EP0915927A1 - Polycarbonates nematiques chiraux - Google Patents

Polycarbonates nematiques chiraux

Info

Publication number
EP0915927A1
EP0915927A1 EP97918961A EP97918961A EP0915927A1 EP 0915927 A1 EP0915927 A1 EP 0915927A1 EP 97918961 A EP97918961 A EP 97918961A EP 97918961 A EP97918961 A EP 97918961A EP 0915927 A1 EP0915927 A1 EP 0915927A1
Authority
EP
European Patent Office
Prior art keywords
chiral
chiral nematic
group
formula
mmol
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Withdrawn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
EP97918961A
Other languages
German (de)
English (en)
Inventor
Peter Schuhmacher
Hans R. Kricheldorf
Shin-Jieh Sun
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
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP0915927A1 publication Critical patent/EP0915927A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/04—Aromatic polycarbonates
    • 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
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/16—Aliphatic-aromatic or araliphatic polycarbonates
    • 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

Definitions

  • the invention relates to liquid-crystalline chiral nematic polycarbonates.
  • 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 created 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 colors which appear different depending on the viewing angle, depend on the pitch of the helical superstructure, which in turn depends on the twisting power of the chiral component.
  • the pitch and thus the wavelength range of the selectively reflected light of a chiral nematic layer can be varied in particular by changing the concentration of a chiral dopant.
  • Such chiral nematic systems offer interesting possibilities for practical use.
  • chiral parts of the molecule into esogenic acrylic acid esters and orientation in the chiral nematic phase, for example after photocrosslinking, a stable, colored network can be produced, the concentration of chiral component of which can then no longer be changed (G. Galli, M Laus, A. Angelon, Makromol. Chemistry 187, 2289 (1986)).
  • nematic acrylic acid esters By adding non-crosslinkable chiral compounds In nematic acrylic acid esters, a colored polymer can be produced by photocrosslinking, which still contains high proportions of soluble components (I. Heyndricks, DJ Broer, ⁇ fol. Cryst. Liq. Cryst. 203, 113 (1991)).
  • 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 limits the selection of the remaining polyester components, for example with regard to 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 ranges.
  • EP-A-682 092 describes paints based on chiral nematic polymers. Examples are only polyesters which have been prepared by polycondensation of dicarboxylic acids and diols. Polycarbonates are not mentioned.
  • Chiral nematic polycarbonates were previously unknown. Because of its nonlinear structure, the carbonate group is less suitable than the ester group for stabilizing a liquid-crystalline phase. Nevertheless, it has been possible to produce aromatic polycarbonates which contain para-linked diphenols, in particular 4, 4'-dihydroxybiphenyl (DHB) and can form a nematic phase over a wide temperature range (Kricheldorf, HR; Lübbers, D., Makromol. Rapid Communc. 1989, 10, 383; Kricheldorf, HR; Lübbers, D., Macromolecules 1990, 23, 2656; Sun, S.-J .; Chang, TzCh., J. Polym. Sei., Part A, Polym. Chem. 1993, 31, 2237). However, the use of chiral comonomers is problematic since they more destabilize the liquid-crystalline phase of polycarbonates than their non-chiral analogues.
  • the invention relates to chiral nematic polycarbonates with carbonate units which comprise a mesogenic group and carbonate units which comprise a chiral group and chiral nematic polycarbonates which additionally contain carbonate units with a photoreactive group and / or carbonate units with a further, non-chiral group, which is, in particular, a mesogenic and / or solubility-improving group.
  • the units mentioned are groups which can be derived from diols by removing the two hydroxyl groups. They are therefore also referred to below as diol units.
  • molar ratio w / x / y / z is about 1 to 20 / about 1 to 5 / about 0 to 10 / about 0 to 10.
  • a molar ratio w / x / y / z of approximately 1 to 5 / approximately 1 to 2 / approximately 0 to 5 / approximately 0 to 5 is particularly preferred.
  • L in the above formulas is alkyl, alkoxy, halogen, COOR, OCOR, CONHR or NHCOR
  • X is S, O, N, CH 2 or a single bond
  • R is alkyl or hydrogen
  • A is a single bond, (CH 2 ) n , 0 (CH 2 ) n / S (Cu 2 ) n , NR (CH 2 ) n .
  • R 1 is hydrogen, halogen, alkyl or phenyl and
  • n is an integer from 1 to 15.
  • R 1 is alkyl, halogen and A is a single bond or when R 1 is H or alkyl and A is 0 ⁇ CH 2 ) n ( S (CH 2 ) n or NR (CH 2 ) n
  • Isosorbide, isomannide and / or isoidide is the preferred chiral component.
