DE19717371A1 - Propargyl-terminated nematic or cholesteric polymers - Google Patents

Abstract

Propargyl-terminated nematic or cholesteric polyesters, polycarbonates or mixtures thereof (I) are new, except for diesters of formula P-A<1>-A-A<2>-P (Ia), in which A = 1,4-phenylene (Phe), 4,4'-biphenylene, 2,6-naphthylene or -Phe-CR=CR-Phe- (with R = H or CH3) (all optionally substituted with halogen, nitro, alkyl, alkoxy, fluoroalkyl, fluoroalkoxy or phenyl); A<1>, A<2> = -Phe-COO- or -Phe-OCO-; and P = HC?=CCH2O-. Also claimed are (i) crosslinked polyesters or polycarbonates or nematic or cholesteric mixtures thereof obtained by heating (I); (ii) pigments and coating materials containing (I) or crosslinked (I); (iii) compounds of formula (II) or their amides or acid halides, in which A<1>-A<4> = H, alkyl, alkoxyalkyl, optionally alkyl- substituted cycloalkyl, halogen or nitro, preferably H; X = S, O or NR<2>; R<2> = H, 1-4C alkyl or phenyl; and R<3> = H, 1-4C alkyl, aryl or aryl-(1-4C alkyl).

Description

The invention relates to propargyl-terminated, nematic or cholesteric polyesters, polycarbonates or mixtures thereof.

When heating anisotropic substances can be liquid crystalline Phases, so-called mesophases, occur. The individual phases differ in the spatial arrangement of the molecule focal points on the one hand and due to the molecular arrangement the longitudinal axes on the other hand (G. W. Gray, P. A. Winsor, Liquid Crystals and Plastic Crystals, Ellis Horwood Limited, Chichester 1974). The nematic liquid crystalline phase draws by the parallel orientation of the molecular longitudinal axes (a dimensional order). Provided that the The molecules that build the nematic phase are chiral a so-called chiral nematic (cholesteric) phase in which the longitudinal axes of the molecules are helical, perpendicular to it Form superstructure (H. Baessler, Solid State Problems XI, 1971). The chiral part of the molecule can be found in both liquid crystalline Molecule itself be present as well as a dopant be given nematic phase, the chiral nematic Phase is induced. This phenomenon was first brought to Choleste rol 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. If 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 perspective, depend on the pitch of the helical superstructure, which in turn depends on the twisting power of the chiral component. In particular, by changing the concentration of a chiral dopant, the pitch and thus the wavelength range of the selectively reflected light of a chiral nematic layer can be varied. Such chiral nematic systems offer interesting possibilities for practical use. Thus, by incorporating chiral moles, cooling parts in mesogenic acrylic acid esters and orientation in the chiral nematic phase, e.g. B. after photocrosslinking, a stable, colored network can be produced whose concentration of chiral component can then no longer be changed (G. Galli, M. Laus, A. Angelon, Makromol. Chemie 187, 2289 (1986)) . 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)) . Furthermore, a chiral nematic network can be obtained by statistical hydrosilylation of mixtures of cholesterol derivatives and acrylate-containing mesogens with defined cyclic siloxanes and subsequent photopolymerization, in which the chiral component can have a share of up to 50% of 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, Freiburg, 1993).

DE-A-35 35 547 describes a method in which a mixture of cholesterol-containing monoacrylates via a photo can be processed into chiral nematic layers can. However, the total proportion of the chiral component is in the mixture approx. 94%. As a pure side chain polymer is a such material is not mechanically very stable, an increase however, stability can be achieved through highly cross-linking diluents can be achieved.

Also numerous chiral nematic polyesters in which the meso structures built into the main chain are known e.g. B. from S. Vilasagar, A. Blumstein, Mol. Cryst. Liq. Cryst. (1980), 56 (8), 263-9; A. Blumstein, s. Vilasagar, S. Ponratham, S. B. Clough, R.B. Blumstein, G. Maret, J. Polym. Sci., Polym. Phys. Ed. (1982), 20 (5), 877-92; E. Chiellini, G. Galli, C. Ma langa, N. Spassky, Polym. Bull. (1983), 9 (6-7), 336-43); H. J. Park, J.I. Jin, R.W. Leng, Polymer (1985), 26 (9), 1301-6; J. I. Jin, E.J. Choi, K.Y. Lee, Polym. J. (1986), 18 (1), 99.101; J.I. Jin, S.C. Lee, S.D. Chi, J.H. Chang; Pollimo (1986), 10 (4), 382-8; J.I. Jin, E.J. Choi, B.W. Jo, Pollimo (1986), 10 (6), 635-40; J.M.G. Cowie, H.H. Wu, Makromol. Chem. (1988), 189 (7), 1511-16; V. V. Zuev, I. G. Denisov, S. S. Skorokhodov, Vysokomol. Soedin., Ser. A (1989, 31 (5), 1056-61; A. S. Ange loni, D. Caretti, C. Carlini, E. Chiellini, G. Galli, A. Alto mare, R. Solaro, M. Laus, Liq. Cryst. (1986), 4 (5), 513-27; K. Fujishiro, R. W. Lenz, Nacromolecules (1992), 25 (1), 88-95; K. Fujishiro, R. W. Lenz, Nacromolecules (1992), 25 (1), 81-7; V. V. Zuev, I. G. Denisov, S. S. Skorokhodov, Vysokomol. Soedin., Ser. B (1992), 34 (3) 1 47-54); V. V. Zuev, I. G. Denisov,  S. S. Skorokhodov Vysokomol. Soedin., Ser. B (1989), 31 (2), 130-2.

