WO1988006179A1

WO1988006179A1 - Polymer materials

Info

Publication number: WO1988006179A1
Application number: PCT/EP1988/000105
Authority: WO
Inventors: Günter LATTERMANN
Original assignee: MERCK Patent Gesellschaft mit beschränkter Haftung
Priority date: 1987-02-17
Filing date: 1988-02-12
Publication date: 1988-08-25
Also published as: DE3704877A1; DE3890094D2; JPH01502432A

Abstract

Polymer materials containing side groups, which are bound through a spacer in 1,3,5- or 1,2,4,5-position substituted carbo- or heterocyclic 6-membered ring systems are suitable as organic substrates in electronics.

Description

Polymer materials

The invention relates to polymer materials containing side groups which are bonded via a spacer to carbo- or heterocyclic six-ring systems which are substituted in the 1,3,5- or 1,2,4,5-position.

A number of liquid-crystalline main chain polymers are already known. A. Ciferri in "Polymer Liquid Crystals", A. Ciferri, WR Kriegbaum and RB Meyer, ed., Academic Press, NY, NY, 1982, p. 62 describe a variety of such systems. Nematic phases of such polymer materials are often at temperatures above 100 °. In many cases, materials with rod-like (mesogenic) groups also show crystalline behavior, combined with the lack of mesomorphic properties. Polymerization of nematic or cholesteric monomers often gives higher-order highly viscous sectic polymers. Discotically liquid-crystalline polymers are often characterized by very complicated synthetic routes and high mesophase transitions. A common structural principle of all discogenes found until 1984 was that they consist of a rigid, flat, central part of the molecule (mostly aromatics, but also metal complexes), the "core", that of at least three, usually six , a maximum of nine flexible side chains is surrounded. Recently discotages with a non-rigid, alicyclic, saturated nucleus (B. Kohne and K. Praefcke, Angew. Chem. 9_6, 70 (1984), "pyramidal" mesogens with a three-dimensional nucleus (H. Zimmermann et al., Z Naturforsch. 40a, 149 (1985) and "tubular" mesogens with flexible crown ether cores (JM Lehn et al., J. Chem. Soc. Chem. Com un. 1985, 1794).

Known discotic liquid crystalline polymers are e.g. Polysiloxanes to which pentasubstituted triphenylene rings are bound as discogenic side groups via a flexible spacer (. Kreuder and H. Ringsdorf, Makromol. Chem., Rapid Commun. 4, 807 (1983)).

Polymers with discogenic groups in the main chain (W. Kreuder, H. Ringsdorf and P. Tschirner, Makromol. Chem., Rapid Commun. 6 ^ 376 (1985) and G. Wenz, ibid. 6_, 577 (1985)) contain bi unctional benzene or triphenylene derivatives as the core, each provided with four lateral alkoxy or alkanoyloxy chains.

The synthetic difficulties in building up such polymers with mesogenic groups based on conventional hexasubstituted central parts are obvious: monomers with a high degree of substitution are required in which one or two of the six side groups differ from the others in that they are capable of polymerization or polycondensation.

It was an object of the present invention to find polymer materials which do not have the disadvantages described or only have them to a lesser extent, and to find corresponding low-molecular compounds or monomers with a lower degree of substitution and a reduced tendency to crystallize. It has been found that polymer materials according to the invention have birefringence which can be varied within wide limits and positive and negative diamagnetic anisotropy. In addition, they can easily be processed into bodies of any shape with the respective properties and have high chemical stability.

The polymer materials according to the invention result in materials with diverse properties of high mechanical stability which can be adapted to the requirements.

The invention relates to polymer materials containing side groups which are bonded via a spacer to carbocyclic or heterocyclic six-ring systems which are substituted in the 1,3,5- or 1,2,4,5-position, but in particular polymer materials whose six-ring systems selected from formulas (1) to (3),

cerium

(1) (2) (3)

wherein M is a carbocyclic side group, X is each independently N or CH and Y O or NH, and polymer materials containing units of the formula

-Q-CO-W-CO-

wherein Q is a group selected from the formulas (1) to (3) and W is the core part of a polymerizable dicarbon means acid and polymer materials whose carbocyclic side group M corresponds to the formula (5),

wherein R ° H, alkyl, alkoxy, alkoxycarbonyl, alkoxycarbonylo alkoxybenzyloxy or alkanoyloxy, each having 1 to 20 carbon atoms, and

^R each independently of one another H, alkyl,

Alkanoyloxy, alkoxycarbonyl, alkoxycarbonyloxy, alkoxybenzyloxy or alkoxy each having 1 to 20 carbon atoms.

The invention further relates to a process for the preparation of polymer materials according to claim 3, characterized in that corresponding dihydroxy compounds of the formula

H-Q-H

with corresponding dicarboxylic acids of the formula

HOOC-W-COOH

or their reactive derivatives, a polycondensation, and carbocyclic compounds of formula I

(I)

in which A denotes a radical selected from the formulas (la), (lb) and (lc),

(la) (lb) (lc)

where X is in each case independently of one another N or CH,

Z -O-CO-, -0-CH ₂ -, -CO-O-, -CH „0- or im

Trap A = (lb) also -NH-CO- or - H-CH ₂ -,

OH, alkoxy, alkanoyloxy, COOH, alkanoyl, alkoxy carbonyl, p-alkoxybenzoyloxy, p-alkylbenzoyloxy or a radical of the formula

P 2 or, in the case A = (lc), 3,

R ° alkoxy, alkanoyloxy, alkoxycarbonyl, alkoxycarbonyl¬ oxy, alkoxybenzyloxy or alkyl, and

R in each case independently of one another denotes H, alkoxy, alkanoyloxy, alkoxycarbonyl, alkoxycarbonyloxy, alkoxybenzyloxy or alkyl,

and the use of the corresponding dihydroxy compounds as intermediates for the production of polymer materials. The invention further relates to the use of the polymer materials according to the invention as organic substrates in electronics for fiber and film technology, for amplitude and / or frequency modulation of laser beams and for optical data storage.

In the six-ring systems of the formulas (1) to (3), the spacer preferably denotes a radical

- (W -) -w - or a single bond.

is alkylene with 1 to 15 carbon atoms. W and w each independently of one another are preferably -O-, -S-, -O-CO-, -CO-O- or -CO-NH-. q is 0 or 1.