  • the proportion of the chiral diol structural units is preferably in the range from 1 to 80 mol% of the total content of diol structural units, particularly preferably 2 to 20 mol%, depending on the desired interference color.
  • Alkyl (also in alkoxy, etc.) is preferably Ci-C ß alkyl, in particular C ⁇ -C 4 alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec- Butyl, tert-butyl, n-pentyl and n-hexyl.
  • the polycarbonates according to the invention can be prepared by various types of polycondensation of diols with phosgene or diphosgene.
  • Densations arten usual polycondensation, for example, interfacial polycondensation, S chmelzpolykondensation and solution polycondensation.
  • the diols forming the mesogenic group, the chiral group and, if appropriate, the photoreactive and the solubility-improving group together with phosgene or preferably the much less dangerous diphosgene (CI-COCCI 3 ) or triphosgene and a catalytic amount of an amine, for example triethylamine or a quaternary ammonium salt such as triethylbenzylammonium chloride in a suitable organic solvent, for example an ether such as tetrahydrofuran or dioxane, a chlorinated hydrocarbon such as dichloromethane or chlorobenzene.
  • a suitable organic solvent for example an ether such as tetrahydrofuran or dioxane, a chlorinated hydrocarbon such as dichloromethane or chlorobenzene.
  • aqueous base for example sodium hydroxide solution
  • An aqueous base for example sodium hydroxide solution
  • the two phases are mixed with one another, for example by vigorous stirring. Cooling is preferably carried out while stirring.
  • the organic phase is separated off and the polycarbonate is obtained therefrom in a customary manner, for example by taking up in methanol and filtering off. If, on the other hand, the polymer precipitates out of the solvent or if gel formation occurs, the reaction mixture is diluted if necessary, for example with methanol, and the polymer is filtered off.
  • the chlorinated carbonic acid diesters of the diols to be condensed can also be used.
  • the dicarbonate of one of the diols forming the mesogenic group, the chiral group and optionally the solubility-improving or the photoreactive group is reacted with the diols forming the remaining groups.
  • the reaction is carried out at a higher 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 polymer obtained is dissolved or suspended in one of the suitable solvents mentioned above and optionally precipitated with methanol.
  • the diols forming the mesogenic group, the chiral group and optionally the further non-chiral group and the photoreactive group are dissolved in an amine, preferably a tertiary or aromatic amine, for example pyridine.
  • Diphosgene dissolved in one of the abovementioned suitable solvents is added to this solution.
  • the reaction temperature is generally in the range from about 0 ° C to ambient temperature, but it can also be higher, in particular to complete the reaction.
  • the mixture is then worked up in the usual way.
  • the chlorinated carbonic acid diesters of the diols to be polymerized can also be used in solution polycondensation. 5
  • the interfacial polycondensation and the solution polycondensation are preferred, the latter particularly when more hydrophilic monomers, such as isosorbide, are used which interfere much more poorly with the interfacial polycondensation from the aqueous phase into the organic phase than the other monomers with them they are to be condensed.
  • a chain terminator e.g. Cinnamic acid chloride can be added.
  • the glass transition temperature (determined by means of DSC) of the polycarbonates according to the invention is generally in the range from about 50 to 25 300 ° C., in particular about 60 to 200 ° C.
  • the melting temperature of the polymers according to the invention is generally in the range from approximately 75 to 450 ° C., in particular approximately 90 to 350 ° C.
  • the polycarbonates according to the invention contain statistically distributed units.
  • the polycarbonates according to the invention are capable of forming a so-called "grand jeans texture", which confirms the cholesteric effect of the chiral groups used.
  • 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 coloring paint system for coating surfaces (e.g. as automotive paint
  • color-giving structure of the polymer can be fixed by rapid cooling or photochemical crosslinking of the chiral nematic phase.
  • the production of color pigments can e.g. by detaching the oriented polymer
  • 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 dimethylform amide). 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.
  • Table 1 shows the physical properties (inherent viscosity ( ⁇ i nh ), rotation value ([ ⁇ ] D ), glass level (T g ) and clearing point (Ti)), the observed textures of the liquid-crystalline phases and the interference colors of polymers 1 to 5 .

