WO1990012831A1

WO1990012831A1 - Branched, dipolar-oriented polymer materials

Info

Publication number: WO1990012831A1
Application number: PCT/EP1990/000546
Authority: WO
Inventors: Dieter Dorsch; Eike Poetsch; Bernhard Rieger
Original assignee: MERCK Patent Gesellschaft mit beschränkter Haftung
Priority date: 1989-04-20
Filing date: 1990-04-06
Publication date: 1990-11-01
Also published as: EP0423268A1; DE3912922A1; JPH03505473A

Abstract

Polymer materials based on main-chain polymers containing polar monomer units, where the polar monomer units contain electron donor/acceptor-substituted conjugated pi-systems and are oriented in the same direction in the polymer main chains, in which the main-chain polymers are branched, are eminently suitable for use in optical components for non-linear optics.

Description

Branched, dipolar oriented polymer materials

The invention relates to polymer materials based on main chain polymers containing polar monomer units, the polar monomer units containing electron donor / acceptor-substituted conjugated π systems and being oriented in the same direction in the polymer main chains, characterized in that the main chain polymers are branched .

Materials which show non-linear optical behavior are characterized by a field strength-dependent dielectric susceptibility. This non-linearity of the dielectric susceptibility results in a number of effects which are of great interest in application technology.

The frequency doubling (second harmonic generation, SHG) is the generation of light which has half the wavelength compared to the incident light. The change in the refractive index of a material with an applied electric field is referred to as the electro-optical effect (Pockels effect); Methods of sum and difference frequency mixing as well as frequency division allow the continuous tuning of laser light.

Nonlinear optical materials are suitable for the production of optical components. These include, for example, electro-optical modulators, electro-optical switches, electro-optical directional couplers and frequency doublers. - 2 -

These components are used e.g. in optical communications technology, for modulation and control of optical signals, as spatial light modulators in optical signal processing, for frequency doubling 5 of semiconductor lasers, for optical data storage, sensor technology and xerography.

Materials with 3rd order electrical susceptibilities are suitable for the manufacture of purely optical switches and thus for use in purely optical computers.

10 um for use in the field of nonlinear optics

To be suitable for the 2nd order, such materials have to meet a number of requirements.

A prerequisite for technical applicability is the highest possible value for the dielectric susceptibility

15 tat χ (2 '). This requires, for example, a non-centrosymmetric molecular arrangement in the crystal.

A number of inorganic substances such as Potassium dihydrogen phosphate or lithium niobate shows non-linear optical properties. All of these connections are

20, however, has various disadvantages. In addition to inadequate values for the second order dielectric susceptibility, inorganic compounds often lack or are insufficient photostability when treated with high light intensities

25 difficult to manufacture and process.

Organic compounds of the nitroaniline type are known from Garito et al., Laser Focus 1 (1982) and EP-0091 838. Their relatively good values for the photochemical However, stability and the dielectric susceptibility of the second order go hand in hand with poor crystallizability and poor mechanical stability. In particular, the production of thin layers, as required by the integrated optics, does not succeed with these materials.

Polymers that are provided with dissolved or covalently bound NLO chromophores generally only acquire a non-linear second-order susceptibility by applying an electrical field in the fluid state, the NLO chromophores being dipolarly oriented (χ (2) ' ) • The dipolar orientation is permanently frozen by cooling below the glass temperature. χ (2 ') is therefore in a first approximation proportional to the concentration of the NLO chromophores, the E-field strength, the hyperpolarizability ß and the dipole moment μ. For this reason, compounds with large dipole moments and at the same time high β values are of significant interest. For this reason, NLO chromophores consisting of a conjugated π system with an electron acceptor or an electron donor bound to them have already been investigated. Polymer materials containing such donor / acceptor substituted π systems in side chains are known, e.g. Polymethacrylates (EP 0231770, EP 0230898), polystyrenes (JP 63041831, JP 61148433) or

Polyester (EP 0297530). Polymers that contain nonlinear optical chromophores as part of the main chain have hardly been studied. Examples include polybenzimidazoles (EP 0265921) and thermotropic liquid crystal main chain polymers, in which non-linear optical chromophores are incorporated as chain links in the main chain (JP 62238538). On the one hand, the known polymers still have unsatisfactory nonlinear optical properties, on the other hand, they do not meet the requirements for economical use as nonlinear optical media, because they have undesirably high values for the optical attenuation, for example.