The choice of the carbocyclic side group M is not critical per se. For example, the radical -Spac.er-M can represent an alkyl, alkoxy or alkanoyloxy group or a conventional "rod-like" or "disk-like" radical known from liquid crystal chemistry (D. Demus et al. Liquid Crystals in Tables II, VEB Deutscher Verlag für Grundstoffindustrie, Leipzig 1984). Preferred "rod-like" radicals are those of the formula II

2 1 1 2 2 R - (A -Z) -A -Z - II

2 wherein R is H, alkyl, alkoxy, alkanoyloxy, alkoxycarbonyl, nitrile or halogen

A 1, A2 in each case independently of one another like 1,4-cyclohexylene group, in which one or more non-bicarbonate groups CCHH _-- <groups can also be replaced by O and / or S, or an 1,4-phenylene group which is unsubstituted or substituted one or more times by halogen and / or nitrile, in which one or more CH groups can also be replaced by N.

Z 1, Z2 each independently of one another -CH ₂ -CH ₂ ~, -CO-O-, -O-CO-, -C≡C-, -OCH -, -CH ^ O- or a single bond, and

n means 1, 2 or 3.

However, radicals M corresponding to formula (5) are particularly preferred

Dicarboxylic acids of the formula HOOC-W-COOH capable of polycondensation are, for example, terephthalic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, thapsic acid, phellogenic acid or their esters with lower alcohols . W preferably denotes unsubstituted C ₂ -C ₅ alkylene, in particular C 1 -C 4 alkylene, in which also preferably one to five, in particular one to three, CH ₂ groups by 1,4-cyclohexylene, 1, 4-phenylene, 1,4-benzoylene and / or 4-oxybenzoylene, in particular 1,4-benzoylene and / or 4-0xybenzoylene, where 2 O atoms or -O- and -COO- are not directly substituted are linked to one another and the benzene rings disubstituted in the 1,4-position are optionally also in the 2-, 3-, 5- and / or 6-position one or more times

2nd . . . can be substituted by R (alkyl, alkoxy or alkanoyloxy, each having up to 20 carbon atoms).

Accordingly, W preferably means: ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, penta- decylene; 1,4-phenylene, 4,4 '- [1,1'] - biphenyldiyl, 4,4 "-p-terphenyldiyl,

- (O> -0- (CH) - © - (n = 1 to 10), - (0> -,

Formula I includes both racemates of these compounds and the optical antipodes and mixtures thereof.

Among the compounds of the formula I, preference is given to those in which at least one of the radicals contained therein has one of the preferred meanings indicated.

Among the compounds of the formula I, those of the sub-formulas Ia-Ie are particularly preferred:

The polycondensation is preferably carried out by heating the components, optionally with the addition of an inert one

Solvent and / or a catalyzing compound, carried out at temperatures of about 50 to 350 °, in particular at about 150 to 300 °. In addition, the polycondensation can also be carried out as melt or interfacial polycondensation. Suitable solvents are, for example, hydrocarbons such as toluene or xylene, halogenated hydrocarbons such as chlorobenzene or dichlorobenzene or ethers such as diphenyl ether. ⁿ

Suitable catalysts can be found, for example, in the group of metal compounds; aluminum (III) or titanium (IV) compounds, such as titanium tetrabutanolate, are particularly suitable. Copolymer compositions according to the invention having liquid-crystalline phases are obtained by copolymerizing polymerizable compounds of the formula HQH, or their polymerizable derivatives with monomers which do not carry any mesogenic residues, which carry other mesogenic residues (for example rod-like), which have chiral residues (for example DE OS 28 31 909) or carry the dye residues (DE-OS 32 11 400).

The copolymerization with monomers that do not carry a mesogenic residue generally leads to a lowering of the glass transition temperature and the clearing point. By suitable selection of the components, it is often possible, for example, to bring the mesophase range into the temperature range suitable for the respective application.

In principle, all such compounds with asymmetric carbon atoms can be used as monomers with a chiral radical. However, compounds are preferably used in which the unit Q or the group M in the radicals R ° or R has one or more asymmetrical C atoms. Chiral polymer materials can also be obtained by reacting suitable hydroxyl-containing polymers with an optically active acid R * -CO-OH or one of their reactive derivatives, where R * means a radical containing an asymmetric C atom.

Finally, there are numerous other possible variations due to the fact that the compounds according to the invention have typical polymer properties, such as the ability to form layers, films and fibers, easy deformability, etc. These properties can be achieved in a manner known per se by copolymerization or mixing with further components, by varying the molecular weights, by adding a wide variety of them - left

inorganic or organic additives and metals and many other treatments known to those skilled in the art of polymers.

The carbocyclic compounds of the formula I according to the invention generate lyotropic phases and are therefore suitable for producing anisotropic polymer materials by a process described in DE 36 13 993. The compounds of formula I are mixed with polymerizable compounds by dissolving or stirring in, and the mixtures are polymerized by heating, irradiation or by adding an initiator.

The anisotropic polymer materials obtained in this way are distinguished by advantageous values of the optical, magnetic and / or electrical anisotropy and by advantageous mechanical and / or thermal properties.

The polymer compositions according to the invention can be used as a starting material for the production of organic glasses with anisotropic properties which can be modified over a wide range.

Such applications arise, for example, in the sector of light and solar collectors or in organic phototropic glasses. An important field of application also opens up in the field of optical memories.

Further application possibilities open up in the field of magnetic memories. In particular, the compositions according to the invention are also suitable as a matrix for the substances with nonlinear optical properties for the production of “nonlinear” optical components. The following examples serve to explain the invention:

All temperatures are in degrees Celsius. The symbols continue to mean as follows:

K: solid crystalline state, M: mesogenic phase, D: discotic phase, N: nematic phase, I: isotropic phase. (Indices indicate the appearance of different phases of the same type).

The numbers between two symbols indicate the phase transition temperature when warming up (in brackets when cooling down).

example 1

A mixture of 252 mg of 1,3,5-trihydroxybenzene (phloroglycine), 4.87 g of 3,4,5-tridecyloxybenzoic acid chloride, 4 g of triethylamine and 130 ml of absolute tetrahydrofuran is boiled under reflux for 48 hours with stirring. The triethylamine hydrochloride is filtered off from the cooled solution, the solvent is removed and the residue is recrystallized from acetone. This gives 1,3,5-tris (3 ^l , 4 ', 5' -tris- (decyloxybenzoyloxy) -benzene, melting process 35-42 °, D 29.5 ° I (monotropic mesophase is many hours at room temperature) stable).

