DD297179A5 - POLYAMIDE AEROS AND DERIVATIVES AND METHOD FOR THE PRODUCTION THEREOF - Google Patents

Abstract

Polyamic acids and their reactive derivatives with chemically bonded nonlinear optically active chromophores which can be converted into polyimides by cyclization, characterized in that the nonlinear optically active chromophores have a positive value for the quadratic hyperpolarizability (b), and the polyimides prepared therefrom are suitable in excellent for the production of non-linear optical arrangements that can be used in optical components.

Description

Field of application of the invention

The invention relates to polyamic acid and its reactive Dorivato with chemically bonded nonlinear optically active chromophores, which can be converted by cyclization in polyimides, characterized in that the nonlinear optically active chromophores have a positive value for the quadratic hyperpolarizability (ß).

The invention further relates to polymer materials based on polyimides obtainable from said polyamic acids

Materials exhibiting nonlinear optical behavior are characterized by field strength dependent dielectric susceptibility. This nonlinearity of dielectric susceptibility results in a number of effects which are of great technical interest.

The second harmonic generation (SHG) is the generation of light that is half the wavelength compared to the incident light. As an electro-optical effect (Pockels effect), the change is called the refractive index of a material with an applied electric field; 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.

These devices find application e.g. in optical communications engineering, for modulating and controlling optical signals, as spatial light modulators in optical signal processing, for frequency doubling of semiconductor lasers, for optical data storage, sensor technology and xerography.

Characteristic of the known technical solutions

Polymers which are provided with dissolved or covalently bonded NLO chromophores usually obtain a second-order nonlinear susceptibility (X ¹²¹ I. Die by applying an electric field in the fluid state, the NLO chromophores being dipolarly oriented dipolar orientation is permanently frozen by cooling to below the glass transition temperature. X ¹²¹ is therefore proportional β in a first approximation to the concentration dei NLO chromophores for the e-field strength to the hyperpolarizability and Dipolmomcnt μ. Datier are compounds mil large dipole moments, while high For this reason, NLO chromophores consisting of a conjugated n system with an electron acceptor or an electron donor attached to it have already been investigated, and polymer matrials containing such donor / acceptor-substituted n- Systems in side chains are known, for example polymethacrylates (EP 0231770, E P 0230898), polystyrenes (JP 63041831, JP 61148433) or polyester (EP 0297530). Polymers containing nonlinear optical chromophores as part of the backbone have scarcely been studied. Examples of these are polybenzimidazoles (EP 0265921) and thermotropic liquid crystal main chain polymers in which partially nonlinear optical chromophores are incorporated as chain links in the main chain (JP 62238538).

EP 0243806 discloses polyimides for nonlinear optics, but exclusively with NLO chromophores with negative values for quadratic hyperpolarizability (β).

Object of the invention

The object of the invention was to find further polymer materials for nonlinear optics, in particular those having improved properties, such as increased, for example thermal, resistance and greater stability.

Explanation of the essence of the invention

The object has been achieved by providing the polyimides according to the invention.

Surprisingly, it has been found that polyimides having NLO chromophores with positive β values are both generally more stable and thermally more resilient than the known NLO polymors.

The invention thus polyamic acids and their reactive derivatives with chemically bonded nonlinear optically active chromophores, which can be converted by cyclization in polyimides, characterized in that the nich'ilinear optically active chromophores have a positive value for the quadratic hyperpolarizability (ß).

The invention particularly relates to polymer materials based on polyimides which have been prepared from the polyamic acids according to the invention or their reactive derivatives.

The invention also relates to non-linear optical arrangements containing the polymers of the invention, processes for their preparation and optical components containing the inventive arrangements.

The polyimides according to the invention are distinguished inter alia by the very high glass transition temperatures and by high solvent resistance. The precursors, the polyamic acids according to the invention and their derivatives can be used advantageously. Due to their good solubility, they can be easily applied to a substrate by, for example, spin coating. Both the polyamic acids according to the invention and their derivatives as well as the polyimides produced therefrom, if appropriate after additional dipolar orientation, are outstandingly suitable as nonlinear optical materials in optical components. By "derivatives" is meant herein generally esters of aliphatic alcohols, preferably having 1 to 12 carbon atoms within the alcohol component.