There is therefore a need for further nonlinear optical materials which have improved nonlinear optical properties and which do not have the disadvantages described or only have them to a small extent.

It has now surprisingly been found that polymer materials based on main chain polymers which contain donor / acceptor-substituted π systems oriented in the same direction as chain links are outstandingly suitable for non-linear optical arrangements if the main chain polymers are branched.

The polymer materials according to the invention are distinguished in particular by a lower optical attenuation compared to previously known nonlinear optical polymers.

This is probably due to the fact that the polymers are amorphous due to the branches, i.e. have neither a crystalline nor a liquid-crystalline morphology.

The invention therefore relates to polymer materials based on main chain polymers containing polar monomer units, the polar monomer units containing electron donor / acceptor-substituted conjugated π systems and being oriented in the same direction in the polymer main chains, characterized in that the main chain polymers are branched. The invention furthermore relates to nonlinear optical arrangements which contain the polymer materials according to the invention.

The invention also relates to a method for producing the nonlinear optical arrangements according to the invention by placing the polymer materials on a. Applying the substrate and aligning it dipolar or by polarizing monomers having branching sites, optionally in a mixture with polar monomers without branching sites, both types of monomer containing electron donor / acceptor-substituted conjugated π systems, polymerized on a substrate and optionally di¬ polar aligns. The invention finally relates to the use of the non-linear optical arrangements according to the invention in optical components, and also optical components which contain the non-linear optical arrangements according to the invention.

The structure of the polar monomer units in the skin chain polymers according to the invention is largely uncritical. Of importance is the presence of a conjugated π system which is substituted at one end by at least one electron donor and at the other end by at least one electron acceptor. In addition, the polar monomers must be such that reactive groups are available at both ends which allow a head-to-tail linkage of the individual molecules. The reactive groups can themselves be electron donor or acceptor groups or a part thereof or at least be in close proximity to the electron donor or acceptor groups, for example geminally on an aromatic system. Some of the polar monomers are equally bifunctionalized at one end and thus have a branching point which can react equally at both positions with the functional group of a second monomer located at the other end of the π system. These monomers are thus trifunctionalized overall. Thus, according to conventional methods of polymerization, for example in the form of a polycondensation or polyaddition, branched main chain polymers are formed with polar monomer units of the same orientation, the degree of branching being predetermined by the relative ratio of the monomers used (bi- / trifunctional) can.

The monomer ratio bi-: trifunctional is preferably in the range from 0: 100 to 90:10, in particular a range from 0: 100 to 70:30 is preferred.

“Polyaddition” here also means reactions in which ionic structures are formed by substitution (A + BX ^• * AB® ^).

The following scheme is used for a more detailed explanation

P = polymerization

X and Y represent the functional groups that react with each other, ii means the conjugated π system, which is substituted at one end by at least one electron donor and at the other end by at least one electron acceptor. X and / or Y can also themselves be an electron donor or acceptor or a part thereof. The arrow (- ») is intended to indicate that the monomers, branched (a) and linear (b), are polar and that the polar monomer units in the branched main chain polymers according to the invention are oriented in the same direction.

The above diagram shows a possible intermediate on the way to the polymers according to the invention. In step I both groups Y of a monomer a reacted with one monomer a each. Of the four reactive positions (I), three reacted further in step II, namely one (IIA) with a monomer a and two (IIB) with a monomer a or b.

The degree of polymerization is preferably 8-1000, more preferably 10-300.

Ultimately, the degree of branching is determined on the one hand by the ratio of the starting materials a / b and on the other hand by the number of branches actually occurring, e.g. IIB / IIA.