The following are produced analogously:

l, 3,5-tris- (3 ', 4,5' -tris- (tetradecyloxy) -benzoyloxy) -benzo l, 3,5-tris- (3 ', 4,5' -tris- (dodecyloxy) - benzoyloxy) benzene l, 3,5-tris- (3 ^r , 4, 5 '-tris- (undecyloxy) -benzoyloxy) -benzene l, 3,5-tris- (3', 4, 5 '-tris- (nonyloxy) benzoyloxy) benzene 1,3,5-tris- (3 ', 4,5' - tris- (octyloxy) benzoyloxy) benzene 1,3,5-tris- (3 ', 4,5) '-tris- (heptyloxy) benzoyloxy) benzene 1,3,5-tris- (3 ^!, 4,5' - ris- (hexyloxy) benzoyloxy) benzene 1,3,5-tris- (3 ', 4,5' -tris- (pentyloxy) -benzoyloxy) -benzene 1,3,5-tris- (3 ', 4,5' -tris- (dodecanoyloxy) - benzoyloxy) -benzo 1,3, 5-tris- (3 ', 4, 5' -tris- (undecanoyloxy) -benzoyloxy) -benzo l, 3,5-tris- (3 ', 4, 5' -tris- (decanoyloxy) -benzoyloxy) -benzene l, 3,5-tris- (3 ', 4, 5' -tris- (nonanoyloxy) -benzoyloxy) -benzene l, 3,5-tris- (3 ', 4, 5 'tris (octanoyloxy) benzoyloxy) benzene l, 3,5 tris (3', 4,5 'tris (heptanoyloxy) benzoyloxy) benzene l, 3,5 tris (3' , 4,5 'tris (hexanoyloxy) benzoyloxy) benzene 1,3,5-tris- (3', 4,5 'tris (pentanoyloxy) benzoyloxy) benzene 1,3,5-tris - (3 ", 4,5 '-tris- (butyryloxy) benzoyloxy) benzene

Example 2

A mixture of 264 mg of ice, cis-1,3,5-trihydroxycyclohexane (cis-phloroglucite), 4.87 g of 3,4, 5-tridecyloxybenzoic acid chloride, 4 g of triethylamine and 130 ml of absolute tetrahydrofuran is taken for 48 hours Stir cooked at reflux. After the solution has cooled and triethylamine hydrochloride is filtered off, the solvent is removed. The residue is recrystallized 4 times from acetone from 300 ml of ethanol. This gives - cis, cis-l, 3,5-tris- [3 ^■ , 4 ', 5' -tris-decyloxybenzoyloxy] - cyclohexane, K 31.3 ° D 61.5 ° I (mesophase is up to + 5 ° subcoolable and stable at room temperature for several weeks)

The following are produced analogously:

cis, cis-l, 3,5-tris- [3 ', 4', 5 '-tris- (tetradecyloxy) -benzoyloxy] -cyclohexane ice, cis-1, 3, 5-tris- [3', 4 ', 5' -tris- (dodecyloxy) -benzoyloxy] -cyclohexane cis, cis-l, 3,5-tris- [3 ', 4', 5 '-tris- (undecyloxy) -ben¬ zoyloxy] -cyclohexane cis, cis-l, 3,5-tris- [3 ', 4', 5 '-tris- (nonyloxy) -ben¬ zoyloxy] -cyclohexane cis, cis-l, 3,5-tris- [3, 5'-tris- (oetyloxy) -benzoyloxy] -cyclohexane-ice, cis-1,3,5-tris- [3, 5 '-tris - (heptyloxy) -benzoyloxy] -cyclohexane ice, cis-1,3, 5-tris- [3 5'-tris- (hexyloxy) -ben-zoyloxy] -cyclohexane ice, cis-1,3, 5- tris [3, 5'-tris (pentyloxy) benzoyloxy] cyclohexane ice, cis-1,3,5-tris [3,5 'tris (dodecanoyloxy) benzoyloxy] cyclohexane ice, cis-1,3,5-tris- [3, 5'-tris- (undecanoylox) -benzoyloxy] -cyclohexane ice, cis-1,3,5-tris- [3, 5'-tris- (decanoyloxy) -benzoyloxy] -cyclohexane ice, cis-1,3,5-tris- [3,5 '-tris- (nonanoyloxy) -ben- zoyloxy] -cyclohexane ice, cis-1,3,5- tris [3, 5'-tris (octanoyloxy) benzoyloxy] cyclohexane ice, cis-1,3, 5-tris- [3,5 'tris (heptanoyloxy) benzoyloxy] cyclohexane ice, cis-1,3,5-tris- [3, 5 '-tris- (hexanoyloxy) -benzoyloxy] -cyclohexane ice, cis-1,3,5-tris- [3, 5' -tris- (pentanoyloxy) -benzoyloxy] cyclohexane cis, cis-l, 3,5-tris- [3,5 '-tris- (butyryloxy) -benzoyloxy] cyclohexane

cis, cis-1,3,5-bis- [3 ', 5' -tris- (tetradecyloxy) -ben¬ zoyloxy] -cyclohexane ice, cis-1,3,5-bis- [3 *, 5 '- tris (dodecyloxy) benzoyloxy] cyclohexane ice, cis 1,3,5-bis [3 ', 5' tris (undecyloxy) benzoyloxy] cyclohexane cis, cis-1,3 , 5-bis- [3 ', 5' -tris- (nonyloxy) -ben¬ zoyloxy] cyclohexane eis, cis-1, 3, 5-bis- [3, 5'-tris-octylox) -benzoyloxy] -cyclohexane cis, cis-l, 3,5-bis- [3, 5'-tris-heptylox ) -ben- zoyloxy] -cyclohexane ice, cis-1,3, 5-bis- [3,5 '-tris-hexylox) -ben- zoyloxy] -cyclohexane ice, cis-1,3, 5-bis- [ 3, 5'-tris-pentylox) -benzoyloxy] -cyclohexane cis, cis-l, 3,5-bis- [3, 5'-tris-dodecanoylox) -ben-zoyloxy] -cyclohexane ice, cis-1 , 3, 5-bis- [3, 5'-tris-undecanoyloxy) -benzoyloxy] -cyclohexane ice, cis-1,3, 5-bis- [3, 5'-tris-decanoyloxy) -benzoyloxy ] -cyclohexane ice, cis-1,3, 5-bis- [3, 5'-tris-nonanoyloxy) -benzoyloxy] -cyclohexane ice, cis-1,3,5-bis- [3, 5'- tris-octanoylox) -benzoyloxy] -cyclohexane ice, cis-1,3,5-bis- [3,5'-tris-heptanoylox) -ben-zoyloxy] -cyclohexane ice, cis-1,3,5- bis- [3, 5'-tris-hexanoyloxy) -benzoyloxy] -cyclohexane ice, cis-1,3, 5-bis- [3,5, -tris-pentanoylox) -ben-zoyloxy] -cyclohexane ice, cis-1,3,5-bis- [3,5'-tris-butyryloxy) benzoyloxy] cyclohexane

Example 3

a) Preparation of 3-phenyl-2,4-dioxa-3-borabicyclo- [3.3.1] nonan-7-yl 3 ', 4', 5 '-tris- (decyloxy) -benzoic acid ester

To a solution of 1.35 g of 3-phenyl-2,4-dioxa-3-borabicyclo [3.3.l] nonan-7-ol (shown according to PN Strong, JFN Keana, J. Org. Chem. 40, 956 (1975) made of ice, ice 1,3,5-cyclohexanetriol) in 15 ml of pyridine, 3.77 g of 3,4,5-trideeyloxybenzoyl chloride dissolved in 10 ml of pyridine are added. After stirring for 2 hours at room temperature and removing the solvent in vacuo, the precipitate is washed with hot toluene. After recrystallization twice, the ester is obtained as a solid, K 28 ° I.