These polyesters generally show narrow areas of existence chiral nematic phase and contain predominantly open-chain chiral components that have a low twistability sit, so that relatively large proportions of these components are necessary are to achieve a color impression. This makes the selection the remaining polyester components e.g. B. regarding their mechanical properties limited.

DE-A-195 04 913 describes chiral nematic polyester with strongly twisting chiral diol components, in particular their dianhydro sugars, and broad liquid-crystalline phases areas. The polymers can contain cinnamic acid groups that can be crosslinked via a [2 + 2] photocycloaddition.

EP-A-682 092 describes paints based on chiral nemati shear polymers by UV radiation, but not thermally can be networked. Examples are polyesters which are produced by poly condensation of dicarboxylic acids and diols have been prepared, called.

DE-A-44 41 651 describes a method for superficial loading layering of substrates with a coating agent that min least a polymerizable low molecular weight liquid crystalline Connection contains, known. It also uses especially photochemically polymerizable, low molecular weight liquid crystalline compounds (oligoesters) in printing inks, Inks and coating systems described.

WO-A-96/02 597 describes a method for coating or for printing substances with a coating or Be pressure medium containing a chiral or achiral liquid crystal lines monomer and a non-liquid crystalline chiral compound manure contains. The liquid crystalline monomers are preferred Photo-polymerizable bisacrylates.

WO-A-95/29 962 describes aqueous coating compositions for the manufacture provision of coatings whose color impression depends on the viewing angle is dependent and the platelet-shaped pigments from oriented, three-dimensionally cross-linked substances of liquid crystalline structure contain chiral phase. As a particularly preferred sub Three-dimensionally crosslinkable polyorganosiloxanes are punched wrote.  

From WO-A-95/29 961 coating agents are also considered angle-dependent color impression and their use in basecoats known for multi-layer coatings. The funds contain flat Chen-shaped pigments with color depending on the viewing angle little, which consists of oriented, three-dimensionally networked sub Punch liquid-crystalline structure with a chiral phase. Three-dimensionally crosslinkable Po are preferred substances lyorganosiloxanes described.

DE-A-44 18 076 describes an effect lacquer or an effect painting using liquid crystalline interference pigments. The interference pigments consist of esterified Cel lulose ethers, in particular from acylated hydroxypropyl cellulose.

From EP-A-724 005 is a pigment with the viewing angle dependent color, its production and use in egg known paint. The pigment is determined by three-dimensional Ver network of oriented substances liquid-crystalline structure obtained with a chiral phase. Preferred substances are three Dimensionally crosslinkable polyorganosiloxanes. To counter the pigment It is suggested to make the paint retain its color over elevated temperatures networking in the presence of at least one other perform color-neutral connection, the at least two ver contains wettable double bonds. As preferred color neutral Compounds are acrylates, polyurethanes, epoxies, siloxanes, Called polyester and alkyd resins.

EP-A-0686 674 and the priority request on which it is based DE-A-44 16 191 describe interference pigments from in chole sterically arranged molecules and their use. The pigments described have a platelet-like structure and a thickness of 1 µm to 20 µm. They contain oriented ones cross-linked substances of liquid crystalline structure with a chi oral phase (preferably polyorganosiloxanes).

EP-A-0601 483 and the priority request on which it is based dung DE-A-42 40 743 describe pigments with the consideration dependent color, their production and use. The described pigments consist of oriented three-dimensional cross-linked substances liquid-crystalline structure with chiral Phase (preferably polyorganosiloxanes) and optionally white dyes and pigments. The existing ones, if any other dyes and pigments do not serve as carriers for the oriented three-dimensionally cross-linked liquid crystals substances with a chiral phase.  

DE-A-196 31 658 describes chiral nematic polycarbonates which through different types of polycondensation of diols with Phosgene or diphosgene can be produced. Photoreactive and / or Thermally crosslinking groups can be in the form of the corresponding Diol compounds are condensed. Propargyl derivatives or their use to terminate the polycarbonate chains not mentioned.

DE-A-197 04 506.5 describes liquid-crystalline chiral nemati cal polyester with flexible chains, the isosorbide, isomannide and / or include isoidide units. The polyesters are not kri stallin and form grandjean textures that cool down as they cool freeze below the glass transition temperature. You are there forth especially as surface coating materials bar.

One of the main problems in providing nematic or is cholesteric oligo- / polyester or oligo- / polycarbonate fixation of their supermolecular order that the desired optical properties of the polymers. Different me methods for fixing the supermolecular order of polymers through cross-linking via σ bonds have recently been published (H.R. Kricheldorf, N. Probst, M. Gurau, M. Berghahn; Macromolecu les (1995) 28, 6565; J. Stumpe, A. Ziegler, M. Berghahn, H.R. Kricheldorf; Macromolecules (1995) 28, 5306; MR. Kricheldorf, N. Rehearsal; High perform. Polym. (1995) 7, 471-480). These methods include photo-crosslinking of UV-sensitive chiral nematic Polymers.