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne des polycarbonates nématiques chiraux mésamorphes.
EP97918961A 1996-08-05 1997-08-05 Polycarbonates nematiques chiraux Withdrawn EP0915927A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19631658A DE19631658A1 (de) 1996-08-05 1996-08-05 Chiral nematische Polycarbonate
DE19631658 1996-08-05
PCT/EP1997/004266 WO1998005698A1 (fr) 1996-08-05 1997-08-05 Polycarbonates nematiques chiraux

Publications (1)

Publication Number Publication Date
EP0915927A1 true EP0915927A1 (fr) 1999-05-19

Family

ID=7801884

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97918961A Withdrawn EP0915927A1 (fr) 1996-08-05 1997-08-05 Polycarbonates nematiques chiraux

Country Status (6)

Country Link
US (1) US6156866A (fr)
EP (1) EP0915927A1 (fr)
JP (1) JP2000515574A (fr)
AU (1) AU740373B2 (fr)
DE (1) DE19631658A1 (fr)
WO (1) WO1998005698A1 (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6410130B1 (en) 1997-09-02 2002-06-25 Basf Aktiengesellschaft Coatings with a cholesteric effect and method for the production thereof
KR100572530B1 (ko) 1997-09-02 2006-04-24 바스프 악티엔게젤샤프트 다중층 콜레스테릭 안료
DE19745647A1 (de) 1997-10-15 1999-04-22 Basf Ag Wärmeisolationsbeschichtung
DE19848130A1 (de) * 1998-10-19 2000-04-20 Basf Ag Verwendung von cholesterisch-flüssigkristallinen Polymeren als UV-Filter in kosmetischen und pharmazeutischen Zubereitungen
DE19940681A1 (de) 1999-08-27 2001-03-01 Basf Ag Cholesterisches Schichtmaterial mit verbesserter Farbbeständigkeit und Verfahren zu dessen Herstellung
DE19940682A1 (de) 1999-08-27 2001-03-01 Basf Ag Cholesterisches Schichtmaterial mit verbessertem Farbeindruck und Verfahren zu dessen Herstellung
US7138479B2 (en) * 2003-12-31 2006-11-21 General Electric Company Aliphatic diol polycarbonates and their preparation
CN1989173B (zh) * 2004-05-31 2010-09-08 三井化学株式会社 脂肪族聚酯共聚物
EP2036937A1 (fr) * 2007-09-13 2009-03-18 Stichting Dutch Polymer Institute Polycarbonate et son procédé de production

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2938464A1 (de) * 1979-09-22 1981-04-09 Bayer Ag, 5090 Leverkusen Thermoplastische polycarbonate, ihre herstellung und ihre verwendung als formkoerper und folien
DE3002762A1 (de) * 1980-01-26 1981-07-30 Bayer Ag, 5090 Leverkusen Verfahren zur herstellung von heterocyclisch-aromatischen oligocarbonaten mit diphenolcarbonat-endgruppen und ihre verwendung zur herstellung von thermoplastischen, hochmolekularen heterocyclisch-aromatischen copolycarbonaten
DE4416993C2 (de) * 1994-05-13 2002-12-12 Daimler Chrysler Ag Thermisch farb-beinflußbare Lackierung
JPH08292432A (ja) * 1995-04-20 1996-11-05 Nippon Oil Co Ltd 光学フィルムの製造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9805698A1 *

Also Published As

Publication number Publication date
AU4298097A (en) 1998-02-25
WO1998005698A1 (fr) 1998-02-12
DE19631658A1 (de) 1998-02-12
US6156866A (en) 2000-12-05
JP2000515574A (ja) 2000-11-21
AU740373B2 (en) 2001-11-01

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