The π system preferably consists of a combination of two, three, four or five of the following radicals: aromatic system, as well as double bond and triple bond, such as, for example, -C = C-, -C = N-, -N = C- , -C≡C-, -N = N-. Particularly preferred π systems are those in which an aromatic with a double bond or a triple bond and in which no more than two double and / or triple bonds are linked to one another. Preferred aromatic systems are carbocycles and heterocycles with up to 18 ring atoms, but with no more than three Heteroatoms, preferably 1,4-phenylene, 2,6- and 2,7-naphthylene, anthracene and phenanthrene diyl, pyrroldiyl, furandiyl, thiophendiyl, imidazole diyl, pyrazole diyl, oxazole diyl, thiazole diyl, pyridinediyl, pyrimidinediyl, triaquinindinediyl , Isoquinolinediyl, quinoxalinediyl, indoldiyl, benzimidazole diyl, benzothiazole diyl.

An electron-rich heteroaromatic is preferably linked to the donor and an electron-poor to the acceptor. Compounds in which no more than two heteroaromatics are present are particularly preferred.

The π system can also be a single aromatic.

Preferred electron donors are amino, alkoxy, alkylthio, and also alkyl, vinyl, hydroxy and thio groups.

Among the electron acceptors, nitro, cyano, alkoxycarbonyl and amide groups, halogen, and ethenylene substituted by -CN and / or -COOR, and also halogen atoms are preferred. Acyl, haloalkyl and alkoxysulfonyl groups are also preferred.

Possible functional groups are, for example, those which are capable of polycondensation or polyaddition. Polymerization processes known and customary to the person skilled in the art, such as e.g. by H. Bartl and J. Falbe in HOUBEN-WEYL, Methods of Organic

Chemistry, Supplement 20, Vol I-III, 4th ed. 1987, Georg Thieme Verlag, Stuttgart, are used. Preferred monomers a and b are those in which electron donor and acceptor groups are linked to aromatic carbon atoms. The functional groups X and Y are then, for example, geminally linked or completely or partially identical to the donor / acceptor groups.

Preferred on the acceptor side are e.g. Phenyl nuclei which are substituted by an electron acceptor indicated above and in the 2- or 3-position by a group capable of polymerization or condensation. Pyridyl nuclei are still preferred. In this case the electron acceptor group is identical to the functional group. The pyridine nitrogen then reacts with poly addition. Additional electron acceptor groups may also preferably be present geminally on the phenyl and pyridyl nucleus. The rest of the conjugated π system is preferably linked para to an electron acceptor group with the ring.

At the other end of the π system, on the donor side, there is preferably also a phenyl nucleus which carries an electron donor group mentioned above in parallel. The second functional group and / or further donor groups can be in the adjacent position. The second functional group can also be identical to or part of a donor group, for example a carboxyl or hydroxyl group, a halide or another suitable leaving group in one or both radicals R of a donor NR ". Suitable monomers a and b are, for example, the compounds of the formula 1

(Sp) 0.1

wherein

X and Y functional groups capable of polyaddition or polycondensation, one Y also hydrogen,

Sp a spacer,

Z 1 and Z 2 each independently represent a single bond, -C = C-, -C = N-, -N = C-, -N = N- or

-C≡C-,

A is a carbo- or heterocyclic aromatic system with 5 to 18 ring atoms, which can consist of C, N, O and S atoms with a total of up to three heteroatoms,

A is an electron acceptor group

D is an electron donor group

n 1 or 2

p 1 or 2 m O, 1 or 2 and

R C -.- C ₁₈ alkylene, in which one or two non-adjacent CH ₂ groups can also be replaced by -O- or -S-,

mean.

The new compounds of formula 1 are also the subject of the invention.

The functional groups X and Y must be in the form of a molecule such that X of one molecule can react with Y of a second molecule. For the sake of simplicity, this is indicated below by the formulation "X / Y".

Groups COOR '/ CΗ or OH / COOR' are preferred which react to form polyester.

Here and below, R 'denotes H or an alkyl radical having up to 6 carbon atoms.

Also preferred are OH / OH or Hal / OH, in which shark is a halide such as F, Cl or Br. The halide is preferably attached to the benzene nucleus in the o-position to the nitro group and can thus be substituted nucleophilically. Also preferred are COOR '/ NR' and COOR '/ SH.

The group X, optionally linked via a spacer, is preferably in the o-position to NO ~, but can also be bound in the m-position. The spacer means an alkylene which may be interrupted by -0- or -NR'- and has up to four carbon atoms. Z1 and Z2 preferably denote a single bond,

-C = C- or -C≡C-.