From P.M. Hergenrother, Encyclopedia of Polymers 1, 61 (1985) Acetylene-terminated prepolymers known (pp. 61-86) and poly mers that contain propargyl groups in the side chains (p. 82f). The connection described can be thermally crosslinked.

From PM Hergenrother et al., Journal of Polymer Science: Part A:
Polymer Chemistry, 32, 3061-3067 (1994), phenylacetylenyl terminated oligo- / polyimides are known which can be crosslinked at high temperatures without the release of volatile substances. The crosslinked polymers described are said to be more stable to thermooxidation than those which have been prepared from acetylene-terminated oligomers.

Kozuch, M. et al. describe in Macromol. Chem. Phys. 196, 2371-2382 (1995) the synthesis and characterization of phenyla cetylene-terminated oligoaryl ether sulfones and oligoaryl ethers ketones. Both compounds are more volatile without release  Substances thermally crosslinkable at elevated temperatures and in ver wetted state solvent-resistant.

From Melissaris, A.P. and Litt, M.H., Macromolecules, 26, 6734-6740 (1993) is N, N'-bis (p-acetylenylphenyl) pyromelliti mid known that without the release of volatile substances and without Mit effect of a catalyst via a radical intermediate can be cross-linked thermally.

Melissaris, A.P. et al. describe in Macromolecules, 28, 860-865 (1995) further p-acetylenyl-substituted monomers which thermal at temperatures well below their glass temperatures can be networked and in the networked state a small li compared to linear thermal expansion and high stability Have thermal oxidation.

Acetylene-terminated oligoether ketones are described by Nunez, F.M. et al. in Polymer, 33, 15, 3286-3291 (1992). The oligo mers can be thermally cross-linked at 150-300 ° C, in a cross-linked state stood insoluble and thermally stable with glass temperatures of un dangerous 250 ° C.

Taguchi, Y. et al. describe the synthesis thermally crosslinkable rer acetylene-terminated polyaryl ether ketones, which in the crosslinked Are insoluble and very moisture-resistant (Macromol. Rapid Commun., 16, 183-187 (1995)).

US-A-4,206,107 describes acetylene-terminated oligoimides, which are very good for use as molding resin, lacquer resin and / or Laminating resin should be suitable.

US-A-4, 166,168 describes acetylene-terminated polyimide esters and their thermal crosslinking to produce insoluble ones non-meltable polymers without formation of by-products.

Grenier-Loustalot, MF and Sanglar, C. describe the thermal crosslinking of propargyl-terminated bisphenol A monomers in the presence of catalysts which considerably reduce the crosslinking temperature. Suitable catalysts are (C ₅ H ₅ ) Co (CO) ₂ , CuCl, CuCl ₂ , (C ₅ H ₅ ) ₂ Ni, ((C ₆ H ₅ ) ₃ P) ₂ NiCl ₂ and RhCl ((C ₆ H ₅ ) ₃ P) ₃ (High Perform. Polym., 8, 533-554 (1996)).

US-A-5,475,133 describes thermally crosslinkable diesters which by 4-propargyloxybenzoic acid or p-propargyloxyphenyloxyre are scheduled. Substituted propargyloxybenzoic acid end groups or propargyloxyphenyloxy end groups will not thinks. Neither polycarbonate nor polyester with a polymer  Degree of tion <2 are described in the cited document. Also cholesteric compounds are not mentioned. Some of the at playfully described diesters have liquid-crystalline properties but that are far below the cross-linking temperature lost. It will not be an example of networking in the liquid crystal phase listed.

The invention is therefore based on the object, polyester, To provide polycarbonates or mixtures thereof, which in the ne matische or cholesteric phase are thermally crosslinkable.

The present invention relates to propargyl-terminated, nematic or cholesteric polyesters, polycarbonates or nematic or cholesteric mixtures which contain them, with the exception of diesters of the formula

P - A ¹ - A - A ² - P,

wherein A is 1,4-phenylene, 4,4'-biphenyl, 2,6-naphthalinyl or -C ₆ H ₄ -CR = CR-C ₆ H ₄ -, where R is H or CH ₃ and A is one or can have several substituents which are selected from halogen, nitro, alkyl, alkoxy, furoalkyl, fluoroalkoxy or phenyl,
A ¹ and A ² for

stand and P stands for HC∼CCH ₂ O-.

Among polyesters or polycarbonates are compounds with to understand at least two ester or carbonate groups.

Unless otherwise stated, alkyl (also in alkoxy etc.) for a branched or unbranched alkyl group, the preferred have 1 to 12 carbon atoms, in particular 1 to 6 carbon atoms fatome and particularly preferably 1 to 4 carbon atoms points.

Aryl or Ar is preferably phenyl or naphthyl. Halo gene preferably means Cl or Br.

Preferred compounds according to the invention are polyesters, polycarbonates or nematic or cholesteric mixtures with at least one propargyl end group of the formula R ³ C∼C-CH ₂ -, in which R ^{3 is} H, C ₁ -C ₄ alkyl, aryl or Ar-C ₁ -C ₄ alkyl (e.g. benzyl or phenethyl), which is bonded directly or via a link to the polyester or polycarbonate. The link is preferably selected from

wherein R ^{4 is} H; C ₁ -C ₄ alkyl or phenyl, X represents O, S or NR ² , and R ^{2 represents} H, C ₁ -C ₄ alkyl or phenyl.