The following are produced analogously:

3-phenyl-2,4-dioxa-3-borabicyclo [3.3.1] onan-7-yl 3 ', 4', 5 '-tris- (tetradecyloxy) -benzoic acid ester 3-phenyl-2,4-dioxa-3 -borabicyclo [3.3.l] nonan-7-yl 3 ', 4', 5 '-tris- (dodecyloxy) -benzoic acid ester 3-phenyl-2,4-dioxa-3-borabicyclo [3.3.1] nonan-7- yl 3 ', 4', 5 '-tris- (undecyloxy) -benzoic acid ester 3-phenyl-2,4-dioxa-3-borabicyclo [3.3.1] nonan-7-yl 3', 4 ', 5' -tris - (nonyloxy) benzoic acid ester

3-phenyl-2,4-dioxa-3-borabicyclo [3.3.1] nonan-7-yl 3 ', 4', 5'-tris- (oetyloxy) benzoic acid ester 3-phenyl-2,4-dioxa-3 -borabicyclo [3.3.1] nonan-7-yl 3 ', 4', 5 '-tris- (heptyloxy) -benzoic acid ester 3-phenyl-2,4-dioxa-3-borabicyclo [3.3.1] nonan-7- yl 3 ', 4', 5 '-tris- (hexyloxy) -benzoic acid ester 3-phenyl-2,4-dioxa-3-borabicyclo [3.3.1] nonan-7-yl 3', 4 ', 5' -tris - (Pentyloxy) benzoic acid ester 3-phenyl-2,4-dioxa-3-borabicyclo [3.3.1] nonan-7-yl 3 ', 4', 5 ^r -tris- (dodecanoyloxy) benzoic acid ester

3-phenyl-2,4-dioxa-3-borabicyclo [3.3.1] nonan-7-yl 3 ', 4', 5 '-tris- (undecanoyloxy) -benzoic acid ester 3-phenyl-2,4-dioxa-3 -borabicyclo [3.3.1] nonan-7-yl 3 ', 4', 5 '-tris- (decanoyloxy) -benzoic acid ester 3-phenyl-2,4-dioxa-3-borabicyclo [3.3.1] nonan-7- yl 3 ', 4', 5 '-tris- (nonanoyloxy) -benzoic acid ester 3-phenyl-2,4-dioxa-3-borabicyclo [3.3.1] nonan-7-yl 3', 4 ', 5' -tris - (oetanoyloxy) benzoic acid ester 3-phenyl-2,4-dioxa-3-borabicyclo [3.3.1] nonan-7-yl 3 ', 4', 5'-tris (heptanoyloxy) benzoic acid ester 3-phenyl-2,4-dioxa-3 -borabicyclo [3.3.1] nonan-7-yl 3 ',', 5'-tris- (hexanoyloxy) -benzoic acid ester 3-phenyl-2,4-dioxa-3-borabicyclo [3.3.l] nonan-7-yl 3 ',', 5'-tris- (pentanoyloxy) benzoic acid ester 3-phenyl-2,4-dioxa-3-borabicyclo [3.3.1] nonan-7-yl 3 ', 4', 5'-tris- ( butyryloxy) benzoic acid ester

3-phenyl-2,4-dioxa-3-borabicyclo [3.3.1] nonan-7-yl p-tetradecyloxybenzoic acid ester

3-phenyl-2,4-dioxa-3-borabicyclo [3.3.1] nonan-7-yl p-dodecyloxybenzoic acid ester, K 58 ° I

3-phenyl-2,4-dioxa-3-borabicyclo [3.3.1] nonan-7-yl p-undecyloxybenzoic acid ester 3-phenyl-2,4-dioxa-3-borabicyclo [3.3.l] nonan-7-yl p -nonyloxybenzoic acid ester

3-phenyl-2,4-dioxa-3-borabicyclo [3.3.1] nonan-7-yl p-octyloxybenzoic acid ester

3-phenyl-2,4-dioxa-3-borabicyclo [3.3.1] nonan-7-yl p-heptyloxybenzoic acid ester

3-phenyl-2,4-dioxa-3-borabicyclo [3.3.1] nonan-7-yl p-hexyloxybenzoic acid ester

3-phenyl-2,4-dioxa-3-borabicyclo [3.3.1] nonan-7-yl p-pentyloxybenzoic acid ester 3-phenyl-2,4-dioxa-3-borabicyclo [3.3.l] nonan-7-yl p -dedecanoyloxybenzoic acid ester

3-phenyl-2,4-dioxa-3-borabicyclo [3.3.1] nonan-7-yl p-undecanoyloxybenzoic acid ester

3-phenyl-2,4-dioxa-3-borabicyclo [3.3.1] nonan-7-yl p-decanoyloxybenzoic acid ester

3-phenyl-2,4-dioxa-3-borabicyclo [3.3.l] nonan-7-yl p-nonanoyloxybenzoic acid ester

3-phenyl-2, -dioxa-3-borabicyclo [3.3.1] nonan-7-yl p-octanoyloxybenzoic acid ester 3-phenyl-2,4-dioxa-3-borabicyclo [3.3.1] onan-7-yl p-heptanoyloxybenzoic acid ester

3-phenyl-2,4-dioxa-3-borabicyclo [3.3.l] nonan-7-yl p-hexanoyloxybenzoic acid ester 3-phenyl-2,4-dioxa-3-borabicyclo [3.3.l] nonan-7-yl p -pentanoyloxybenzoic acid ester

3-phenyl-2,4-dioxa-3-borabicyclo [3.3.l] nonan-7-yl p-butyryloxybenzoic acid ester

b) Preparation of cis, cis-l- (3,4,5-tris- (decyloxy) - benzoyloxy) -3, 5-cyclohexanediol

Bicyelischen the compound prepared in accordance with Example 3a herge¬ g is 1 ml propane _r 3-diol in 5 ml of acetone to a solution of 1.26. After stirring for 3 hours at room temperature and removing the volatile constituents in vacuo, the residue is taken up in 5 ml of ethyl acetate and washed with water. After drying the organic phase, removing the solvent and U - crystallization from toluene, the diol is obtained as a solid with K -5 ° (-15.5 °) M 96.6 ° (94.5 °) I.