A is preferably 1,4-phenylene, 2,6- and 2,7-naphthylene, anthracene and phenanthrenediyl, pyrroldiyl, furandiyl, thiophendiyl, imidazole diyl, pyrazole diyl, oxazole diyl, thiazole diyl, pyridinediyl, pyrimidinediyl, triazinediyl, quinolinediyl , Isoquinolinediyl, quinoxalinediyl, indoldiyl, benzimidazole diyl or benzothiazole diyl.

Also preferred are compounds of formula 1 in which no more than two heteroaromatics are present and a substituent A or D is bonded.

Preferred electron donors D are amino, alkoxy, alkylthio, and also alkyl, vinyl, hydroxy and thio groups.

Among the electron acceptors A, nitro, cyano, alkoxycarbonyl and amide groups, halogen, and ethenylene substituted by -CN and / or -COOR, and also halogen atoms are preferred. Acyl, haloalkyl and alkoxysulfonyl groups are also preferred.

m is preferably 0 or 1. Particular preference is given to those compounds of the formula 1 which have the given preferred meanings for X, Y, Z 1, Z2, A1, A,

D, Sp, m and R. Are very particularly preferred

Stilbene derivatives of Formula 1. Other suitable monomers a and b for the preparation of the polymer materials according to the invention are pyridine derivatives which are structured like the compounds of formula 1, but in which the nitrophenyl radical is replaced by a pyridin-4-yl radical. The grouping (Sp) ₀ . -X is then no longer present, the pyridine nitrogen thus reacts with polyaddition with the part -RY of a second molecule. In the case of the pyridine derivatives, Y preferably denotes a halide such as Cl, Br or I or another easily substitutable group such as mesylate or tosylate. In the case of the reactive groups Br, I, mesylate and tosylate, the polymerization can already partially occur in situ. In the pyridine derivatives, a functional group is therefore identical to the electron acceptor group.

The monomers a and b used to prepare the polymer materials according to the invention can be prepared by standard processes in organic chemistry.

The reaction conditions can be found in the standard works of preparative organic chemistry, for example ^' HOUBEN-WEYL, Methods of Organic Chemistry, Georg

Thieme Verlag, Stuttgart, ORGANIC SYNTHESES, J. Wiley, New York - London - Sydney, or HETEROCYCLIC COMPOUNDS, Vol. 14, J. Wiley, New York - London - Sydney.

For example, compounds having a —C =C double bond can be prepared by condensing alkyl compounds with a corresponding aldehyde or ketone in a manner which is conventional per se. The condensation is advantageously carried out with the addition of a dehydrating agent such as acetic anhydride, a base such as ammonia, ethylamine, piperidine, pyridine or a salt such as ammonia acetate or piperidinium acetate. Also proves to be expedient Addition of an inert solvent such as hydrocarbons such as hexane, cyclohexane, benzene, toluene or xylene. The reaction temperature is usually between 0 ° and + 250 ° C, preferably between + 20 ° and +150 ° C. At these temperatures, the reactions are usually complete after 15 minutes to 48 hours. Stilbene derivatives can be prepared, for example, by a Wittig reaction or also by a Wittig-Horner reaction from corresponding aromatic aldehydes and corresponding arylmethylphosphonium salts or phosphonates.

C = N or N = N double bonds can be obtained by analogous condensation reactions from aldehydes and primary amines, or nitroso compounds and primary amines in a manner known to those skilled in the art.

In a further process for the preparation of said compounds, a (He ero) aryl halide is reacted with an olefin in the presence of a tertiary arain and a palladium catalyst (cf. RF Heck, Acc. Chem. Res. If2_ (1979) 146). Suitable (he ero) aryl halides are, for example, chlorides, bromides and iodides, in particular bromides. The tertiary amines required for the coupling reaction to succeed, such as triethylamine, are also suitable as solvents. Suitable palladium catalysts are, for example, its salts, in particular Pd (II) acetate, together with organic phosphorus (III) compounds such as triarylphosphines. You can work in the presence or absence of an inert solvent at temperatures between about 0 ° and +150 ° C, preferably between about + 20 ° and +100 ° C; Examples of solvents are nitriles such as acetonitrile or hydrocarbons such as benzene or Consider toluene. The (hetero) aryl halides and olefins used as starting materials are widely available commercially or can be prepared by processes known from the literature, for example by halogenation of corresponding parent compounds or by elimination reactions on corresponding alcohols or halides.