In the polyesters according to the invention, the propyl end group is preferably above

bound.

The polyesters according to the invention preferably contain

• a) at least one aromatic or araliphatic dicarboxylic acid purity and / or at least one aromatic or aralipha tables hydroxycarboxylic acid unit and
• b) at least one diol unit.

Preferred dicarboxylic acid units are those of the formula

especially those of the formula

where each of the phenyl groups or the naphthyl group can have 1, 2 or 3 substituents which are selected independently of one another from C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen or phenyl, in the formulas above
W represents NR, S, O, (CH ₂ ) _p O (CH ₂ ) _q , (CH ₂ ) _m or a single bond,
R represents alkyl or hydrogen,
m represents an integer from 1 to 15, and
p and q stand independently for integers from 0 to 10.

Preferred hydroxycarboxylic acid units are those of the formula

where each phenyl group or the naphthyl group may have 1, 2 or 3 substituents which are independently selected from C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen or phenyl.

Preferred diol units are those of the formula

especially the formula

being in the formulas above
L represents alkyl, alkoxy, halogen, COOR, OCOR, CONHR or NHCOR,
X represents S, O, N, CH ₂ or a single bond,
A is a single bond, (CH ₂ ) _n , O (CH ₂ ) _n , S (CH ₂ ) _n , NR (CH ₂ ) _n ,

or

means
R represents alkyl or hydrogen,
R ^{1 is} hydrogen, halogen, alkyl or phenyl and
n is an integer from 1 to 15.

A preferred embodiment are polyesters which have at least one dicarboxylic acid unit of the formula

and at least one diol unit of the formula

where R ³ for
H, halogen, C ₁ -C ₄ alkyl, in particular CH ₃ or C (CH ₃ ) ₃ , or phenyl is contained.

Further preferred compounds according to the invention are diesters of the formula PYB-CO-OAO-CO-BYP, where P represents a propargyl end group of the formula defined above, Y represents O, S or NR ² (R ² = C ₁ -C ₄ -alkyl) stands for B for

stands, where
each phenyl group or the naphthyl group may have 1, 2 or 3 substituents which are independently selected from C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen or phenyl, and A (together with the neighboring oxygen atoms ) stands for one of the diol units mentioned above.

Particularly preferred diesters are those of the above-mentioned mel, in which B for

stands, and
especially diesters of the formula

HC∼CCH ₂ OB-CO-OAO-CO-B-OCH ₂ -C∼CH, wherein

• a) B for
  and
  A for
  stands, or
• b) B for
  stands, and

A has the meanings mentioned under a).

Further preferred compounds according to the invention are polycarbonates, which contain at least one diol unit of the formulas mentioned above, in particular of the formulas

built-in included.

Preferred polycarbonates are those which have at least one mesogenic unit of the formula as diol units

and
at least one chiral unit of the formula

and optionally a non-chiral unit of the formula

contain, wherein R ^{1 has} the meanings given above and in particular represents H or CH ₃ .

Particularly preferred polycarbonates are those with propargyl end groups of the formula HC∼CCH ₂ OR ⁵ -CO, where R ^{5 is}

stands.

The polyesters according to the invention can be prepared by ver Different types of polycondensation take place, among others from H.R. Kricheldorf, N. Probst; Macromol. Rapid. Commun. (1995)  16, 231 and N. Probst, H.R. Kricheldorf; High perform. Polym. (1995) 7, 461 are known.

Acid component and alcohol component are in a molar ratio nis from about 2.5 to 4.5: 2.5 to 4.5.

The reaction time can vary within a wide range. In all in general it is 1 to 48 h, in particular 1 to 24 h.

The reaction is carried out at elevated temperature, however below the crosslinking temperature of the reactants or react tion products, generally in the range of 120 ° C to 300 ° C, where with the temperature in this area also gradually increased that can.

Preferred for the production of the polyesters according to the invention th condensation process, the free diols with an ak tivated derivative of dicarboxylic acids, eg. B. the dichloride and Propargyl derivatives with free hydroxyl function or chlorides of Propargyl derivatives in a suitable organic solvent, e.g. B. an ether such as dioxane, a chlorinated hydrocarbon such as dichloromethane, 1,1,2,2-tetrachloroethane, 1-chloronaphthalene or 1,2-dichlorobenzene. Conveniently the condensation in the presence of a base, e.g. B. pyridine, performed as an HCl acceptor. Is suitable as a reaction for example a pressure-resistant stirred tank with gas on and off drain lines.

The process is preferably carried out under nitrogen. The butt won lyester is dried at elevated temperature, for example at about 120 ° C in a vacuum. If necessary, the polyester is one Cleaning step by redissolving in one of the above Subject to solvents and precipitates with methanol.

If the polymer is soluble in the solvent used, the organic phase is separated off and the polyester is converted into won in the usual way, e.g. B. by taking up in methanol and Filter off. However, if the polymer falls out of the solvent or if gel formation occurs, the reaction mixture is countered also diluted, e.g. B. with methanol and the polymer is off filtered.

The preparation of the polycarbonates according to the invention can be the same if by different types of polycondensation, which under are known from DE-A-19631658.  

