EP0958316A1 - Polyesters nematiques chiraux - Google Patents

Polyesters nematiques chiraux

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Publication number
EP0958316A1
EP0958316A1 EP98909394A EP98909394A EP0958316A1 EP 0958316 A1 EP0958316 A1 EP 0958316A1 EP 98909394 A EP98909394 A EP 98909394A EP 98909394 A EP98909394 A EP 98909394A EP 0958316 A1 EP0958316 A1 EP 0958316A1
Authority
EP
European Patent Office
Prior art keywords
chiral nematic
units
polyester according
range
polyesters
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP98909394A
Other languages
German (de)
English (en)
Inventor
Hans R. Kricheldorf
Thorsten Krawinkel
Andreas Gerken
Peter Schuhmacher
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP0958316A1 publication Critical patent/EP0958316A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0295—Liquid crystals
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/85—Polyesters
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q3/00—Manicure or pedicure preparations
    • A61Q3/02—Nail coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/672—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/676—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
    • C08G63/6854—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/6856—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0098—Organic pigments exhibiting interference colours, e.g. nacrous pigments
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/38—Polymers
    • C09K19/3804—Polymers with mesogenic groups in the main chain
    • C09K19/3809—Polyesters; Polyester derivatives, e.g. polyamides
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/54—Polymers characterized by specific structures/properties