Furthermore, for the coupling of (hetero) aromatic (hetero) aryl halides with (hetero) aryltin compounds or (hetero) arylboronic acids. These reactions are preferred with the addition of a catalyst such as e.g. of a palladium (O) complex in inert solvents such as hydrocarbons at high temperatures, e.g. in boiling xylene, carried out under protective gas.

The polymers according to the invention also include copolymers consisting of different monomer units a, optionally in a mixture with one or different monomer units b.

The monomer ratio a / b depends on various factors, for example the application and the

Nature of the monomers. It is preferably in the range from 100: 0 to 10:90, a range from 100: 0 to 30:70 is particularly preferred. In addition, the degree of branching is influenced, among other things, by steric conditions. On the one hand, sterically demanding monomers are less prone to branching, and on the other hand the degree of branching is to a certain extent also dependent on the space available for branching. If, for example, an LB film (Langmuir-Blodgett) of a monomer a is applied to a substrate in the form of a monolayer, then a second layer is applied, polymerized and the process repeated, the degree of branching is in some cases considerably lower than in the polymerization of a "diluted""Monomers, for example in solution. The nonlinear optical arrangements according to the invention can be manufactured in various ways. For example, they can be prepared by first preparing a polymer according to the invention in an inert solvent, applying it to a substrate surface, for example glass, by spin coating, brushing, printing or dipping, and then aligning it dipolar. The alignment is expediently carried out at a temperature which is in the vicinity of the glass transition temperature of the polymer, preferably by means of an electrical field. The temperature can be both above and below the glass transition temperature.

Furthermore, the monomers can also be in bulk, i.e. can be poly erized without solvent, for example on the substrate surface. If the polymerization is carried out in bulk on the substrate surface, then either after the polymerization, as mentioned, can be dipolar-oriented or the polymerization is already polymerized with an applied field, preferably an electric field, a dipolar orientation already occurring.

However, the polymerization on the substrate surface can also be designed in such a way that the monomers are applied to the surface from the gas phase by selecting the test conditions such that the monomers polymerize at the same time. This method is advantageous, for example, in the case of monomers which interact strongly with the surface, for example on account of amphiphilic properties. The monomers predominantly interact selectively with the surface, a first monomer layer oriented overall in the same direction being formed, so that the subsequent polymerization proceeds in such a way that the finished polymer material already has a diplomatic orientation. Suitable for this are, for example, monomers with terminal nitrogen heterocycles, for example pyridine derivatives, in which the ring nitrogen can interact with the substrate surface. However, other monomers from the gas phase can also be applied and then polymerized, in which case a dipolar orientation induced by an external field may be required.

As mentioned above, non-linear optical arrangements can also be produced using the LB method.

The nonlinear optical polymer materials according to the invention are amorphous and are therefore distinguished by their low optical attenuation of <1dB cm ^" . Light-scattering effects, such as occur with crystalline or partially crystalline polymers, adversely affect the usability of the materials in nonlinear optics These effects do not occur or only occur to an insignificant extent in the arrangements according to the invention.

Due to their pyro- and piezoelectric properties, the polymer materials according to the invention open up a further broad field of application.

The polymer materials according to the invention are suitable, for example, for use in optical components. They can thus be used in bulk materials, on the one hand, and in waveguide structures, on the other hand, using the electro-optical effect or for frequency doubling and frequency mixing. The polymer materials according to the invention may themselves function as waveguides. The thickness of the polymer layers depends on the application. When used as a single-mode waveguide, a layer thickness in the micrometer range of approximately 1-10 μm is advantageous, in particular up to approximately 7 μm. Nonlinear optically active overlay materials on a waveguide structure usually have layer thicknesses in the nanometer range of approximately 50-500 nm.

The polymer materials according to the invention are thus suitable, for example, in components in the field of integrated optics, sensor and communications technology, for frequency doubling of laser light, for the production of directional couplers, switching elements, modulators, parametric amplifiers, waveguide structures, light valves, and others Optical components known to those skilled in the art. Optical components are described, for example, in EP 0218938.

The following examples serve to explain the invention.