The response time is variable over a wide range; they be generally wears 10 minutes to 24 hours, especially 10 Minutes to 5 hours. The reaction temperature is generally NEN in the range of about 0 ° C to ambient temperature, it can but also be higher, especially to complete the reaction standing.

In the case of the production of the polycarbonates according to the invention Preferred condensation processes are the free diols in one Amine, preferably a tertiary or aromatic amine for example pyridine, dissolved. Phosgene, diphosgene or triphosgene is in a suitable organic solvent, e.g. B. one Ethers such as tetrahydrofuran or dioxane, a chlorinated carbon hydrogen, such as dichloromethane, 1,1,2,2-tetrachloroethane, 1-chlorine Naphtalin, chlorobenzene or 1,2-dichlorobenzene dissolved. This Lö solution is added to the solution containing the diols with stirring ben. If the polymer is soluble in the solvent used is, the organic phase is separated and the polycarbonate obtained from it in the usual way, e.g. B. by inclusion in metha nol and filtering off. However, if the polymer falls out of solution medium or if gel formation occurs, the reaction gene mix diluted if necessary, e.g. B. with methanol and the polymer trated. As an alternative to phosgene, diphosgene or triphosgene also the chlorinated carbonic acid diesters of those to be condensed Diols are used.

The chain length of the polyester or polycarbo according to the invention nate can above all use the amount of propargyl derivatives be riied.

The polyesters and polycarbonates according to the invention can coexist others to be mixed to "blends", for example to improve their physi optimize the calic properties. If necessary, too Isotropic (non-liquid-crystalline) polymers are added, especially if they have the cholesteric properties of the Ge improve the mix. Mixtures of propar are particularly preferred gyl-terminated diesters of isosorbide, chirality and a have great twistability, with propargyl-terminated nematic or cholesteric diesters. These mixtures that up to 30 mol%, preferably 5 to 20 mol%, of propargyl-terminated Diesters of isosorbide contain exhibit thermal crosslinking permanent fixable Grandjean textures.  

The polyesters according to the invention have an inherent viscosity η _inh of about 0.01 to 3 dl / g, in particular about 0.01 to 1.5 dl / g, measured at 20 ° C. with c = 2 g / l in dichloromethane / trifluoroacetic acid (Volume ratio 4 / l).

The glass transition temperature (determined by means of DSC) of the invention Polyester is generally in the range from about 50 to 300 ° C. especially around 60 to 200 ° C.

The polycarbonates according to the invention have an inherent viscosity η _inh of approximately 0.01 to 3 dl / g, in particular approximately 0.01 to 2 dl / g, measured at 20 ° C. with c = 2 g / l in dichloromethane / trifluoroacetic acid ( Volume ratio 4 / l).

The glass temperature of the invention determined by means of DSC Polycarbonates generally range from about 50 to 300 ° C, especially about 50 to 250 ° C.

The polyesters and polycarbonates according to the invention contain the Dicarboxylic acid or the diol units in a statistical distribution.

The compounds of the invention are without a catalyst a temperature of about 120 to 340 ° C, especially about 200 to 315 ° C thermally cross-linkable.

In order to be able to carry out the crosslinking at lower temperatures, it is also possible to work in the presence of catalysts, especially those in high perform. Polym., 8, 533-554 (1996): (C ₅ H ₅ ) Co (CO) ₂ , CuCl, CuCl ₂ , (C ₅ H ₅ ) ₂ Ni, ((C ₆ H ₅ ) ₃ P) ₂ NiCl ₂ and RhCl ((C ₆ H ₅ ) ₃ P) ₃ . The catalysts or mixtures thereof are preferably used in an amount of about 0.01 to 3% by weight of the reaction mixture, particularly preferably about 0.1 to 1% by weight of the reaction mixture. Depending on the catalyst and catalyst concentration, the crosslinking temperature is up to about 100 ° C. lower than that for crosslinking without a catalyst.

The polymers and mixtures according to the invention are particularly suitable others as surface coating materials, as optical construction elements and as a colorant. You can use it as a coloring varnish system for coating surfaces (e.g. as automotive paint or effect foils), or for the production of color pigments Find use. The coloring structure of the polymer can Thereby through thermal cross-linking of the nematic or choleste phase can be permanently fixed. The production of color pigments can e.g. B. by peeling the oriented polymer film from the coated surface and milling to platelet-shaped against pigments. The application of the polymer as a coating system  can be used as a powder coating, in the melt or in solution (e.g. in water, N-methylpyrrolidone or dimethylformamide). In the simplest case, the system is oriented through Annealing the coated surface and can by the Einwir mechanical, electrical or magnetic forces be improved if necessary.

The polymers according to the invention can be used to adjust the viscosity verity and the course behavior with additional components to be mixed.

As such, they are particularly suitable for paint-like coatings Components polymeric binders and / or monomeric compounds, which is converted into a polymeric binder by polymerization can be. Such means are suitable for. B. in organi Solvent-soluble polyester, cellulose ester, polyure thane, silicones, polyether or polyester modified silicones. Cellulose esters such as cellulose acetate are particularly preferred tyrat used.

