dianhydrides (in Viscosity Imidization Polymer % mol ratio) % mol ratio) dL/g degree (%) P2 4 (70) 5(30) TCA (100) 0.26 0 Analytical data of polymer P2: .sup.1H NMR/DMSO d6 300 MHz
(51) 12.38 (s, 1.0H), 10.22-10.05 (m, 0.6H), 9.70-9.40 (m, 0.3H), 8.12-8.01 (m, 1.4H), 7.79-7.50 (m, 3.5H), 7.32-7.06 (m, 3.5H), 6.64-6.51 (m, 0.7H), 4.90 (m, 1.4H), 4.25 (s, 0.7H), 4.10 (s, 0.7H), 3.33-2.70 (m, 8H), 2.49 (m, 1.8H), 1.90 (m, 1.8H)
(52) TABLE-US-00004 Diamines (in Dianhydrides (in Viscosity Imidization Polymer % mol ratio) % mol ratio) dL/g degree (%) P3 1 (50) 12 (50) CBDA (100) 0.36 0 Analytical data of polymer P3: .sup.1H NMR/DMSO d6 300 MHz
(53) 12.47 (s, 1.6H), 10.41 (s, 0.7H), 10.19 (s, 0.4H), −9.58 (s, 0.4H), 8.38-7.10 (m, 7.7H), 6.60 (m, 0.4H), 5.39 (s, 0.4H), 4.71 (s, 0.5H), 4.29-3.59 (m, 5.3), 3.03 (s, 0.9H), 2.49 (m, 1.5H), 2.17-0.64 (m, 20H)
(54) TABLE-US-00005 Diamines (in Dianhydrides (in Viscosity Imidization Polymer % mol ratio) % mol ratio) dL/g degree (%) P4 1 (70) 12 (30) CBDA (100) 0.30 0 Analytical data of polymer P4: .sup.1H NMR/DMSO d6 300 MHz
(55) 12.47 (s, 1.0H), 10.41 (s, 0.3H), 10.19 (s, 0.5H), −9.82-9.58 (m, 0.5H), 8.38-7.10 (m, 8.5H), 6.60 (m, 0.7H), 5.39 (s, 0.3H), 4.71 (s, 0.3H), 4.29-3.59 (m, 3.7), 2.94-2.80 (m, 1.2H), 2.49 (m, 1.6H), 2.17-0.64 (m, 14H)
(56) TABLE-US-00006 Diamines (in Dianhydrides (in Viscosity Imidization Polymer % mol ratio) % mol ratio) dL/g degree (%) P5 1 (90) 12 (10) TCA (100) 0.21 0 Analytical data of polymer P5: .sup.1H NMR/DMSO d6 300 MHz
(57) 12.38 (s, 1.0H), 10.05-9.46 (m, 1.0H), 8.07 (s, 1.0 H), 7.79-7.10 (m, 5.0H), 6.60 (m, 0.5H), 5.39 (s, 0.1H), 4.71 (s, 0.1H), 4.24-4.14 (m, 2.0H), 3.3-2.51 (m, 2.4H), 2.49 (m, 2.0H), 2.17-0.64 (m, 3.8H)
(58) TABLE-US-00007 Diamines (in Dianhydrides (in Viscosity Imidization Polymer % mol ratio) % mol ratio) dL/g degree (%) P6 9 (5) 1 (95) TCA (100) 0.21 0 Analytical data of polymer P6: .sup.1H NMR/DMSO d6 300 MHz
(59) 12.40 (s, 1.0H), 10.22-9.40 (m, 1.0H), 8.15-8.01 (m, 1.3H), 7.85-7.06 (m, 6.3H), 6.65-6.55 (d, 0.7H), 4.25-4.10 (m, 2.5H), 3.33-2.70 (m, 10H), 2.49 (m, 1.9H), 1.90 (m, 1.9H)
(60) TABLE-US-00008 Diamines (in Dianhydrides (in Viscosity Imidization Polymer % mol ratio) % mol ratio) dL/g degree (%) P7 3 (20) 1 (80) TCA (100) 0.23 0 Analytical data of polymer P7: .sup.1H NMR/DMSO d6 300 MHz
(61) 12.40 (s, 1.0H), 10.22-9.40 (m, 1.0H), 8.10 (s, 1.1H), 7.90-7.06 (m, 5.7H), 6.65-6.55 (d, 0.6H), 4.25-4.10 (m, 2.3H), 3.33-2.70 (m, 9.8H), 2.49 (m, 1.9H), 1.90 (m, 1.9H)