Preparation of monomers a and b:

example 1

a) 4-Acetylamino-3'-cyano-4'-nitrostilbene

A solution of 135 g (0.83 mol) of 2-nitro-5-methylbenzonitrile (prepared by nitriding m-tolunitrile), 135 g (0.83 mol) of 4-acetylamino-benzaldehyde and 80 ml of piperidine in 600 ml Pyridine is heated to 140 ° C for 4 h. The mixture is allowed to cool and the precipitate formed is filtered off. Orange crystals with a melting point (mp): 217-218 ° C. are obtained. b) 4-amino-3 ^• -cyano-4'-nitrostilbene

A suspension of 135 g (0.44 mol) of 4-acetylamino-3'-cyano-4'-nitrostilbene in a mixture of 260 ml of 37% aqueous hydrochloric acid and 1100 ml of ethanol is boiled for 48 hours. The mixture is allowed to cool and the precipitate is filtered off. This is poured into 200 ml of 35% sodium hydroxide solution, the mixture is then stirred for 4 hours and filtered. The residue is recrystallized from acetone / ethanol. Dark red crystals are obtained.

c) N, N-bis- (6-hydroxyhexyl) -4-amino-3 * -cyano-4'-nitrostilbene

To a solution of 50.0 g (188 mmol) of 4-amino-3'-cyano-4'-nitrostilbene and 77.1 g (564 mmol) of 6-chloro-hexanol in 300 ml of N-methylpyrrolidin-2-one (NMP) 47.5 g of sodium hydrogen carbonate and 84.5 g (564 ml) of sodium iodide are added and the mixture is heated to 100 ° C. for 44 h. The mixture is poured onto water and the precipitate is filtered off. The residue is chromatographed on a silica gel column using dichloromethane / methanol 9: 1 as the eluent. Purple, shimmering green crystals are obtained.

d) N, N-bis (6-hydroxyhexyl) -4-amino-4 * -nitrostilbenyl-3'-carboxylic acid

A suspension of 20.0 g (43.0 mmol) of N, N-bis- (6-hydroxyhexyl) -4-amino-3'-cyano- '-nitrostilbene in a mixture of 150 ml of 5 N sodium hydroxide solution and 100 ml of ethanol becomes 6 h heated to boiling. One leaves cool, neutralize with 25% hydrochloric acid and filter the precipitate. A deep red solid is obtained.

Example 2

a) N-Hexyl-4-amino-3'-cyano-4'-nitrostilbene

A solution of 52.9 g (0.20 mol) of 4-amino-3 * -cyano-4'-nitrostilbene (Example 1b) and 33.0 g (0.20 mol) of 1-bromohexane in 170 ml l, 3-dimethyl 16.8 g (0.20 mol) of sodium hydrogen carbonate are added to -2-imidazolinone and the mixture is heated at 100 ° C. for 3 h. The mixture is allowed to cool, poured onto water and extracted with dichloromethane. The organic phase is dried over sodium sulfate, evaporated and the residue is chromatographed on a silica gel column using petroleum ether / ethyl acetate 1: 1 as the eluent. Dark red crystals are obtained, m.p. 134-135 ° C

b) N-Hexyl-N- (6-hydroxyhexyl) -4-amino-3'-cyano-4'-nitrostilbene

To a solution of 15.0 g (42.9 mmol) of N-hexyl-4-amino-3'-cyano-4'-nitrostilbene and 8.80 g

(64.4 mmol) 6-chlorohexanol in 100 ml NMP, 5.41 g (64.4 mmol) sodium hydrogen carbonate and 9.65 g (64.4 mmol) sodium iodide are added and the mixture is heated to 100 ° C. for 44 h. The mixture is poured onto water and the precipitate is filtered off. The residue is chromatographed on a silica gel column using dichloromethane / methanol 95: 5 as the eluent. A violet solid is obtained. c) N-Hexyl-N- (6-hydroxyhexyl) -4-amino-4 * -nitrostil-benyl-3'-carboxylic acid

The compound is prepared from the product 2b) as described in Example ld).