The polyamic acids according to the invention and their reactive derivatives can be represented by the general formula I, the polyimides according to the invention obtainable therefrom by the general formula II. Both formulas represent recurring structural units of both polymer types.

O O

ΑΛνη-AJ

Γ /

⁰ "

O O

Y Y OO

II

^J h

Accordingly, regardless of the synthesis route, the polyamic acids or acid derivatives and polyimides according to the invention are composed of an acid moiety (contains Z), an amine moiety (contains A) and optionally an alcohol moiety (contains R ^ H). For the sake of simplicity, the formulations "Z-part", "Α-part" and "R-part" will accordingly be used hereinafter The non-linear optical chromophores may be covalently bound both in the Α-part and in the Z-part of the polymers according to the invention In either case, they may be either main- or site-chain-linked according to the following schemes (a) to (d).

Backbone-like

(A)

ί ">

Il

O O

Μ O

(B)

Side chain-like

O Il

• Ν,

Il

o U o

(C)

 I

° (d) ^DJ

The schemes (a) to (d) are analogous to the precursors, the polyamic acid according to the invention and their reactive derivatives transferable. In the schemes (a) to (d) means

The structure of the nonlinear optical Chromophoro, in the above schemes as Γ  I presented, is wholeheartedly

critical. Preferably, they are conjugated n systems substituted at one end by one or more electron donors and at the other end by one or more electron acceptors. In the case of the structures (c) and (d), the coupling sites with the main polymer capillaries themselves may already be electron donors or acceptors or parts thereof. Particularly preferred NLO chromophores are p, p'-aminonitrostilbenes and chromophores derivable therefrom. They are, for example, by shortening or by extending the rt system with aromatic or auoh heteroaromatic radicals, double bonds, triple bonds or additional substitution, preferably at the ends of the conjugated n-system, adjacent and, seen electronically, in the same direction to the existing electron donor or acceptor, structurally derivable from the ρ, ρ'-aminonitrostilbene skeleton. Furthermore, NLO chromophores are preferred in which, instead of the amino or nitro group of the stilbene derivatives mentioned, other electron donor or acceptor groups are bonded.

In structures (a) and (b), the NLO chromophore as a whole must be a divalent organic radical. The linking sites to Z 'and A' are respectively on the donor and the Akezptorseite the chromophore. On the donor side, the linkage can take place, for example, via an alkyl radical, an amino or ether group, on the acceptor side, for example via the alcohol component of an ester group. This can be clarified, for example, by the following structural scheme (e)

O R

- (Α ', Ζ · J (Sp) ₀ ^ ₁ -OC- (B-JX-N- (Sp) ₀ ^ ₁ - (Z ^1, A ¹⁾ - ^(β)

Here and below, B denotes at least one electron acceptor, X denotes a ρ, ρ'stilbene skeleton or a π skeleton derivable therefrom as described above, R denotes an alkyl radical and Sp denotes a spacer, for example an alkylene chain which is also e.g. by NR-or-O-can be interrupted.

In the polymers according to the invention, the NLO chromophores are preferably linked side-chainwise according to the schemes (c) and (d). This generally leads to an advantageous lowering of the glass transition temperature.

Dio NLO chromophores may, for example, be linked to the polymer main chain via the donor, it being possible for the donor itself to be the main chain link. Particularly preferred are amino, ether and thioether groups as donors, in particular amino groups. The preferred structures can be illustrated by the following schemes (f) and (g).

^(Sp) 0 1 '

¹ '(f)

(NR / 0, S) ^(l)

(Α ', Ζ ¹ ) -Sp-N-Sp- (Z ¹ , A ¹ )

x ^(gl

I B

In scheme (f), Y is CH. The NLO chromophore is therefore completely bound in a side chain of the polymer. If the Sp associated with (Z ', A') in Scheme (f) are absent ((Sp) ₀ ], then Y can also be an aromatic C atom.) In this case, the groups Z 'and A' are bonded to other than this aromatic C atom According to scheme (g), the donor moiety of the NLO chromophore is part of the polymer backbone.