(62) TABLE-US-00009 Diamines (in Dianhydrides (in Viscosity Imidization Polymer % mol ratio) % mol ratio) dL/g degree (%) P10 7 (70) 3 (30) TCA (100) 0.50 60 Analytical data of polymer P10: .sup.1H NMR/DMSO d6 300 MHz
(63) 12.39 (s, 0.2H), 10.03 (s, 0.2H), 8.02 (m, 1.0H), 7.87-7.10 (m, 4.9), 6.60 (m, 0.4H), 4.29-2.59 (m, 4.0), 2.49 (m, 1.3H), 1.97 (m, 1.3H)
(64) TABLE-US-00010 Diamines (in Dianhydrides (in Viscosity Imidization Polymer % mol ratio) % mol ratio) dL/g degree (%) P11 1 (70) 3 (30) TCA (100) 0.39 50 Analytical data of polymer P11: .sup.1H NMR/DMSO d6 300 MHz
(65) 12.59 (s, 0.4H), 10.06 (s, 0.4H), 8.05 (s, 1.0H), 7.90-7.05 (m, 4.6H), 6.61 (m, 0.5H), 4.14 (br, 2.0H), 4.08-2.75 (m, 2.3H), 2.49 (m, 1.4H), 1.96 (m, 1.4H)
(66) TABLE-US-00011 Diamines (in Dianhydrides (in Viscosity Imidization Polymer % mol ratio) % mol ratio) dL/g degree (%) P12 1 (50) 6 (50) TCA (100) 0.27 80 Analytical data of polymer P12: .sup.1H NMR/DMSO d6 300 MHz
(67) 12.59 (s, 0.0H), 10.06 (s, 0.0H), 7.99 (s, 1.0H), 7.87-7.06 (m, 4.5H), 6.57 (br, 0.5H), 4.36 (br, 0.6H), 4.12 (br, 1.3H), 4.08-2.75 (m, 1.3H), 2.49 (m, 1.2H), 1.96 (m, 1.2H)
(68) TABLE-US-00012 Diamines (in Dianhydrides (in Viscosity Imidization Polymer % mol ratio) % mol ratio) dL/g degree (%) P13 1 (70) 6 (30) TCA (100) 0.34 80 Analytical data of polymer P13: .sup.1H NMR/DMSO d6 300 MHz
(69) 12.61 (s, 0.1H), 10.04 (s, 0.1H), 8.04 (m, 1.0H), 7.90-7.09 (m, 3.7H), 6.60 (br, 0.4H), 4.46 (br, 0.5H), 4.12 (s, 1.3H), 4.08-2.75 (m, 2.3H), 2.49 (m, 1.1H), 1.96 (m, 1.1H)
(70) TABLE-US-00013 Diamines (in Dianhydrides (in Viscosity Imidization Polymer % mol ratio) % mol ratio) dL/g degree (%) P14 7 (70) 10 (30) TCA (100) 0.30 80 Analytical data of polymer P14: .sup.1H NMR/DMSO d6 300 MHz
(71) 12.51 (s, 0.2H), 10.04 (s, 0.2H), 8.03 (d, 1.0H), 7.79-7.06 (m, 6.8H), 6.73 (d, 0.6H), 6.58 (m, 0.3H), 4.34-3.35 (m, 4.7H), 2.49 (m, 1.4H), 1.96-0.85 (m, 6.5H)
(72) TABLE-US-00014 Diamines (in Dianhydrides (in Viscosity Imidization Polymer % mol ratio) % mol ratio) dL/g degree (%) P15 1 (70) 8 (30) TCA (100) 0.20 80 Analytical data of polymer P15: .sup.1H NMR/DMSO d6 300 MHz
(73) 12.60 (s, 0.1H), 10.03 (s, 0.1H), 8.12 (m, 1.0H), 7.90-7.09 (m, 4.3H), 6.60 (br, 0.5H), 4.46-4.12 (br, 1.8H), 4.08-2.75 (m, 1.9H), 2.49 (m, 1.3H), 1.96 (m, 1.3H)
(74) TABLE-US-00015 Diamines (in Dianhydrides (in Viscosity Imidization Polymer % mol ratio) % mol ratio) dL/g degree (%) P16 8 (30) 7 (70) TCA (100) 0.50 100 Analytical data of polymer P16: .sup.1H NMR/DMSO d6 300 MHz
(75) 8.01 (d, 1.0H), 7.77-7.05 (m, 4.9H), 6.67 (br, 0.5H), 4.46-2.63 (m 3.6H), 2.49 (m, 1.2H), 1.96 (m, 1.2H)