The following are produced analogously:

ice, cis-1- (3,4,5-tris (tetradecyloxy) benzoyloxy) -3,5-cyclohexanediol ice, cis-1- (3,4,5-tris (dodecyloxy) benzoylox) -3 , 5-cyclohexanediol ^π ice, ice-1- (3, 4,5-tris (undecyloxy) benzoyloxy) -3,5-cyclohexanediol ice, cis-1- (3,4, 5-tris (nonyloxy) -benzoyloxy) -3,5- cyclohexanediol ice, cis-1- (3,4,5-tris (oetyloxy) -benzoyloxy) -3,5-cyclohexanediol ice, cis-1- (3,4,5-tris - (heptyloxy) benzoyloxy) -3, 5-cyclohexanediol cis, cis-1- (3,4,5-tris (hexyloxy) benzoyloxy) -3,5-cyclohexanediol ice, cis-1- (3,4,5-tris (pentyloxy) benzoyloxy) -3 , 5-cyclohexanediol ice, cis-1- (3,4, 5-tris (butyloxy) benzoyloxy) -3, 5-cyclohexanediol ice, cis-1- (3,4, 5-tris (dodecanoyloxy) - benzoyloxy) -3, 5-cyclohexanediol cis, cis-l- (3,4, 5-tris (undecanoyloxy) -benzoyloxy) -3, 5-cyclohexanediol ice, cis-1- (3,4, 5-tris (decanoyloxy) benzoyloxy) -3,5-cyclohexanediol cis, cis-l- (3,4,5-tris (nonanoyloxy) -benzoyloxy) -3,5-cyclohexanediol ice, cis-1- (3, 4, 5-tris (octanoyloxy) benzoyloxy) -3,5-cyclohexanediol ice, cis-1- (3,4,5-tris (heptanoyloxy) benzoyloxy) -3,5-cyclohexanediol ice, cis-1- ( 3,4,5-tris (hexanoyloxy) benzoyloxy) -3,5-cyclohexanediol ice, cis-1- (3,4,5-tris (pentanoylox) benzoyloxy) -3,5-cyclohexanediol ice, cis -1- (3,4,5-tris- (butyryloxy) benzoyloxy) -3,5-cyclohexanediol

ice, cis-l-tetradecyloxybenzoyloxy-3, 5-cyclohexanediol ice, cis-l-dodecyloxybenzoyloxy-3, 5-cyclohexanediol ice, cis-l-undecyloxybenzoyloxy-3, 5-cyclohexanediol ice, cis-l-decyloxy-5-benzoyloxy -cyclohexanediol, K 84.4 ° (75.5 °) M ₁ 99.8 ° (92.3 °) 102 ° (100.5 °) I ice, cis-l-nonyloxybenzoyloxy-3, 5-cyclohexanediol ice, cis-l-octyloxybenzoyloxy-3, 5-cyclohexanediol ice, cis-l-heptyloxybenzoyloxy-3, 5-cyclohexanediol ice, cis-l-hexyloxybenzoyloxy-3, 5-cyclohexanediol ice, cis-l-pentyloxybenzoyloxy-3iol, 5-cyclohexane ice, cis-l-butyloxybenzoyloxy-3,5-cyclohexanediol ice, cis-l-dodecanoyloxybenzoyloxy-3, 5-cyclohexanediol ice, cis-l-undecanoyloxybenzoyloxy-3,5-cyclohexanediol ice, cis-l-decanoyloxybenzoyloxy-3,5-cyclohexanediol ice, cis-l-nonanoyloxybenzoyloxy -cyclohexanediol ice, cis-l-octanoyloxybenzoyloxy-3,5-cyclohexanediol ice, cis-l-heptanoyloxybenzoyloxy-3,5-cyclohexanediol ice, cis-l-hexanoyloxybenzoyloxy-3,5-cyclohexanediol ice, cis-l-pentanoyloxybenzoyl , 5-cyclohexanediol ice, cis-l-butyriloxybenzoyloxy-3,5-cyclohexanediol

c) Preparation of ice, cis-1- (3 ', 4', 5'-tris (decyloxy) benzoyloxy) -3,5-bis (undecanoyloxy) cyclohexane

1 g of the diol from Example 3b is esterified with 0.75 g of undecanoyl chloride analogously to Example 3a. The triacyloxy compound shows the following phase behavior:

K ₂ : 16.8 °, K ₃ : 20.8 ° I K- _{j ^} : 40.7 ° II -42.6 °, M -32 °, I -10.6 ° K _£

The following are produced analogously:

ice, cis-1- (3 ', 4', 5 '-Tris- (tetradecylox) benzoyloxy) - 3,5-bis (undecanoyloxy) cyclohexane ice, cis-1- (3 ^r , 4', 5 '-Tris- (dodecyloxy) benzoyloxy) -

3,5-bis- (undecanoyloxy) -cyclohexane ice, cis-l- (3 ', 4', 5 '-Tris- (undecyloxy) -benzoyloxy) -

3,5-bis- (undecanoylox) -cyclohexane ice, cis-1- (3 ', 4', 5 '-Tris- (nonyloxy) -benzoyloxy) -

3, 5-bis (undecanoyloxy) cyclohexane ice, cis-1- (3 ', 4', 5 '-Tris- (oetyloxy) benzoyloxy) -

3,5-bis (undecanoyloxy) cyclohexane cis, cis-1- (3 ', 4', 5 '-Tris- (heptyloxy) benzoyloxy) -3,5-bis (undecanoyloxy) cyclohexane ice, cis-1- (3 ', 4', 5'-tris- (hexyloxy) benzoylox) -

3, 5-bis (undecanoyloxy) cyclohexane ice, cis-1- (3 ', 4', 5 'tris (pentylox) benzoyloxy) -

3, 5-bis (undecanoyloxy) cyclohexane ice, cis-1- (3 ', 4', 5 'tris (butyloxy) benzoyloxy) -

3, 5-bis (undecanoyloxy) cyclohexane ice, cis-1- (3 ', 4', 5 'tris (dodecanoyloxy) benzoyloxy) -

3, 5-bis (undecanoyloxy) cyclohexane ice, cis-1- (3 ', 4', 5 'tris (undecanoyloxy) benzoylox) -3,5-bis (undecanoyloxy) cyclohexane ice, cis -1- (3 ', 4', 5 '-Tris- (decanoyloxy) benzoylox) -

3, 5-bis- (undecanoyloxy) -cyclohexane ice, cis-l- (3 ', 4', 5 '-Tris- (nonanoyloxy) -benzoyloxy) -

3, 5-bis- (undecanoyloxy) -cyclohexane ice, cis-l- (3 ', 4', 5 '-Tris- (oetanoyloxy) -benzoyloxy) -

3, 5-bis (undecanoylox) cyclohexane ice, cis-1- (3 ', 4', 5 'tris (heptanoyloxy) benzoylox) -