If desired, the paints according to the invention can also be stabilizers lisators against UV and weather influences can be added. Therefor are z. B. Derivatives of 2,4-dihydroxybenzophenone, Deri vate of 2-cyan-3,3-diphenyl acrylate, derivatives of 2,2 ', 4,4'-tetrahydroxybenzophenone, derivatives of orthohydroxyphenyl benztriazole, salicylic acid ester, orthohydroxyphenyl-S-triazine or sterically hindered amines. These substances can be used alone or preferably used in the form of mixtures.

Pigments, dyes and fillers can also be the inventive modern paint systems can be added.

The surface coating can also be done by means of a pressure ver driving.

All common printing processes (e.g. portrait, Gravure, flexo, offset, screen printing).

Methods suitable for coating and printing according to the invention of substrates are described in WO 96/02597, to which here with full reference.

The present invention further relates to the compounds of the formula

wherein
A ¹ to A ⁴ independently of one another represent hydrogen, alkyl, alkoxyalkyl, optionally alkyl-substituted cycloalcyl, halogen or nitro;
X represents S, O or NR ² , where R ^{2 represents} H, C ₁ -C ₄ alkyl or phenyl,
R ^{3 represents} hydrogen, C ₁ -C ₄ alkyl, aryl or aryl-C ₁ -C ₄ alkyl, or
Amides or halides thereof.

Another object of the present invention is Ver use of this compound as thermal or photochemical ver wettable end group in polymers.

The following examples illustrate the invention without, however, restricting it thereto:
The physical properties of the compounds described in the examples are given in Tables 1 to 7.

example 1

6-Hydroxy-2-naphthoic acid (0.1 mol.) Was dissolved in a solution of KOH (0.2 mol.) Dissolved in 50 ml of water. Propargyl chloride (0.2 mol.) was added and the reaction mixture was 20 hours which stirred in reflux. It was dissolved in water (100 ml) KOH (0.1 mol.) Added and heated for a further two hours. After After cooling, the reaction mixture was acidified with 4 N hydrochloric acid and the precipitated product is isolated by filtration. After The product was dried in vacuo from an ethanol / water mixture (Volume ratio 1: 4) recrystallized. This was 6-Propargyloxy-2-naphthoic acid with a yield of 98% nen. The melting point (Tm) of the product was 239 to 241 ° C.

Example 2

6-propargyloxy-2-naphthoic acid (0.25 mol.) Was suspended in a mixture of dry chloroform (150 ml) and distilled thionyl chloride (150 ml). The mixture was stirred under reflux under nitrogen for 2.5 to 3 hours until no more NH _{3 was} formed. Chloroform and thionyl chloride were partially distilled off under normal pressure and partially in vacuo. The residual product was dissolved in dry toluene and the solution evaporated in vacuo. Finally, the crude product was recrystallized from mixtures of chloroform and ligroin. 6-Propargyl oxy-2-naphthoic acid chloride was obtained in a yield of 77%. The melting point of the product was 93 to 95 ° C.

Example 3

Isosorbide (20 mmol.) And 4'-propargyloxy-4-biphenylbenzoic acid chloride (41 mmol.) Were dissolved in dry chloroform (100 ml) and placed in a cylindrical glass reactor equipped with a mechanical stirrer and gas inlet and outlet was provided. A solution of dry pyridine (41 mmol.) In chloroform (10 ml) was added dropwise with stirring. The reaction mixture was stirred under nitrogen at room temperature for 24 hours, diluted with chloroform (100 ml) and then washed three times with 1N HCl and three times with water. The chloroform solution was dried with Na ₂ SO ₄ and concentrated in vacuo. The product 3a

crystallized. Analogously, four further diesters (3b-e) by reacting the dihydroxy-substituted compounds b, c, d and e with 4'-propargyloxy-4-biphenylbenzoic acid chloride poses.  

Example 4 Analogously to Example 3, the diesters 4a-f

by reacting 6-propargyloxy-2-naphthoic acid chloride with Isosorbide or the dihydroxy-substituted compounds b-f posed.

Table 1 shows the physical properties (rotation value ([α] _D ), melting temperature (T _m ), clarification temperature (T _i ) and crosslinking temperature (T _x )) as well as the yield and the characterization of the melt.

Table 1

Example 5

Mixtures of diesters 3a and 3c, 3b and 3c, 4a and 4c and 4b and 4c were produced with the molar ratios given in Tables 2 to 5. These tables also show the clarification temperature (T _i ), the crosslinkability in the liquid-crystalline phase and the characterization of the melt of the respective mixture.

Mixture of 3a and 3c

Mixture of 3a and 3c

Mixture of 3b and 3c

Mixture of 3b and 3c

Mixture of 4a and 4c

Mixture of 4a and 4c

Mixture of 4b and 4c

Mixture of 4b and 4c

Example 6

A concentrated solution of terephthalic acid dichloride (A) (8 mmol.) in dry chloroform was added dropwise with stirring an ice-cold solution of phenylhydroquinone (W) (2 mmol.), Isosorbide (I) (1 mmol.) And 4-propargylthiophenol (Y) (2 mmol.) In given dry pyridine (20 ml). The reaction mixture was then stirred for 20 hours at 20 to 25 ° C and finally 2 hours refluxed. The reaction mixture was concentrated in vacuo and the reaction product precipitated in cold methanol. The received one Oligoester was isolated by filtration with cold methanol washed and dried at 65 ° C in a vacuum. Analogously to this a concentrated solution of biphenyl-4,4'-dicarboxylic acid dichlo rid (C) (6 mmol.) and 6-propargyloxy-2-naphthoic acid chloride (Z) (4 mmol.) In dry chloroform while stirring dropwise a solution of phenylhydroquinone (6 mmol.) and isosorbide (2 mmol.) In dry pyridine (20 mmol.) And as above described implemented. 15 other oligomes were made analogously Risks using varying molar amounts of the above Starting compounds as well as from naphthalene-2,6-dicarboxylic acid loride (B), tert-butyl hydroquinone (V) and propargyl alcohol (X) carried out. The molar amounts of the monomers used and the  Yields, the observed textures and the physical egg Properties of the polymers obtained are shown in Table 6 poses.  