Example 3

a) 4-bromo-N, N-bis (3-hydroxypropyl) aniline

A solution of 18.9 g (0.11 mol) of 4-bromoaniline and 61.4 g (0.33 mol) of 3-iodopropanol in 100 ml of 1,3-dimethyl-2-imidazolidinone is mixed with 27.7 g (0 , 33 mol) of sodium hydrogen carbonate are added and the mixture is heated at 100 ° C. for 1 h. The reaction mixture is poured onto water and washed with tert. Butyl methyl ether extracted. The organic phase is dried over sodium sulfate and evaporated. The residue is on a silica gel column with dichloroethane / methanol

Chromatographed 95: 5 as eluent, colorless crystals are obtained.

The following is prepared analogously: 4-bromo-N, N-bis (6-hydroxyhexyl) aniline (yellowish oil).

b) 4- (2- (4-bis (3-hydroxypropyl) amino) phenyl) ethenyl) pyridine

A solution of 21.6 g (75 mmol) 4-bromo-N, N-bis (3-hydroxypropyl) aniline, 15.8 g (150 mmol) 4-vinylpyridine, 7.6 g (75 mmol) Triethyla in, 168 mg (0.75 mmol) palladium (II) acetate and 457 mg (0.75 mmol) tris (o-tolyl) -phosphane in 80 ml acetonitrile becomes 20 h Boiling heated. The reaction mixture is poured onto water, the precipitate is filtered off with suction and recrystallized from ethanol. Yellow crystals are obtained, mp: 200-202 ° C.

The following is prepared analogously: 4- (2- (4-bis (6-hydroxyhexyl) amino) phenyl) ethenyl) pyridine (yellow oil).

c) 4- (2- (4-Bis (3-chloropropyl) amino) phenyl) ethenyl) pyridine

A mixture of 9.3 g (29.8 mmol) of 4- (2- (4-Biε (3-hydroxypropyl) amino) phenyl) ethenyl) pyridine and 20 ml of thionyl chloride is stirred for 3 hours at room temperature. The reaction mixture is poured onto ice water and extracted with dichloromethane. The organic phase is dried over sodium sulfate, evaporated and the residue is chromatographed on a silica gel column using dichloromethane / methanol 95: 5 as the eluent. Yellow crystals are obtained.

The following is prepared analogously: 4- (2- (4-bis (6-chlorohexyl) amino) phenyl) ethenyl) pyridine (yellow oil).

Polymers

Example 4

A mixture of 3.0 g of N, N-bis (6-hydroxyhexyl) -4-amino-4'-nitrostilben-3'-carboxylic acid and 20 mg of p-toluenesulfonic acid is applied for 4 hours under a pressure of 10 torr 200 ° C, then heated to 230 ° C under a pressure of 0.1 Torr. A deep red, amorphous glass-like polymer is obtained. Example 5

Analogously to Example 4, 1.5 g of N, N-bis (6-hydroxyhexyl) -4-amino-5'-nitrostilbenyl-3 ^" carboxylic acid, 1.5 g of N-hexyl-N- (6-hydroxyhexyl) -4-amino-4 • -nitrostilbenyl-3'-carboxylic acid and 20 mg p-toluenesulfonic acid produced a deep red, amorphous glass-like polymer.

Example 6

A 15% by weight solution of the polymer from Example 5 is prepared in the NMP.

The solution is filtered (filter with a pore diameter of 2 μ) to remove dust particles.

A glass plate (4 cm x 4 cm, thickness: 1.1 mm) coated with ITO (indium tin oxide) is ultrasonically cleaned in neutral soap solution (Extran, Merck) for 10 minutes, then in double distilled Rinsed water and rinsed with isopropanol. The polymer solution is spun onto this glass plate (1000 rpm), then dried in vacuo at 100 ° C. for 4 hours. The film thickness is approximately 1.3 μm. A semitransparent gold electrode is deposited on this film.

The film is heated to 140 ° C in a vacuum oven; then a DC voltage of 100 V is applied for 10 minutes at 150 ° C. In the electric field, the sample is at 1 ° C / min. cooled to room temperature, then switched off the field. Finally, the film is placed in the beam path of an Nd: YAG laser (λ = 1.06 μm, pulse duration 7 nsec, pulse energy 0.5 mJ, 50 "angle to the film surface). The light is partially doubled in frequency.