(76) TABLE-US-00016 Diamines (in Dianhydrides (in Viscosity Imidization Polymer % mol ratio) % mol ratio) dL/g degree (%) P17 1 (70) 10 (30) TCA (100) 0.16 90 Analytical data of polymer P17: .sup.1H NMR/DMSO d6 300 MHz
(77) 12.60 (s, 0.0H), 10.03 (s, 0.0H), 8.06 (s, 1.0H), 7.930-7.10 (m, 5.4H), 6.59 (br, 0.3H), 4.46-4.12 (br, 1.9H), 4.08-2.75 (m, 1.8H), 2.49 (m, 1.1H), 2.17 (m, 2.0H), 1.96 (m, 1.3H), 1.77-0.55 (m, 5.8H)
(78) TABLE-US-00017 Diamines (in Dianhydrides (in Viscosity Imidization Polymer % mol ratio) % mol ratio) dL/g degree (%) P18 6 (70) 7 (30) TCA (100) 0.49 90 Analytical data of polymer P18: .sup.1H NMR/DMSO d6 300 MHz
(79) 12.60 (s, 0.0H), 10.03 (s, 0.0H), 8.12 (m, 1.0H), 7.90-7.05 (m, 3.9H), 6.710 (br, 0.4H), 4.34-4.12 (br, 1.6H), 4.08-2.75 (m, 1.6H), 2.49 (m, 1.1H), 1.96 (m, 1.1H)
(80) TABLE-US-00018 Diamines (in Dianhydrides (in Viscosity Imidization Polymer % mol ratio) % mol ratio) dL/g degree (%) P19 6 (50) 7 (50) TCA (100) 0.55 80 Analytical data of polymer P19: .sup.1H NMR/DMSO d6 300 MHz
(81) 12.60 (s, 0.1H), 10.03 (s, 0.1H), 8.12 (m, 1.0H), 7.86-7.05 (m, 4.4H), 6.60 (br, 0.4H), 4.46-2.75 (m, 3.2H), 2.49 (m, 1.1H), 1.96 (m, 1.1H)
(82) TABLE-US-00019 Diamines (in Dianhydrides (in Viscosity Imidization Polymer % mol ratio) % mol ratio) dL/g degree (%) P20 6 (30) 7 (70) TCA (100) 0.64 80 Analytical data of polymer P20: .sup.1H NMR/DMSO d6 300 MHz
(83) 12.60 (s, 0.1H), 10.03 (s, 0.1H), 8.12 (m, 1.0H), 7.86-7.05 (m, 4.8H), 6.60 (br, 0.5H), 4.46-2.75 (m, 3.6H), 2.49 (m, 1.1H), 1.96 (m, 1.1H)
(84) TABLE-US-00020 Diamines (in Dianhydrides (in Viscosity Imidization Polymer % mol ratio) % mol ratio) dL/g degree (%) P21 1 (70) 2 (30) TCA (100) 0.48 100 Analytical data of polymer P21: .sup.1H NMR/DMSO d6 300 MHz
(85) 8.12 (m, 1.0H), 7.90-7.11 (m, 4.7H), 6.60 (br, 0.3H), 4.46-4.12 (br, 2.0H), 4.08-2.75 (m, 3.2H), 2.49 (m, 1.6H), 1.96 (m, 1.6H), 2.72-0.75 (m, 3.4)
(86) TABLE-US-00021 Diamines (in Dianhydrides (in Viscosity Imidization Polymer % mol ratio) % mol ratio) dL/g degree (%) P22 3 (70) 2 (30) TCA (100) 0.40 0 Analytical data of polymer P22: .sup.1H NMR/DMSO d6 300 MHz
(87) 12.38 (s, 1.0H), 10.06 (m, 0.5H), 9.50 (m, 0.5H), 8.08 (d, 0.8H), 7.78-7.10 (m, 5.0H), 6.70 (m, 0.5H), 4.13 (m, 1.8H), 3.30-2.75 (m, 2.5H), 2.49 (m, 1.9H), 2.20-0.84 (m, 2.6H)
(88) TABLE-US-00022 Diamines (in Dianhydrides (in Viscosity Imidization Polymer % mol ratio) % mol ratio) dL/g degree (%) P23 11 (30) 1 (70) TCA (100) 0.17 50 Analytical data of polymer P23: .sup.1H NMR/DMSO d6 300 MHz
(89) 12.51 (s, 0.4H), 10.20-9.39 (m, 0.5H), 8.12 (m, 1.0H), 7.90-7.09 (m, 8.0H), 6.60 (br, 0.9H), 4.46-3.35 (m, 3.0H), 3.30-2.75 (m, 5.9H), 2.49 (m, 1.3H), 1.96 (m, 1.3H)