If the NLO chromophore is bound in the Α-part (Schemes b and d) in the polymers according to the invention, the Z-part preferably consists of the skeleton of a tetracarboxylic acid, for example pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, cyclobutane, cyclopentane or cyclohexanetetracarboxylic. If the NLO chromophore is bound in the polymers of the invention in the Z-TeN (Schemes a and c), the Α part preferably consists of the skeleton of a diamine such as p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 4.4 'Diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 2,2-bis (4-aminophenyl) propane, diaminodiphenylsulfone, diaminobenzophenone, 1,5-diaminonaphthalene, 1,3-bis (4-aminophenoxy) benzene, 1,4- bis (4-aminophenoxy) benzene, 4,4'-di (4-aminophenoxy) diphenylsulfone, 2,2-bis [4- (4-aminophenoxyphenyl) -propane], 2,2-bis (4-aminophenyl) -hexafluoropropane , 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 1,4-diaminocyclohexane, 1,3-diaminocylcohexane, 4,4'-diaminodicyclohexylmethane, 4,4'-diamino-3,3 ' Dimethyldicyclohexylmethane, 4,4'-diaminodicyclohexylsulfone, 4,4'-diaminodicyclohexyl ether, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1 , 7-diaminoheptane or 1,8-diaminooctane.

However, other carboxylic acid or diamine components can also be used, as described, for example, in DE 3107519, EP 0209114, EP 0219336, EP 0231781 and EP 0249881.

The polymers according to the invention also include copolymeric polyamic acids or their reactive derivatives and copolymeric polyimido. After application, it is possible to react the carboxylic acid and / or diamine components with one another. This also means copolymers in which the NLO chromophores are not contained in all A or Z parts.

If the NLO chromophore is bound in the Z-Toil, the carbonyl groups which form the imide moiety of the polyimides of the invention are preferably bonded to aromatic C atoms. Z in this case particularly preferably means according to Formol I odor Il a structural unit of the formula (h) or (i)

(Op-e-Sp-Sp-N-E-iCjp

(H)

(I)

ρ is O or 1, E is -NH or -N (alkyl) -, - O or -S-. Particular preference is given to - (- C0) _p -EO -, - CO-O-, -CC-NH- and -CO-NIAIkyl) - with alkyl is methyl, ethyl, propyl, butyl, pentyl or hexyl.

If the NLO chromophore is bound in the A-part, then A according to formula I or II preferably denotes a structural unit of the formula (k).

- (CyO ₀ J-

(K)

Cyc is an aromatic or cycloaliphatic system, for example 1,3-phenylene or 1,4-cyclohexylene. In formula (k) at least Cyc or Sp is present.

Of the structures (h) and (k), in particular the symmetric ones are preferred.

The compounds on which the preferred NLO chromophores in the polymers according to the invention are based can be represented by the general formula III '.

Ill

-NR '^ - OR'or-SR ¹ , each independently of one another -H, -NR ^ - OR' or SR ¹ ,

-NO ₂ , -CN,

NC ^ ₌ . ^ - CN ^ CN

CN '

COOR

or

B ¹ and B ^{2 are} each independently H, -NO ₂ , -CN, halogen, -CF ₃ , -COOR ', - CONRj.-SOaR' .- SOjR ',

-SOR ', or -SO ₂ NR ₂ ,

G ¹ and G ^{2 are} each independently a single bond - + - C (R ² ) = C (R ² ) -4 _m -, - N = N -, - C = N -, - N = C or-C = C, m 1 or 2,

L is a carbo- or heterocyclic system with 5-18 ring atoms containing up to three hetero ring atoms,

selected from the group N, O and S,

η 0,1,2 or 3,

ρ 0 or 1,

R ^{1 are} each independently H or Ci-C ₂₄ -AlkVl and

R ^{2 are} each independently H or C ₁ -C ₆ -alkyl

with the proviso that B ^{1 is} hydrogen if ρ is 1.

The main chain-like bound in the erfinclungsgomäßon polymers NLO chromophores (Schemes a and b) are on the one hand on Donorsoito (D, D ¹ ) and on the other hand on the acceptor side (B, B ¹ , B ² ) covalently linked to the polymer main chain. The linkage preferably takes place within D, for example via a radical R ¹ in -NR ' ₂ or -OR'. The linkage in the acceptor oil preferably takes place via a radical R ¹ in B ¹ or B ² , for example a carboxyl group. The substituents B 'or B ^{2 which} are suitable for this purpose can also be attached via a spacer to the phenyl nucleus in formula III, ie they do not necessarily function as B additional acceptor groups in this hall (Scheme e).