Example 7

A mixture of 99.5% by weight of N, N-bis (6-hydroxyhexyl) -4-amino-4'-nitrostilbenyl-3'-carboxylic acid and 0.5% by weight of p-toluenesulfonic acid is coated with ITO on one ¬ th glass plate heated to 250 ° C. The melt is spread to form a uniform, approximately 10 μm thin film. After 4 h, the mixture is allowed to cool to room temperature. The resulting polymer film is, as described in Example 6, vaporized with gold, poled in an electric field and transversely irradiated with laser light. The laser light is partially frequency-doubled.

Example 8

A mixture of 99.5% by weight of N, N-bis (6-hydroxyhexyl) -4-amino-4'-nitrostilbenyl-3'-carboxylic acid and 0.5% by weight of p-toluenesulfonic acid is coated with ITO between two ¬ teten glass plates, which are arranged at a distance of 20 microns from each other, heated to 240 ° C at an applied electrical voltage of 100 V. After 1 h, the mixture is allowed to cool to room temperature and the voltage is switched off. Transversely irradiated laser light (example 6) is partially frequency-doubled. Example 9

A sample of 4- (2- (4-bis (3-chloropropyl) aminophenyl) ethenyl) pyridine (Example 3 c) is, as described in Example 8, polymerized between two ITO electrodes with applied voltage. However, the temperature is

200 ° C. When the laser light is transversely transmitted, the frequency of the light is partially doubled.

Example 10

In a vacuum chamber, which is evacuated to 10 -7 torr, there is a flat glass vessel with 200 mg of 4- (2- (4- bis (3-chloropropyl) amino) phenyl) ethenyl) pyridine and one 200 ^Λ C heated glass plate. A thin transparent red polymer film forms on the glass plate for 2 hours. With transversal radiation with laser light, the frequency of the light is partially doubled.

Example 11

Egg .ni.ge drops of egg 10-3 m solution of 4- (2- (4-Bιs- (3-chloropropyl) amino) phenyl) ethenyl) pyridine (example

3 c) are placed on the water surface of a Langmuir trough (commercially available from Messgeräte

Lauda, Lauda-Königshofen). The molecules on the surface are compressed into a monolayer ^" by means of a movable barrier. This monolayer is transferred to a polished germanium single crystal plate by immersion and extraction. FTIR-ATIR measurements (Fourier transform infrared) atte- nuated total internal reflection) show strong IR - 26 -

Dichroism and thus a high degree of axial orientation of the molecules. The film is then heated to 200 ° C. for 30 minutes. FTIR-ATIR measurements now show, on the one hand, that the polymerization has proceeded quantitatively and, on the other hand, due to the lack of an IR dichroism, that the axial orientation is complete or at least has almost completely collapsed.

These steps are repeated three times. The measurements always show good axial orientation of the monomer molecules and breakdown of the axial orientation after the polymerization.

Light from an Nd: YAG laser, which shines through the polymer multilayer film produced in this way (analogously to Example 6), is partially frequency-doubled.

Analogously, 30 layers of the same polymer are produced on a glass substrate and then irradiated. The laser light is also partially frequency-doubled.

Example 12

An optical component as described by R. Lytel et al. in proc. SPIE, Vol. 824, p. 152 (1988), with the polymer id (spin coating). The material shows excellent waveguiding properties due to the very low optical attenuation.

Claims

1. Polymer materials based on main chain polymers containing polar monomer units, the polar monomer units containing electron donor / acceptor-substituted conjugated π systems and being oriented in the same direction in the polymer main chains, characterized in that the main chain polymers are branched are.

2. Nonlinear optical arrangements, characterized in that they contain polymer materials according to claim 1.

3. A method for producing nonlinear optical arrangements according to claim 2, characterized gekennzeich¬ net that the polymer materials according to claim 1 is applied to a substrate and dipolar alignment.

4. A process for the production of nonlinear optical arrangements according to claim 2, characterized gekennzeich¬ net that one has branching points, polar monomers, optionally in a mixture with polar monomers without branching points, both types of monomers containing electron donor / acceptor-substituted conjugated π systems , polymerized on a substrate and optionally dipolar aligned. Use of nonlinear optical arrangements according to claim 2 in optical components.

Optical component containing non-linear optical arrangements according to claim 2.