Definitions

  • the invention relates to liquid-crystalline chiral nematic polyesters.
  • liquid-crystalline phases When heating anisotropic substances, liquid-crystalline phases, so-called mesophases, can occur.
  • the individual phases differ in the spatial arrangement of the molecular centers on the one hand and in the molecular arrangement with respect to the longitudinal axes on the other (G. Gray, P A. Winsor, Liquid Crystals and Plastic Crystals, Ellis Horwood Limited, Chichester 1974).
  • the nematic liquid-crystalline phase is characterized by the parallel orientation of the longitudinal axes of the molecules (one-dimensional order).
  • a so-called chiral nematic (cholesteric) phase is formed in which the longitudinal axes of the molecules form a helical superstructure that is perpendicular to it (H.
  • the chiral part of the molecule can either be present in the liquid-crystalline molecule itself or be added to the nematic phase as a dopant, the chiral nematic phase being induced.
  • This phenomenon was first investigated on cholesterol derivatives (e.g. H. Baessler, M. M. Labes, J. Chem. Phys. 52, 631 (1970).
  • the chiral nematic phase has special optical properties: high optical rotation and a pronounced circular dichroism, which is created by selective reflection of circularly polarized light within the chiral nematic layer.
  • the pitch corresponds to the helical superstructure of the wavelength of visible light, a so-called grandjean texture is formed.
  • the colors, which appear different depending on the viewing angle, depend on the pitch of the helical superstructure, which in turn depends on the twisting relationship of the chiral component.
  • the pitch and thus the wavelength range of the selectively reflected light of a chiral nematic layer can be varied by changing the concentration of a chiral dopant.
  • Such chiral nematic systems offer interesting possibilities for practical use.
  • chiral parts of the molecule By incorporating chiral parts of the molecule into mesogenic acrylic acid esters and orientation in the chiral nematic phase, for example after photocrosslinking, a stable, colored network can be produced, but the concentration of the chiral component can then no longer be changed (G. Galli, M. Laus, A. Angelon, Makromol. Chemie 187, 2289 (1986)).
  • concentration of the chiral component can then no longer be changed (G. Galli, M. Laus, A. Angelon, Makromol. Chemie 187, 2289 (1986)).
  • non-crosslinkable chiral compounds By adding non-crosslinkable chiral compounds to nematic acrylic acid esters, a colored polymer can be produced by photocrosslinking which still contains high proportions of soluble components (I. Heyndricks, DJ Broer, Mol. Cryst. Liq. Cryst. 203, 113 (1991)) .
  • a chiral nematic network can be obtained in which the chiral component can have a share of up to 50% in the material used; however, these polymers still contain significant amounts of soluble fractions (Kreuzer University of Applied Sciences, R. Mauerer, Ch. Müller-Rees, J. Stohrer, Lecture No. 7, 22nd Working Conference on Liquid Crystals, Freeburg, 1993).
  • DE-A-35 35 547 describes a process in which a mixture of cholesterol-containing monoacrylates can be processed to chiral nematic layers by means of photocrosslinking.
  • the total proportion of the chiral component in the mixture is approximately 94%.
  • a pure side chain polymer such a material is not mechanically very stable, but an increase in stability can be achieved by highly crosslinking diluents.
  • polyesters generally show narrow areas of existence of the chiral nematic phase and contain predominantly open-chain chiral components which have a low twistability, so that relatively large proportions of these components are necessary in order to achieve a color impression. This makes the selection of the remaining polyester components e.g. limited in their mechanical properties.
  • DE-A-19504913.6 describes chiral nematic polyesters with chiral diol components with a strong twisting action, in particular dianhydro sugars, and broad liquid-crystalline phase regions.
  • EP-A-682 092 describes paints based on chiral nematic polymers. Examples which are mentioned are polyesters which have been prepared by polycondensation of dicarboxylic acids and diols.
  • DE-A-19631658 describes chiral nematic polycarbonates which have been prepared by various types of polycondensation of diols with phosgene or diphosgene.
  • DE-A-44 41 651 discloses a method for the surface coating of substrates with a coating agent which contains at least one polymerizable low molecular weight liquid-crystalline compound.
  • a coating agent which contains at least one polymerizable low molecular weight liquid-crystalline compound.
  • photochemically polymerizable, low molecular weight liquid-crystalline compounds oligoesters
  • WO-A-96 02 597 also describes a process for coating or printing substances with a coating or printing agent which contains a chiral or achiral liquid-crystalline monomer and a non-liquid-crystalline chiral compound.
  • the liquid-crystalline monomers are preferably photochemically polymerizable bisacrylates.
  • WO-A-95 29 962 describes aqueous coating compositions for the production of coatings whose color impression depends on the viewing angle and which contain platelet-shaped pigments from oriented, three-dimensionally crosslinked substances of liquid-crystalline structure with a chiral phase.
  • a particularly preferred sub- Three-dimensionally crosslinkable polyorganosiloxanes are described.
  • WO-A-95 29 961 discloses coating compositions with a color impression depending on the viewing angle and their use in basecoats for multi-layer coatings.
  • the compositions contain platelet-shaped pigments with a color that is dependent on the viewing angle and consist of oriented, three-dimensionally crosslinked substances of liquid-crystalline structure with a chiral phase. Three-dimensionally crosslinkable polyorganosiloxanes are described as preferred substances.
  • the interference pigments consist of esterified cellulose ethers, in particular of acylated hydroxypropyl cellulose.
  • EP-A-724 005 discloses a pigment with a color that is dependent on the viewing angle, its production and use in a lacquer.
  • the pigment is obtained by three-dimensional crosslinking of oriented substances of liquid-crystalline structure with a chiral phase.
  • Preferred substances are three-dimensionally crosslinkable polyorganosiloxanes.
  • it is proposed to carry out the crosslinking in the presence of at least one further, color-neutral compound which contains at least two crosslinkable double bonds.