(90) TABLE-US-00023 Diamines (in Dianhydrides (in Viscosity Imidization Polymer % mol ratio) % mol ratio) dL/g degree (%) P24 7 (70) 1 (30) TCA (100) 0.39 70 Analytical data of polymer P24: .sup.1H NMR/DMSO d6 300 MHz
(91) 12.40 (s, 0.2H), 10.03 (m, 0.2H), 8.12-7.05 (m, 6.2H), 6.70 (m, 0.5H), 4.13 (m, 1.1H), 4.10-2.75 (m, 3.1H), 2.49 (m, 1.1H), 1.95 (m, 1.1H), 1.83-0.85 (m, 6.8H)
(92) TABLE-US-00024 Diamines (in Dianhydrides (in Viscosity Imidization Polymer % mol ratio) % mol ratio) dL/g degree (%) P25 7 (70) 2 (30) TCA (100) 0.38 80 Analytical data of polymer P25: .sup.1H NMR/DMSO d6 300 MHz
(93) 12.40 (s, 0.2H), 10.03 (m, 0.2H), 8.09 (d, 1.0H), 7.77-7.05 (m, 5.9H), 6.70 (m, 0.5H), 4.13 (m, 1.2H), 4.10-2.75 (m, 3.1H), 2.49 (m, 1.3H), 2.10-0.84 (m, 3.5H)
(94) TABLE-US-00025 Diamines (in Dianhydrides (in Viscosity Imidization Polymer % mol ratio) % mol ratio) dL/g degree (%) P26 7 (30) 1 (70) TCA (100) 0.44 40 Analytical data of polymer P26: .sup.1H NMR/DMSO d6 300 MHz
(95) 12.54 (s, 1.0H), 10.03 (m, 1.0H), 8.06 (m, 4.8H), 7.77-7.08 (m, 23.2H), 6.66 (m, 2.3H), 4.32-3.34 (m, 10.7H), 3.30-2.75 (m, 9.1H), 2.49 (m, 6.6H), 1.97 (m, 6.6H)
(96) TABLE-US-00026 Diamines (in Dianhydrides (in Viscosity Imidization Polymer % mol ratio) % mol ratio) dL/g degree (%) P27 7 (50) 1 (50) TCA (100) 0.35 80 Analytical data of polymer P27 .sup.1H NMR/DMSO d6 300 MHz
(97) 12.60 (s, 0.3H), 10.03 (s, 0.3H), 8.12 (m, 1.0H), 7.90-7.09 (m, 5.0H), 6.60 (br, 0.5H), 4.46-4.12 (br, 2.0H), 4.08-2.75 (m, 1.6H), 2.49 (m, 1.3H), 1.96 (m, 1.3H)
(98) TABLE-US-00027 Diamines (in Dianhydrides (in Viscosity Imidization Polymer % mol ratio) % mol ratio) dL/g degree (%) P28 11 (30) 7 (70) TCA (100) 1.01 60 Analytical data of polymer P28: .sup.1H NMR/DMSO d6 300 MHz
(99) 12.40 (s, 0.2H), 10.03 (m, 0.2H), 8.02 (d, 1.0H), 7.77-7.06 (m, 7.3H), 6.70 (m, 0.7H), 4.13 (m, 1.2H), 4.10-2.75 (m, 2.6H), 2.49 (m, 1.3H), 2.10-0.84 (m, 5.8H)
(100) TABLE-US-00028 Diamines (in Dianhydrides (in Viscosity Imidization Polymer % mol ratio) % mol ratio) dL/g degree (%) P29 4 (30) 5 (70) TCA (100) 0.36 70 Analytical data of polymer P29: .sup.1H NMR/DMSO d6 300 MHz
(101) 12.38 (s, 0.3H), 10.50 (s, 0.3H), 8.10-7.05 (m, 12.9H), 6.56 (d, 1.0H), 4.95 (br, 2.1H), 4.38-3.65 (m, 3.1H), 3.26-2.70 (m, 2.5H), 2.49 (m, 2.1H), 1.91 (m, 2.1H)
(102) TABLE-US-00029 Diamines (in Dianhydrides (in Viscosity Imidization Polymer % mol ratio) % mol ratio) dL/g degree (%) P30 1 (90) 13 (10) TCA (100) 0.27 0 Analytical data of polymer P18: .sup.1H NMR/DMSO d6 300 MHz