3, 5-bis (undecanoyloxy) cyclohexane ice, cis-1- (3 ', 4', 5 'tris (hexanoyloxy) benzoyl "oxy) -3,5-bis (undecanoyloxy) cyclohexane ice , cis-1- (3 ', 4', 5 '-Tris- (pentanoyloxy) benzoyloxy) -

3, 5-bis (undecanoyloxy) cyclohexane ice, cis-1- (3 ', 4', 5 'tris (butyryloxy) benzoyloxy) -

3,5-bis (undecanoyloxy) cyclohexane

eis, cis-1- (3 ', 4', 5 '-Tris- (deeyloxy) -benzoyloxy) -3, 5-bis- (p-decyloxy-benzoyloxy) -cyclohexane, K. ^ 87.5 ° (83 , 2 °) K ₂ 95.2 ° (93.9 °) ML 116 ° M ₂ 118 ° N 140 ° (138 °) I ice, cis-1- (3 ', 4', 5 '-Tris- ( tetradecyloxy) -benzoyloxy) - 3,5-bis- (p-decyloxy-benzoyloxy) -cyclohexane ice, cis-1- (3 ', 4', 5 '-Tris- (dodecyloxy) -benzoylox) - 3, 5- bis- (p-decyloxy-benzoyloxy) cyclohexane ice, cis-1- (3 ', 4', 5 '-Tris- (undecyloxy) -benzoyloxy) - 3, 5-bis- (p-decyloxy-benzoyloxy) - cyclohexane ice, cis-1- (3 ', 4', 5 '-Tris- (nonyloxy) -benzoyloxy) - 3, 5-bis- (p-decyloxy-benzoyloxy) -cyclohexane ice, cis-1- (3 ', 4', 5'-tris- (oetyloxy) -benzoyloxy) - 3,5-bis- (p-decyloxy-benzoyloxy) -cyclohexane ice, cis-1- (3 ', 4 ', 5'-tris (heptyloxy) benzoyloxy) - 3,5-bis (p-decyloxy-benzoyloxy) cyclohexane ice, cis-1- (3', 4 ', 5'-tris (hexyloxy ) -benzoyloxy) - 3,5-bis- (p-decyloxy-benzoyloxy) -cyclohexane ice, cis-1- (3 ', 4', 5'-tris (pentyloxy) -benzoyloxy) - 3,5-bis - (p-decyloxy-benzoyloxy) cyclohexane ice, cis-1- (3 ', 4', 5'-tris (butyloxy) benzoylox) - 3,5-bis- (p-decyloxy-benzoyloxy) cyclohexane ice, cis-1- (3 ', 4', 5'-tris- (dodecanoyloxy) benzoyloxy) -3,5-bis (p-decyloxy-benzoyloxy) cyclohexane ice, cis-1- (3 ', 4 ', 5'-tris- (undecanoyloxy) benzoyloxy) - 3,5-bis- (p-decyloxy-benzoyloxy) cyclohexane cis, cis-l- (3', 4 ', 5'-tris- (decanoyloxy ) -benzoyloxy) - 3,5-bis- (p-decyloxy-benzoyloxy) -cyclohexane ice, cis-1- (3 ', 4', 5'-tris- (nonanoyloxy) -benzoyloxy) - 3,5-bis - (p-decyloxy-benzoyloxy) cyclohexane ice, cis-1- (3 ', 4', 5'-tris- (octanoyloxy) benzoyloxy) - 3,5-bis (p-decyloxy-benzoyloxy) cyclohexane ice, cis-1- (3 ', 4', 5'-tris (hept anoyloxy) -benzoyloxy) -. 3,5-bis (p-decyloxy-benzoyloxy) cyclohexane. ice, cis-1- (3 ', 4', 5'-tris- (hexanoyloxy) -benzoyloxy) - 3,5-bis- (p-decyloxy-benzoyloxy) -cyclohexane ice, cis-1- (3 ', 4 ', 5'-tris- (pentanoyloxy) benzoyloxy) - 3,5-bis- (p-decyloxy-benzoyloxy) cyclohexane ice, cis-1- (3', 4 ', 5'-tris- (butyryloxy ) -benzoyloxy) - 3,5-bis- (p-decyloxy-benzoyloxy) cyclohexane Example 4

a) Preparation of 2, 5-di [3 ', 4', 5 '-trideeyloxybenzoyl-oxy] -benzoquinone-1,4

A mixture of 700 mg of 2,5-dihydroxybenzoquinone, 8 g of 3,4,5-tridecyloxybenzoic acid chloride, 1.33 g of triethylamine and 50 ml of absolute tetrahydrofuran is refluxed for 48 hours with stirring. After cooling the dark brown reaction solution and filtering off the triethylamine hydrochloride, the red-brown, oily residue is dissolved in hot pentane. A greenish precipitate precipitates out of this solution at the freezer temperature. The recrystallization is repeated 2 more times.

b) Reduction of 2,5-di [3 ', 4', 5 '-tridecyloxybenzoyl-oxyl] -benzoquinone

2 g of the quinone compound are dissolved in THF and 10 min. shaken with a saturated aqueous sodium dithionite solution. The solvents are removed and the residue is extracted with warm acetone. The product is recrystallized twice from acetone. 2,5-Di- [3 ', 4', 5 '-tris- (deeyloxy) -benzoyloxy] -1, -dihydroxybenzene M 68 ° (69 °) M ₂ 108 ° (99 °) I.

The following are produced analogously:

2, 5-Di- [3 ', 4', 5 '-tris- (tetradecyloxy) -benzoyloxy) -1,4-dihydroxybenzene 2, 5-di- [3', 4 ', 5'-tris- (dodecyloxy ) -benzoyloxy) -l, 4-dihydroxybenzene