Example 7

A solution of diphosgene (12.8 mmol.) In 20 ml dichloromethane was added dropwise to a solution of 4,4'-dihydroxybiphenyl (10th mmol.), methylhydroquinone (5 mmol.), isorbide (5 mmol.) and Pro Pargyl alcohol (10 mmol.) added in 30 ml of pyridine. The mixture was at 5 to 10 ° C for 30 minutes and at room temperature a further 4 Hours stirred. The mixture was then placed in methanol and filtered. The isolated polymer was dissolved in dichloromethane and precipitated again in methanol. Eventually the polycar bonat vacuum dried at 90 ° C. This reaction and 5 others too their analog are illustrated by the following reaction scheme light.  

The product of the reaction described above is in Formula I as Polycarbonate 10e shown. By changing molar use the polycarbonate 10f was synthesized. Use of a by an additional ester function of modified dihydroxybiphenyl led to the carbonates 10g and 10h. Use of 2,6-dihydroxy naphthalene instead of methylhydroquinone led to those in formula II shown polycarbonates 10i and 10j. Yield and the Physical properties of these polymers are shown in Table 7 refer to.

Example 8

4-propargyloxybenzoic acid chloride (10 mmol.) Was dissolved in 10 ml of Pyri din dissolved and to a cold solution of 4,4'-dihydroxybiphenyl (10 mmol.), Methylhydroquinone (5 mmol.) And isosorbide (5 mmol.) placed in 20 ml of dry pyridine. After 10 minutes, in 20 ml of diphosgene (12.8 mmol.) dissolved in dichloromethane is added dropwise given the above solution. The mixture was left at 5 for 30 minutes react to 10 ° C and for a further 4 hours at room temperature. The The mixture was then placed in methanol and filtered. That iso gated polymer was dissolved in dichloromethane and again in metha nol failed. Finally, the polycarbonate at 90 ° C in Vacuum dried. The following reaction scheme illustrates this implementation.  

The reaction described above resulted in the polycarbonate 10a Formula III. The polycarbonate 10b was changed accordingly derate molar amounts. Use of 6-Propargy Ioxy-2-naphthoic acid chloride led to polycarbonates 10c and 10d. Yields and physical properties of the polymers 10a to 10d are shown in Table 7.  

Claims (27)

1. Propargyl-terminated, nematic or cholesteric polyesters, polycarbonates or nematic or cholesteric mixtures containing them, with the exception of diesters of the formula
P - A ¹ - A - A ² - P,
wherein A is 1,4-phenylene, 4,4'-biphenyl, 2,6-naphthalinyl or -C ₆ H ₄ -CR = CR-C ₆ H ₄ -, where R is H or CH ₃ and A is one or can have several substituents which are selected from halogen, nitro, alkyl, alkoxy, fluoroalkyl, fluoroalkoxy or phenyl,
A ¹ and A ² for
stand and P stands for HC∼CCH ₂ O-. 2. polyesters, polycarbonates or nematic or cholesteric mixtures according to claim 1 with at least one propargyl end group of the formula R ³ C∼C-CH ₂ -, wherein R ^{3 is} hydrogen, C ₁ -C ₄ alkyl, aryl or Ar-C ₁ -C ₄ alkyl, which is directly or via a link to the polyester or polycarbonate bound. 3. polyesters, polycarbonates or nematic or cholesteric mixtures according to claim 2, wherein the propargyl end group is bonded directly to a hydroxy end group or via a link which is selected from
wherein R ^{4 is} H, C ₁ -C ₄ alkyl or phenyl and X is O, S or NR ² , where R ^{2 is} H, C ₁ -C ₄ alkyl or phenyl. 4. Polyester according to any one of the preceding claims, the

• a) at least one aromatic or araliphatic dicarboxylic acid unit and / or at least one aromatic or araliphatic hydroxycarboxylic acid unit and
• b) contain at least one diol unit.