(103) 12.38 (s, 1.0H), 10.05-9.36 (m, 1.0H), 8.08 (d, 1.0H), 7.94-7.02 (m, 5.2H), 6.91 (m, 0.1H), 6.63 (m, 0.5H), 4.26-4.13 (m, 2.3H), 4.10-2.75 (m, 2.5H), 2.49 (m, 1.6H), 1.96 (m, 1.6H)
(104) TABLE-US-00030 Diamines (in Dianhydrides (in Viscosity Imidization Polymer % mol ratio) % mol ratio) dL/g degree (%) P31 1 (50) 13 (50) TCA (100) 0.18 0 Analytical data of polymer P31: .sup.1H NMR/DMSO d6 300 MHz
(105) 12.38 (s, 1.0H), 10.05-9.36 (m, 1.0H), 8.08 (m, 0.7H), 7.94-6.77 (m, 3.6H), 6.64 (m, 0.5H), 4.26-4.13 (m, 1.3H), 3.90-2.75 (m, 2.5H), 2.49 (m, 2.4H), 1.96 (m, 0.8H), 1.72 (s, 1.0H), 1.41-1.21 (m, 2.2H)
(106) TABLE-US-00031 Diamines (in Dianhydrides (in Viscosity Imidization Polymer % mol ratio) % mol ratio) dL/g degree (%) P32 1 (95) 14 (5) TCA (100) 0.13 0 Analytical data of polymer P32: .sup.1H NMR/DMSO d6 300 MHz
(107) 12.38 (s, 1.0H), 10.05-9.36 (m, 1.0H), 8.08 (d, 0.9H), 7.94-7.02 (m, 5.2H), 6.91 (m, 0.1H), 6.63 (m, 0.5H), 5.12 (s, 0.1H), 4.26-4.13 (m, 2.3H), 4.10-2.75 (m, 2.5H), 2.49 (m, 1.6H), 1.96 (m, 1.6H)
(108) TABLE-US-00032 Diamines (in Dianhydrides (in Viscosity Imidization Polymer % mol ratio) % mol ratio) dL/g degree (%) P33 5 (90) 15 (10) TCA (100) 0.55 0 Analytical data of polymer P33: .sup.1H NMR/DMSO d6 300 MHz
(109) 12.40 (s, 1.0H), 10.22 (m, 1.0H), 8.04 (d, 2.0H), 7.86-7.06 (m, 9.8H), 6.57 (m, 1.0H), 6.45-5.83 (m, 0.3H), 4.91 (br, 2.0H), 4.11 (s, 1.9H), 4.10-2.75 (m, 1.3H), 2.49 (m, 2.8H), 1.96 (m, 2.8H)
(110) TABLE-US-00033 Diamines (in Dianhydrides (in Viscosity Imidization Polymer % mol ratio) % mol ratio) dL/g degree (%) P34 1 (100) TCA (100) 0.30 40 comparative example 1 Analytical data of polymer P34: .sup.1H NMR/DMSO d6 300 MHz
(111) 0.26-9.45 (m, 1.2H), 8.11 (d, 2.0H), 7.87-6.95 (m, 10.0H), 6.65 (m, 1.0H), 4.37-3.94 (m, 4.0H), 3.46-2.68 (m, 10.0H), 2.49 (m, 2.0H), 1.96 (m, 2.0H)
(112) TABLE-US-00034 Diamines (in Dianhydrides (in Viscosity Imidization Polymer % mol ratio) % mol ratio) dL/g degree (%) P35 7 (100) TCA (100) 0.58 70 comparative example 2 Analytical data of polymer P35: .sup.1H NMR/DMSO d6 300 MHz
(113) 12.35 (s, 0.3H), 10.04 (m, 0.3H), 8.02 (d, 4.0H), 7.86-7.06 (m, 22.0H), 6.57 (m, 2.0H), 4.13-3.39 (m, 8H), 3.30-2.75 (m, 12.0H), 2.49 (m, 4.0H), 1.96 (m, 4.0H)
(114) TABLE-US-00035 Diamines (in Dianhydrides (in Viscosity Imidization Polymer % mol ratio) % mol ratio) dL/g degree (%) P36 1 (90) 16 (10) TCA (100) 0.22 0 Analytical data of polymer P36: .sup.1H NMR/DMSO d6 300 MHz
(115) 12.34 (s, 1H), 10.05 (m, 1H), 9.28 (m, 0.1), 8.07 (d, 1.1H), 7.91-7.06 (m, 6.3H), 6.58 (m, 0.7H), 4.25-4.14 (m, 2.2H), 3.30-2.75 (m, 10.0H), 2.49 (m, 1.8H), 1.96 (m, 2.2H)
(116) Applicatory Examples