2,5-di- [3 ', 4', 5 '-tris- (undecyloxy) -benzoyloxy) -1,4-dihydroxybenzene

2, 5-Di- [3 ', 4', 5 '-tris- (nonyloxy) -benzoyloxy) -1,4-dihydroxybenzene 2, 5-di- [3 ', 4', 5 -tris- (octyloxy) -benzoyloxy) - !, 4-dihydroxybenzene 2,5-di- [3 ', 4', 5 -tris- (heptyloxy) - benzoyloxy) - !, 4-dihydroxybenzene 2,5-di- [3 ', 4', 5 -tris- (hexyloxy) -benzoyloxy) -1,4-dihydroxybenzo1 2,5-di- [3 ', 4' , 5 -tris- (pentyloxy) -benzoyloxy) -1, - dihydroxybenzene 2, 5-di- [3 ', 4', 5 -tris- (dodecanoyloxy) -benzoyloxy) -1,4-dihydroxybenzene 2,5-di - [3 ', 4', 5 -tris- (undecanoyloxy) -benzoyloxy) -1,4- dihyd oxybenzo1 2,5-di- [3 ', 4', 5 -tris- (decanoyloxy) -benzoyloxy) -1 , 4- dihydroxybenzo1 2,5-di- [3 ', 4 ", 5 -tris- (nonanoyloxy) -benzoyloxy) -1,4-dihydroxybenzene 2,5-di- [3', 4 ', 5 -tris- {octanoyloxy) benzoyloxy) -1,4-dihydroxybenzene 2,5-di- [3 ', 4', 5-tris- (heptanoyloxy) -benzoyloxy) -1,4-dihydroxybenzene 2,5-di- [3 ^l , 4 ', 5 -tris- (hexanoyloxy) benzoylox) -1,4- dihydroxybenzo1 2,5-di- [3', 4 ', 5 -tris- (pentanoyloxy) benzoyloxy) -1,4- dihydroxybenzene 2 , 5-di- [3 ', 4 ", 5-tris- (butyryloxy) benzoyloxy) -1,4-dihydroxybenzene

2,5-di- [3 ', 5' -bis- (tetradecyloxy) benzoyloxy) -1,4-dihydro ybenzo1

2,5-di- [3 ', 5'-bis (dedecyloxy) benzoyloxy) -1,4-dihydroxybenzene

2,5-di- [3 ', 5' -bis- (undecyloxy) benzoyloxy) -1,4-dihydroxybenzene

2,5-di- [3 ', 5'-bis (nonyloxy) benzoyloxy) -1,4-dihydroxybenzene 2,5-di- [3 ', 5'-bis-octyloxy) benzoyloxy) -1,4-dihydroxybenzene 2,5-di- [3', 5'-bis-heptylox) benzoyloxy) -1,4 - dihydroxybenzene 2,5-di- [3 ', 5'-bis-hexyloxy) benzoyloxy) - !, 4-dihydroxybenzene, 2,5-di- [3', 5 ^'-bis- pentyloxy) benzoyloxy) -1 , 4-dihydroxybenzene 2,5-di- [3 ', 5'-bis-dodecanoyloxy) benzoyloxy) - !, 4-dihydroxybenzene

2,5-di- [3 ', 5'-bis-undecanoyloxy) benzoylox) -1,4-dihydroxybenzene 2,5-di- [3', 5'-bis-decanoyloxy) benzoyloxy) -1.4 - dihydroxybenzene 2,5-di- [3 *, 5'-bis-nonanoyloxy) benzoyloxy) -1,4-dihydroxybenzene 2,5-di- [3 ', 5'-bis-octanoyloxy) benzoylox) -1 , 4-dihydroxybenzene 2,5-di- [3 ', 5'-bis-heptanoylox) benzoyloxy) -1,4-dihydroxybenzene

2,5-di- [3 ', 5'-bis-hexanoylox) benzoyloxy) -1,4-dihydroxybenzene 2,5-di- [3', 5'-bis-pentanoyloxy) benzoyloxy) -1.4 - dihydroxybenzene 2,5-di- [3 ', 5'-bis-butyryloxy) benzoyloxy) -1,4-dihydroxybenzene

Example 5

By reacting 2, 5-di- [3 ', 4', 5 '-tris- (deeylox) benzoyloxy] -1,4-dihydroxybenzene with 3,4,5-tridecyloxybenzoic acid chloride analogously to Example 1, 1 is obtained. 2,4,5-tetrakis (3 ', 4', 5 '-tris- (decyloxybenzoyloxy) benzene. The following are produced analogously

1,2,4,5-tetrakis (3 etradecylox) - benzoyloxy) -benzene 1,2,4,5-tetrakis (3 odecylox) - benzoyloxy) -benzene 1,2,4,5-tetrakis (3rd ndecyloxy) benzoyloxy) benzene 1,2,4,5-tetrakis (3 onyloxy) benzoylox) benzene 1,2,4,5-tetrakis (3 ctyloxy) benzoyloxy) benzene 1,2,4 , 5-tetrakis (3 eptyloxy) - benzoyloxy) benzene 1,2,4,5-tetrakis (3 exylox) - benzoyloxy) benzene 1,2,4,5-tetrakis (3 entyloxy) - benzoyloxy) -benzene 1,2,4,5-tetrakis (3-odecanoylox) - benzoyloxy) -benzene 1,2,4,5-tetrakis (3-decanoyloxy) -benzoyloxy) -benzene 1,2,4,5-tetrakis (3 ecanoyloxy) - benzoyloxy) benzene 1,2,4,5-tetrakis (3 onanoyloxy) - benzoyloxy) benzene 1,2,4,5-tetrakis (3 ctanoylox) - benzoylox) benzene 1,2 , 4,5-tetrakis (3 eptanoyloxy) - benzoyloxy) -benzene 1,2,4,5-tetrakis (3 exanoylox) - benzoyloxy) -benzene 1,2,4,5-tetrakis (3 pentanoyloxy) - benzoyloxy) benzene 1,2,4,5-tetrakis (

butyryloxy) benzoyloxy benzene Example 6

Preparation of 2,4, 6-tris- (3 ', 4', 5 '-tris- (deeylox) - benzoylox) -triazine

42 mg of melamine and 1.38 g of 3,4,5-tris (deeyloxy) benzoic anhydride are heated to 172 ° C. with stirring. A precipitate forms in the melt, which turns brown after a further hour of heating. After cooling, the reaction mixture is taken up in ethyl acetate, solid constituents are filtered off, and the filtrate is evaporated to dryness. After purification by recrystallization and chromatography, the tris-aroyloxytriazine is obtained as a solid.

The following are produced analogously:

2,4,6-tris (3, 4, 5 '-tris-tetradecyloxy) benzoyloxy) triazine 2,4,6-tris (3, 4, 5'-tris-dodecyl) benzoyloxy) triazine

2, -4,6-tris- (3, 4, 5'-tris-undecyl) -benzoylox) - triazine 2,4,6-tris- (3, 4, 5'-tris-nonyl) -benzoyloxy) - triazine

2,4,6-tris- (3, 4, 5'-tris-ethyl) benzoylox) triazine

2,4,6-tris (3,4,5'-trisheptyl) benzoyloxy) triazine

2,4,6-tris (3,4,5'-trishexyl) benzoyloxy) triazine

2,4,6-tris (3,, 5 '-tris-pentyl) -benzoyloxy) - triazine 2,4,6-tris (3, 4, 5' -tris-butyl) -benzoyloxy) - triazine 2,4,6-tris- (3 *, 4, 5 '-tris- (dodecanoyl) benzoyloxy) triazine