5. Polyester according to claim 4, wherein the dicarboxylic acid unit is selected from dicarboxylic acid units of the formula
especially those of the formula
where each of the phenyl groups or the naphthyl group can have 1, 2 or 3 substituents which are selected independently of one another from C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen or phenyl, in the formulas above
W represents NR, S, O, (CH ₂ ) _p O (CH ₂ ) _g , (CH ₂ ) _m or a single bond,
R represents alkyl or hydrogen,
m is an integer from 1 to 15 and
p and q independently represent integers from 0 to 10. 6. Polyester according to claim 4 or 5, wherein the Hydroxycarbonsäu reeinheit is selected from
where each phenyl group or the naphthyl group can have 1, 2 or 3 substituents which are selected independently of one another from C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen or phenyl. 7. Polyester according to any one of claims 4 to 6, wherein the diol units are selected from diol units of the formula
especially those of the formula
being in the formulas above
L represents alkyl, alkoxy, halogen, COOR, OCOR, CONHR or NHCOR,
X represents S, O, N, CH ₂ or a single bond,
A is a single bond, (CH ₂ ) _n , O (CH ₂ ) _n , S (CH ₂ ) _n , NR (CH ₂ ) _n ,
or
means
R represents alkyl or hydrogen,
R ^{1 is} hydrogen, halogen, alkyl or phenyl and
n is an integer from 1 to 15. 8. Polyester according to one of claims 5 or 6, the at least one dicarboxylic acid unit of the formula
and at least one diol unit of the formula
included, where
R ^{1 represents} H, halogen, C ₁ -C ₄ alkyl, in particular CH ₃ or C (CH ₃ ) ₃ , or phenyl. 9. The polyester of claim 8, wherein the propargyl end group via
is bound. 10. Diester according to one of the preceding claims of the formula PYB-CO-OAO-CO-BYP, wherein P stands for a propargyl end group of the formula defined in claim 2, Y for O, S or NR ² (R ² = C ₁ -C ₄ -Alkyl), B stands for
stands, where
each phenyl group or the naphthyl group may have 1, 2 or 3 substituents which are independently selected from C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen or phenyl, and A (together with the neighboring oxygen atoms) stands for the diol units defined in claim 7. 11. Diester according to claim 10, wherein Y, A and P have the meanings given in claim 10 and B for
is, wherein each phenyl group or the naphthyl group may have 1, 2 or 3 substituents which are independently selected from C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen or phenyl. 12. Diester according to claim 10 or 11 of the formula
HC∼CCH ₂ OB-CO-OAO-CO-B-OCH ₂ -C∼CH, wherein

• a) B for
  and
  A for
  stands, or
• b) B for
  stands, and

A has the meanings mentioned under a). 13. Polycarbonates according to one of claims 1 to 3, the at least one diol unit as defined in claim 7, in particular a diol unit of the formula
contain. 14. Polycarbonates according to claim 13, which at least one mesogenic unit of the formula as diol units
and at least one chiral unit of the formula
and optionally a non-chiral unit of the formula
contain, wherein R ^{1 has} the meanings given in claim 7 and in particular represents H or CH ₃ . 15. Polycarbonates according to claim 13 or 14, with propargyl end groups of the formula HC∼CCH ₂ OR ⁵ -CO, wherein R ^{5 is}
stands. 16. Mixture according to one of claims 1 to 12, up to about 30 mol%, in particular about 5 to 20 mol% propargyl termi nated diesters of isosorbide and nematic or cholesteric contains diester. 17. Cross-linked polyester, polycarbonate or nematic or cho esteric mixtures containing these are available from After heating the polyesters, polycarbonates or the mixtures any of the preceding claims. 18. Cross-linked polyester, polycarbonate or nematic or cho esteric mixtures containing these are available from Heating at a temperature of about 120 to 340 ° C, esp especially around 200 to 315 ° C. 19. Crosslinked polyesters, polycarbonates or nematic or choesteric mixtures containing them according to claim 17, obtainable by heating in the presence of a catalyst, in particular (C ₅ H ₅ ) Co (CO) ₂ , CuCl, CuCl ₂ , (C ₅ H ₅ ) ₂ Ni, ((C ₆ H ₅ ) ₃ P) ₂ NiCl ₂ and RhCl ((C ₆ H ₅ ) ₃ P) ₃ . 20. Cross-linked polyester, polycarbonate or nematic or cho esteric mixtures containing them according to claim 18, obtainable by adding the catalysts in an amount from about 0.01 to 3% by weight of the reaction mixture, in particular whose uses about 0.1 to 1 wt .-% of the reaction mixture. 21. Use of the polyesters, polycarbonates or mixtures after one of claims 1 to 16 as an optical component or as a surface coating material. 22. Use of the polyesters, polycarbonates or mixtures according to one of claims 1 to 16 as a colorant, in particular as coloring component of paint systems for coating of surfaces or as part of printing inks. 23. Pigments containing polyesters, polycarbonates or mixtures or crosslinked polyesters, polycarbonates or mixtures one of claims 1 to 20. 24. coating compositions containing at least one polyester, a polycarbonate or a mixture according to one of claims 1 to 16, or at least one pigment according to claim 23. 25. Compounds of the formula
wherein
A ¹ to A ⁴ independently of one another represent hydrogen, alkyl, alkoxyalkyl, optionally substituted by alkyl cycloalkyl, halogen or nitro;
X represents S, O or NR ² , where R ^{2 represents} H, C ₁ -C ₄ alkyl or phenyl,
R ^{3 represents} hydrogen, C ₁ -C ₄ alkyl, aryl or aryl-C ₁ -C ₄ alkyl, or
Amides or halides thereof. 26. Compounds according to claim 25, wherein A ¹ to A ^{4 are} H, R ^{3 is} H, C ₁ -C ₄ alkyl, aryl or Ar-C ₁ -C ₄ alkyl and X has the meanings given in claim 25 owns. 27. Use of the compounds according to claim 25 or 26 as thermally or photochemically crosslinkable end group in polyme ren.