Example 1 (Comparative Example)
(117) A liquid crystal cell is prepared as described in the procedure below, wherein the liquid crystal is aligned by photo reactive polymer P34.
(118) A 5.0 wt % solution is prepared by mixing the polymer P34 in solvent of N-methyl-2-pyrrolidone (NMP) and a second solvent butyl cellulose (BC) and the whole composition is stirred thoroughly and filtered to obtain the final solution. The solvent ratio between N-methyl-2-pyrrolidone and butyl cellulose is 50:50.
(119) The above polymer solution is spin-coated onto the two ITO coated glass substrates at a spin speed of 2700 rpm for 30 seconds. After spin coating, the substrates are subjected to baking procedure consisting of pre-baking for 5 minutes at 130° C. and post-baking for 40 minutes at a temperature of 220° C. The resulting layer thickness is around 67 nm.
(120) The substrates with the coated polymer layer on top are exposed to linearly polarized UV light (LPUV) at an incidence angle of 40° relative to the normal of the substrate surface. The plane of polarization is within the plane spanned by the substrate normal and the propagation direction of the light. The applied exposure dose is 48 mJ/cm.sup.2.
(121) After LPUV exposure, a cell is assembled with the 2 substrates, the exposed polymer layers facing to the inside of the cell. The substrates are adjusted relative to each other such that the induced alignment directions are parallel to each other (corresponds to the anti-parallel rubbed configuration in case of alignment by rubbing procedure). The cell is capillary filled with liquid crystal MLC6610(Merck KGA), which had a negative dielectric anisotropy.
(122) The liquid crystal in the cell shows well defined homeotropic orientation. A tilt angle of 86.72° is measured using the crystal rotation method.
Example 2 (Comparative Example)
(123) Another cell ss prepared in similar manner as in Example 1. Voltage holding ratio of this cell is measured at room temperature. The voltage decay V (at T=20 ms) of a voltage surge if 64 μs with V.sub.0(V at t=0)=5V is then measured over a period of T=20 ms. The voltage holding ratio is then determined, given by VHR=V.sub.rms(t=T)/V.sub.o is 99.50% at room temperature.
Example 3 (Comparative Example)
(124) A liquid crystal cell is prepared in similar manner as in Example 1 but with a 4% solution of polymer P35, with spin speed of 2800 rpm-30 seconds and exposure dose of 48 mJ with an incidence angle of 40°. The liquid crystal in the cell shows well defined homeotropic orientation. A tilt angle of 88.14° is measured using the crystal rotation method.