  • Acrylates, polyurethanes, epoxies, siloxanes, polyesters and alkyd resins are mentioned as preferred color-neutral compounds.
  • EP-A-0686 674 and the priority application on which it is based DE-A-44 16 191 describe interference pigments from molecules fixed in a cholesteric arrangement and their use.
  • the pigments described have a platelet-like structure and a thickness of 1 ⁇ m to 20 ⁇ m. They contain oriented cross-linked substances of liquid crystalline structure with a chiral phase (preferably polyorganosiloxanes).
  • EP-A-0601 483 and the priority application on which it is based DE-A-42 40 743 describe pigments with a color that is dependent on the viewing angle, their production and use.
  • the pigments described consist of oriented three-dimensionally crosslinked substances of liquid-crystalline structure with a chiral phase (preferably polyorganosiloxanes) and, if appropriate, further dyes and pigments. Any other dyes and pigments present do not serve as carriers for the oriented three-dimensionally cross-linked liquid-crystalline substances with a chiral phase.
  • polyesters which comprise diol or dicarboxylic acid units which contain flexibilizing alkylene groups and which comprise isosorbide, isomannide or isoidide units and the polyester chain form stable Grandjean textures without developing a higher tendency to crystallize. They can be fixed without networking without the disadvantages described above and can be produced simply and inexpensively.
  • the present invention therefore relates to chiral nematic polyesters with flexible chains which comprise isosorbide, isomannide and / or isoidide units, preferably isosorbide units, and which contain at least one unit which is selected from (and derived from) to make the chains more flexible.
  • the polyesters according to the invention are not crystalline and form 5 stable Grand Jeans textures which can be frozen when they cool below the glass transition temperature. Despite the flexibility, the glass transition temperatures of the polyesters are above 80 ° C., preferably above 90 ° C., in particular above 100 ° C. 0
  • polyesters according to the invention are preferably composed of dicarboxylic acids and diols.
  • polyesters according to the invention preferably contain, as units (a), those of the formula
  • n is a number in the range from 3 to 15, in particular 4 to 30 12 and particularly preferably adipic acid;
  • A represents (CH 2 ) n , 0 (CH 2 ) n O or (CH 2 ) o -0- (CH 2 ) p , n is particularly preferably a number in the range from 3 to 15, in particular 4 to 12, 40 Is 4 to 10 and o and p are independently a number in the range of 1 to 7;
  • units (c) preferably those of the formula 45 0 (CH 2 ) n 0 or 0 (CH 2 CH 2 0) m where n is a number in the range from 3 to 15, in particular 4 to 12, particularly preferably 4 to 10 and m is a number in the range from 1 to 10; and
  • A is (CH 2 ) n , 0 (CH 2 ) n 0 or (CH 2 ) o -0- (CH 2 ) p , n is a number in the range from 3 to 15, in particular 4 to 12, particularly preferably 4 to 10 and o and p independently represent a number in the range from 1 to 7.
  • polyesters according to the invention also preferably contain dicarboxylic acid units of the formula as the non-flexible acid component
  • L represents alkyl, alkoxy, halogen, COOR, OCOR, CONHR or NHCOR, X represents S, 0, N, CH 2 or a single bond,
  • R 1 is hydrogen, halogen, alkyl or phenyl and R represents alkyl or hydrogen
  • polyesters according to the invention optionally contain additional flexible diol units of the formula
  • R 1 is hydrogen, halogen, alkyl or phenyl, A (CH 2 ) n , 0 (CH 2 ) n , S (CH 2 ) n or NR (CH 2 ) n and n is a number from 1 to 15.
  • the units mentioned are advantageously distinguished by a very high twisting capacity and by great chemical and thermal stability.
  • the proportion of the units which make the polyester chain flexible is preferably about 1 to 50 mol%, in particular 5 to 30 mol%, of the total content of structural units.
  • the polyesters according to the invention can be produced by various types of polycondensation or by transesterification of polyesters with a mixture of acid component and acylated alcohol component.
  • Typical types of polycondensation are, for example, the “HCl process”, the “silyl process” and the “transesterification process”. These processes are from HR Kricheldorf, N. Probst, among others; Macromol. Rapid. Commun. (1995) 16, 231 and N. Probst, HR Kricheldorf; High perform. Polym. (1995) 7, 461.
  • Acid component and alcohol component are used in a molar ratio of approximately 1: 1.
  • the reaction time can vary within a wide range. In general, it is 1 to 48 hours, in particular 1 to 24 hours.
  • the reaction is carried out at elevated temperature, generally in the range from 120 ° C. to 300 ° C., the temperature in this range also being able to be increased in stages.
  • the free diols are mixed with the dichlorides of the dicarboxylic acids in a suitable organic solvent, e.g. an ether such as dioxane, a chlorinated hydrocarbon such as 1, 1,2,2-tetrachloroethane, 1-chloronaphthalene or 1,2-dichlorobenzene, dissolved in a suitable reaction vessel.
  • a suitable organic solvent e.g. an ether such as dioxane, a chlorinated hydrocarbon such as 1, 1,2,2-tetrachloroethane, 1-chloronaphthalene or 1,2-dichlorobenzene
  • a pressure-resistant stirred vessel with gas inlet and outlet lines is suitable as the reaction vessel, for example.
  • the released hydrogen chloride is preferably removed in a gentle stream of nitrogen.
  • the polyester obtained is dried at elevated temperature, for example at about 120 ° C. in vacuo.
  • the polyester is optionally subjected to a cleaning step by redissolving in one of the abovementioned solvents and precipitating in methanol.
  • the organic phase is separated off and the polyester is obtained therefrom in a conventional manner, e.g. by taking up in methanol and filtering off.
  • the reaction mixture is diluted if necessary, e.g. with methanol and the polymer is filtered off.
  • the bissilylated diols are dissolved with the dichlorides of the dicarboxylic acids in the presence of a catalytic amount of a quaternary ammonium salt such as, for example, triethylbenzylammonium chloride in bulk or with one of the abovementioned solvents in a suitable reaction vessel described above. is heating.
  • a quaternary ammonium salt such as, for example, triethylbenzylammonium chloride in bulk or with one of the abovementioned solvents in a suitable reaction vessel described above. is heating.
  • the polyester obtained is worked up as described above.