2,4,6-tris- (3 ', 4, 5' -tris- (undecanoyl) benzoyloxy) triazine

2,4,6-tris- (3 ', 4, 5' -tris- (decanoyl) benzoyloxy) triazine

2,4,6-tris- (3 *, 4, 5 '-tris- (nonanoyl) benzoyloxy) triazine

2,4,6-tris- (3 ', 4, 5' -tris- (octanoyl) benzoyloxy) triazine

2,4,6-tris- (3 ^!, 4, 5'-tris- (heptanoyl) benzoyloxy) triazine

2,4,6-tris- (3 ', 4, 5' -tris- (hexanoyl) benzoyloxy) triazine

2,4,6-tris- (3 ', 4, 5' -tris- (pentanoyl) benzoyloxy) triazine

2,4,6-tris- (3 ', 4, 5'-tris- (butyryl) benzoyloxy) triazine

Example 7

By reacting 2,5-di- [3 ', 4', 5 '-tris- (deeyloxy) - benzoyloxy] -1,4-dihydroxybenzene with 2,5-bis-decyloxy-terephthalic acid chloride analogously to Example 1 or according to M. Ballauf, Makromol. Chem., Rapid. Commun. l_ _r 407 (1986) there is obtained a polymeric material which can optionally be dissolved for further purification in N-methylpyrrolidone and material ausgefält by addition of ethanol as a white amorphous Fest¬.

Analog polycondensation can be carried out with terephthaloyl

chloride or be carried out with.

Example 8

A mixture of 0.5 mmol ice, cis-1,3-dihydroxy-5- [3 ', 4', 5 '-tris- (deeyloxy) -benzoyloxy) -cyclohexane, from Example 3b, is heated to 115 mg ( 0.5 mmol) dimethyl sebacate, 4.9 mg (0.014 mmol) titanium tetrabutanolate and 2 ml o-dichlorobenzene at 160 ° for 2 hours. During this time, the solvent is removed by a slow stream of nitrogen. The residue is then gradually heated to 250 ° in vacuo. The polymer obtained is dissolved in 10 ml of N-methylpyrrolidone and the product falls through

Adding methanol made a white, fibrous material.

Example 9

To a mixture of 0.5 mmol ice, cis-1- (3 ', 4', 5'-tris- (deeylox) benzoyloxy) -3,5-cyclohexanediol from Example 3b, 2 ml 1,1,2, 2-tetrachloroethane and 0.3 ml pyridine is a solution of 0.5 mmol terephthaloyl dichloride in 4 under protective gas at 0 ° C according to literature (B. Beck, H. Ringsdorf, Makromol. Chem. Rapid Commun. 7 389 (1986)) ml of 1,1,2,2-tetrachloroethane. After stirring for 4 days at room temperature and one day at 55 ° C, the solution is dropped into methanol after cooling, a white fibrous material precipitating.

Polycondensates of the diol from Example 3b with dicarboxylic acid chlorides such as sebacic acid dichloride or 2,5-bis (deeyloxy) terephthaloyl dichloride are obtained analogously.

Claims

1. Polymer materials containing carbocyclic side groups which are bonded via a spacer to carbo- or heterocyclic six-ring systems substituted in the 1,3,5- or 1,2,4,5-position.

2. Polymer materials according to claim 1, characterized gekenn¬ characterized in that the six-ring systems are selected from the formulas (1) to (3),

Spacer-M Spacer-M Spacer-M

where M is a carbocyclic side group, X is each independently N or CH and YO or NH.

3. Polymer materials according to claim 2, containing units of the formula

-Q-CO-W-CO-

wherein Q_ is a group selected from formulas (1) to (3) and W is the core part of a polymerizable dicarboxylic acid. Polymer materials according to claim 1, 2 and 3, characterized in that the carbocyclic side group M corresponds to the formula (5),

wherein R ° H, alkyl, alkoxy alkoxycarbonyl, alkoxycarbonyl alkoxybenzyloxy or alkanoyloxy, each with 1 b 20 C atoms. and

R ¹ each independently denotes H, alkyl, alkanoyloxy, alkoxycarbonyl, alkoxycarbonyloxy, alkoxybenzyloxy or alkoxy each having 1 to 20 C atoms.

5. A process for the preparation of polymer materials according to claim 3, characterized in that corresponding dihydroxy compounds of the formula

H-Q-H

with corresponding dicarboxylic acids of the formula

HOOC-W-COOH

or _d older reactive derivatives, is subjected to a polycondensation. 6. Carbocyclic compounds of the formula I.

in which A denotes a radical selected from the formulas (la), (lb) and (lc),

where X is each independently N or CH, 2 -o-CO-, -0-CH ₂ -, -CO-O-, -CH ₂ 0- or im

Trap A = (lb) also -NH-CO- or -NH-CH ₂ ~,

Q OH, alkoxy, alkanoyloxy, COOH, alkanoyl, alkoxycarbonyl, p-alkoxybenzoyloxy, p-alkylbenzoyloxy or a radical of the formula

P 2 or, in the case A = (lc), 3,

R ° alkoxy, alkanoyloxy, alkoxycarbonyl, alkoxycarbon oxy, alkoxybenzyloxy or alkyl, and

R in each case independently of one another denotes H, alkoxy, alkanoy oxy, alkoxycarbonyl, alkoxycarbonyloxy, alkoxybe oxy or alkyl. 7. Compounds according to claim 6, characterized in that A represents a radical of the formula (Ia),

P 2 and Q means OH.

8. Compounds according to claim 7, characterized in that Z means -O-CO-.

9. Compounds according to claim 6, characterized in that at least one of the radicals R is different from H.

10. Compounds according to claim 6, characterized gekennzeich¬ net that A is a radical of the formula (Ib) and Q is a radical of the formula

represents.

11. Compounds according to claim 10, characterized in that X denotes N.

12. he _V _b in _d Ungen according to claim 6, characterized in ^¬ net as _{ß A} is a radical of formula (lc), one of Q is a radical of formula

un _d two of the radicals Q -OH, alkoxy, alkanoyloxy, - _COO H, _A lkanoyl or alkoxycarbonyl. 13. Compounds according to claim 12, characterized gekennzeich¬ net that the two radicals Q, which are -OH, alkoxy, alkanoyloxy, -COOH, alkanoyl or alkoxycarbonyl, are P-hour at the rest of the formula (lc).

14. Compounds according to claim 12, characterized gekennzeich¬ net that in the two radicals of the formula

one of the radicals R H.

15. Use of dihydroxy compounds of formula I according to claim 6 (P = 2 / = OH) as intermediates for the production of polymer materials.

16. Use of polymer materials according to claim 1, 2, 3 or 4 as organic substrates in electronics for the fiber and film technology.

17. Use of polymer materials according to claim 1, 2, 3 or 4 for amplitude and / or frequency modulation of laser beams.

18. Use of polymer materials according to claim 1, 2, 3 or 4 for optical data storage.