Example 4 (Comparative Example)
(125) Another cell is prepared in similar manner as in Example 3. Voltage holding ratio of this cell measured as in Example 2 is 99.60% at room temperature.
Example 5
(126) A liquid crystal cell is prepared in similar manner as in Example 1 but with a 5% solution of polymer P24, with spin speed of 2800 rpm-30 seconds and exposure dose of 48 mJ with an incidence angle of 40°. The liquid crystal in the cell shows well defined homeotropic orientation. A tilt angle of 87.82° is measured using the crystal rotation method. This shows the advantage of fine-tuning the optical properties by copolymerization.
Example 6
(127) Another cell is prepared in similar manner as in Example 5. Voltage holding ratio of this cell measured as in Example 2 is 99.60% at room temperature. This shows the flexibility of fine-tuning the electro-optical properties without worsening by copolymerization.
Example 7
(128) A liquid crystal cell is prepared in similar manner as in Example 1 but with a 4% solution of polymer P20, with spin speed of 2400 rpm-30 seconds and exposure dose of 48 mJ with an incidence angle of 40°. The liquid crystal in the cell shows well defined homeotropic orientation. A tilt angle of 87.62° is measured using the crystal rotation method. This again shows that the optical properties could be fine-tuned by copolymerization.
Example 8
(129) Another cell is prepared in similar manner as in Example 7. Voltage holding ratio of this cell measured as in Example 2 is 99.60% at room temperature. This shows the flexibility of fine-tuning the electro-optical properties without worsening by copolymerization.
Example 9
(130) A liquid crystal cell is prepared in similar manner as in Example 1 but with a 4% solution of polymer P5, with spin speed of 1600 rpm-30 seconds, but with post-baking temperature of 40 min-200° C. and exposure dose of 48 mJ with an incidence angle of 40°. The liquid crystal in the cell shows well defined homeotropic orientation. A tilt angle of 88.68° is measured using the crystal rotation method. This again shows the flexibility of fine-tuning the optical properties by copolymerization.
Example 10
(131) Another cell is prepared in similar manner as in Example 9. Voltage holding ratio of this cell measured as in Example 2 is 99.60% at room temperature. This again shows the flexibility of fine-tuning the electro-optical properties without worsening by copolymerization.
Example 11
(132) A liquid crystal cell is prepared in similar manner as in Example 9 but with a 5% solution of polymer P7, with spin speed of 2200 rpm-30 seconds. The liquid crystal in the cell shows well defined homeotropic orientation. A tilt angle of 87.63° is measured using the crystal rotation method.
Example 12
(133) A liquid crystal cell is prepared in similar manner as in Example 9 but with a 5% solution of polymer P22, with spin speed of 2200 rpm-30 seconds. The liquid crystal in the cell shows well defined homeotropic orientation. A tilt angle of 87.93° is measured using the crystal rotation method.
Example 13
(134) A liquid crystal cell is prepared in similar manner as in Example 1 but with a 5% solution of polymer P25, with spin speed of 2800 rpm-30 seconds and exposure dose of 48 mJ with an incidence angle of 40°. The liquid crystal in the cell shows well defined homeotropic orientation. A tilt angle of 87.75° is measured using the crystal rotation method.
Example 14
(135) A liquid crystal cell is prepared in similar manner as in Example 1 but with a 5% solution of polymer P23, with spin speed of 2000 rpm-30 seconds and exposure dose of 48 mJ with an incidence angle of 40°. The liquid crystal in the cell shows well defined homeotropic orientation. A tilt angle of 87.59° is measured using the crystal rotation method.
Example 15
(136) A liquid crystal cell is prepared in similar manner as in Example 1 but with a 5% solution of polymer P28, with spin speed of 5500 rpm-30 seconds and exposure dose of 48 mJ with an incidence angle of 40°. The liquid crystal in the cell shows well defined homeotropic orientation. A tilt angle of 88.03° is measured using the crystal rotation method.
Example 16
(137) A liquid crystal cell is prepared in similar manner as in Example 9 but with a 4% solution of polymer P30, with spin speed of 1500 rpm-30 seconds. The liquid crystal in the cell shows well defined homeotropic orientation. A tilt angle of 88.10° is measured using the crystal rotation method. This shows again the flexibility of fine-tuning the optical properties by copolymerization.