  • the free dicarboxylic acids with the acetylated diols in the presence of catalytic amounts of an alkali or alkaline earth metal oxide (for example MgO) or in the presence of zinc, tin, zirconium-manganese and bismuth salts are used in a suitable manner as described above Reaction vessel converted into substance.
  • the polyester obtained is worked up as described above.
  • the reactants in the molar mass ratio A: B: C are from about 1 to 5: 1 to 5: 1 to 5, in particular about 1 : 2: 2 used.
  • the reaction is carried out in a suitable reaction vessel, preferably in the presence of catalytic amounts of an early transition metal alkylate, e.g. Titanium tetrabutylate.
  • the reaction vessel is purged with nitrogen several times to remove air.
  • the acetic acid released during the reaction is preferably removed in a gentle stream of nitrogen.
  • the reaction is preferably continued in vacuo.
  • the polyester obtained is worked up as described above.
  • polyesters are in particular polyethylene terephthalate (PET), polybutylene terephthalate (PBT) and polyethylene naphthalate (PEN).
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PEN polyethylene naphthalate
  • the “HCl process”, the “silyl process” and the transesterification are particularly preferred.
  • polyesters according to the invention contain statistically distributed units.
  • the polymers according to the invention are particularly suitable as surface coating materials, as optical components and as chiral nematic colorants. They can be used as a color-imparting lacquer system for coating surfaces (eg as automotive lacquer or effect foils) or for the production of color pigments.
  • the color-giving structure of the polymer can be achieved by rapidly cooling the chiral nematic phase be fixed.
  • the polymers according to the invention advantageously have high glass transition temperatures (determined by means of DSC) of approximately 80 to 300 ° C., in particular approximately 100 to 220 ° C. At temperatures below the respective glass temperature, the coloring structure of the polymer is permanently preserved without additional crosslinking.
  • Color pigments can be produced, for example, by detaching the oriented polymer film from the coated surface and grinding it into platelet-shaped pigments. In contrast to the processes described in DE-A 42 40 743, crosslinking of the polymer is not necessary.
  • the polymer can be used as a coating system as a powder coating, in the melt or in solution (for example in N-methylpyrrolidone or dimethylformamide). In the simplest case, the system is oriented by tempering the coated surface and can be improved if necessary by the action of mechanical, electrical or magnetic forces.
  • the polymers according to the invention can be mixed with additional components to adjust the viscosity and the leveling behavior.
  • polymer binders and / or monomeric compounds which can be converted into a polymeric binder by polymerization, are particularly suitable for paint-like coatings.
  • agents are z. B. in organic solvents soluble polyesters, cellulose esters, polyurethanes, silicones, polyether- or polyester-modified silicones. Cellulose esters such as cellulose acetobutyrate are particularly preferably used.
  • z. B derivatives of 2,4-dihydroxybenzophenone, derivatives of 2-cyan-3,3-diphenylacrylate, derivatives of 2,2 ', 4,4' -tetrahydroxybenzophenone, derivatives of orthohydroxyphenyl-benzotriazole, salicylic acid esters, orthohydroxyphenyl-S-triazines or sterically hindered amines. These substances can be used alone or preferably in the form of mixtures.
  • Pigments, dyes and fillers can also be added to the coating systems according to the invention.
  • Inorganic pigments include iron oxides, titanium dioxide and the various types of carbon black.
  • Organic pigments are, for example, those from the class of the monoazo pigments (for example products which are derived from acetoacetic acid derivatives or from ⁇ -naphthol derivatives), monoazo dyes and their metal salts, such as ⁇ -oxynaphthoic acid dyes, disazo pigments, condensed disazo pigments, and disazo pigments, and Derivatives of naphthalene or perylene tetracarboxylic acid, anthraquinone pigments, thioindigo derivatives, azomethine derivatives, quinacridones, dioxazines, pyrazoloquinazolones, phthalocyanine pigments or basic dyes such as triarylmethane dyes and their salts.
  • monoazo pigments for example products which are derived from acetoacetic acid derivatives or from ⁇ -naphthol derivative
  • Effect pigments such as aluminum particles, mica or coated mica, micas or the commercially available platelet-shaped effect pigments with different chemical structures can be considered as further pigments.
  • fillers such. B. rutile, anatase, chalk, talc and barium sulfate.
  • Suitable as additional dyes are all which dissolve in the coating composition at least in a concentration of 0.1 mol%.
  • Dichroic dyes are particularly suitable.
  • the proportion of pigments, dyes or fillers is generally up to 40% by weight, preferably 0 to 10% by weight, based on the mass of the polymers according to the invention.
  • the surface coating can also be carried out by means of a printing process.
  • All common printing processes e.g. high, low, flexo, offset, screen printing
  • All common printing processes e.g. high, low, flexo, offset, screen printing
  • the molar ratio v / w / x / z is 19/1/2/18 (la).
  • five other polyesters with the molar ratio v / w / x / z 19/1/4/16 (lb), 19/1/6/14 (lc), 19/1/8/12 (ld), 18/2/6/14 (le) and 18/2/8/12 (lf) manufactured.
  • the yield was 97% for the polyester ld and 98% for the polyesters la, lb, lc, le and lf.
  • polyesters were prepared analogously to Example 1. Instead of tert-butyl hydroquinone, phenyl hydroquinone was used. There were three polyesters of Formula 2
  • polyester of formula 3 was alternatively produced using the "silyl process”.
  • the dichloride of compound I (2 mmol) and the dichloride of N- (4 '-carboxyphenyl) trimellitic acid imide ( 18 mmol) and triethylbenzylammonium chloride (10 mg) were placed in a cylindrical glass reactor with a mechanical stirrer and gas inlet and outlet.
  • the reaction vessel was placed in a metal bath preheated to 150 ° C.
  • the temperature was raised to 260 ° C and maintained for 3 hours.
  • a vacuum was applied for 15 minutes.
  • the polyester obtained was worked up as described above.
  • the yield for this polymer (3fs) was 99%.
  • Polymers 3a, 3b, 3d and 3e were also produced alternatively using the "silyl process".
  • the corresponding process products are referred to as 3as, 3bs, 3ds and 3es.
  • the yields were 99% for the polyesters 3as, 3bs and 3ds and 97% for 3es.
  • N- (4-carboxyphenyl) trimellitic acid imide dichloride 5 mmol
  • tert-butylhydroquinone 4.5 mmol
  • hexanediol 0.25 mmol
  • isosorbide 0.25 mmol

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • General Health & Medical Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

L'invention concerne des polyesters nématiques chiraux à cristaux liquides, à chaînes flexibles comprenant des motifs isosorbide, isomannide et/ou isoidide. Les polyesters ne sont pas cristallisés et forment des textures de Grandjean stables qui se congèlent par refroidissement au-dessous de la température de transition vitreuse. Ils sont donc utilisables plus particulièrement comme matériaux de revêtement de surfaces.
EP98909394A 1997-02-06 1998-02-05 Polyesters nematiques chiraux Withdrawn EP0958316A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19704506 1997-02-06
DE19704506A DE19704506A1 (de) 1997-02-06 1997-02-06 Chiral nematische Polyester
PCT/EP1998/000620 WO1998034974A1 (fr) 1997-02-06 1998-02-05 Polyesters nematiques chiraux

Publications (1)

Publication Number Publication Date
EP0958316A1 true EP0958316A1 (fr) 1999-11-24

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP98909394A Withdrawn EP0958316A1 (fr) 1997-02-06 1998-02-05 Polyesters nematiques chiraux

Country Status (7)

Country Link
US (1) US6291629B1 (fr)
EP (1) EP0958316A1 (fr)
JP (1) JP2001511205A (fr)
KR (1) KR20000070763A (fr)
CN (1) CN1252078A (fr)
DE (1) DE19704506A1 (fr)
WO (1) WO1998034974A1 (fr)

Families Citing this family (21)

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KR100572530B1 (ko) 1997-09-02 2006-04-24 바스프 악티엔게젤샤프트 다중층 콜레스테릭 안료
DE59807086D1 (de) 1997-09-02 2003-03-06 Basf Ag Cholesterische effektschichten und verfahren zu deren herstellung
DE19745647A1 (de) 1997-10-15 1999-04-22 Basf Ag Wärmeisolationsbeschichtung
DE19940681A1 (de) 1999-08-27 2001-03-01 Basf Ag Cholesterisches Schichtmaterial mit verbesserter Farbbeständigkeit und Verfahren zu dessen Herstellung
US6485819B2 (en) * 2000-12-19 2002-11-26 E. I. Du Pont De Nemours And Company Aliphatic-aromatic copolyesters
JP4024012B2 (ja) 2001-05-15 2007-12-19 富士フイルム株式会社 光学活性ポリエステル、光反応型キラル剤、液晶組成物、液晶カラーフィルタ、光学フィルム及び記録媒体、並びに液晶の螺旋構造を変化させる方法、液晶の螺旋構造を固定化する方法
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DE19704506A1 (de) 1998-08-13
WO1998034974A1 (fr) 1998-08-13
KR20000070763A (ko) 2000-11-25
CN1252078A (zh) 2000-05-03
JP2001511205A (ja) 2001-08-07
US6291629B1 (en) 2001-09-18

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