If the preferred NLO chromophores are linked side-chain-like in the polymers according to the invention (Schemes c and d), then they can in principle be bonded to the C-atom of the formula III which is linked to jadom. Preferably, the NLO chromophore of Formula III is linked to the poly moiety within the donor moiety (D, D '). Particularly preferred is the linkage via D according to the formulas (h), (i) and (k).

In the formula III preferably D 'represents -NR ₂ or -OR. ¹

B is preferably -NO ₂ and -CN.

Each D ¹ is independently of one another preferably -H, -NR ₂ or -OR ¹ .

Each of B ¹ and B ² independently represents H or an electron acceptor group such as -NO ₂ , -CN or halogen, such as

z. B. -F, -Cl or -Br, -CF ₃ , -COOR ', -CONR ₂ and sulfoxide, sulfonate and sulfonamide groups, preferably -NO ₂ , -CN, -F, -Cl, -CF ₃ and - COOR ¹ . However, in the case of ρ equal to 1, both grids B 'are equal to H.

The bridge members G 'and G ^{2 are} each independently a single bond, -fC (R ² ) = C (R ² H _m where m is equal to or 2, -C = C -, - C = N, -N = C-, Particularly preferred are single bond, -C (R ² ) - = C (R ² ) -and-CsC-.

L is a carbocyclic or oteroterocyclic η system with 5 to 18 Rinnatomen. These are in particular 1,4-phenylene, 2,6- and 2,7-naphthylene or anthracene, 2,5-pyrrolidyl, furandiyl and thiophenediyl, and also pyridinediyl, pyrimidinediyl, triazinediyl and indolediyl. However, other heteroaromatics may also be L, but with not more than three hetero ring atoms. Preferred polymers according to the invention contain no more than two heteroaromatics in a side chain.

R 'is H or a branched or straight-chain alkyl radical having up to 24 carbon atoms. Preferably R 'is H or a straight chain radical and is preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl, eicosyl and docosyl.

R ² is preferably H, methyl, ethyl, propyl, butyl, pentyl or hexyl.

Particularly preferred nonlinear optical chromophores of the formula III correspond to the subformulae III a to III u. For the sake of simplicity, Phe here and in the following means 1,4-phenylene,

PlIe ₁ - <()> -, Phe _o - <( )> -, Phe " - (() \ - and

Het one of the preferred heteroaromatic groups selected from the group consisting of 2,5-pyrrolidinyl, -Franandiyl and -Thiophendiyl, Pyridindiyl, Pyrimidindiyl, triazinediyl and Indoldiyl.

D-Phe, -B HIa

D-Phe ₃ -B IHb

D-PhB ₁ -PhO ₂ -B IHc

D-Phe, -G ² -Phej-B IHd

D-Phe, -Phe-Phe ₂ -B IH

D-Pher-Het-PherB IHf

D-Pher-Het-G ^ Phez-B IHg

D-Phe, -Het-G ² -Phe ₂ -B III h

D-Phe, G'-Phe-P; ie ₂ -B Uli

D-Phe.-G'-Het-Phej-B HIj

D-Phe, -G'-Phe-G ² -Phe ₂ -B III k

D-Phe, -G'-Het-G ² -Pher B III I

D-Phe, -Phe-Phe-G ² -Pher-B Ulm

D-Phe, -Phe-Het-G ² -Phe ₂ -BHl η

D-Phe, -Het-Phe-G ² -Pher-B IHo

D-Phe.-G'-Phe-Phe-G'-Pher-B IHp

D-Phe ^ G'-Phe-Het-G ^ Phej-B IHq

D-Phe ^ G'-Het-Phe-G ^ Phe ^ B III r

D-Phe.-G'-Phe-Phe-Phe ^ B Ills

D-Phe ^ G'-Phe-Het-Phez-B IHt

D-Phe ^ G'-Het-Phe-Phez-B IHu

Of the polymers according to the invention with the non-linear optical chromophores according to the sub-formulas III a to III u are

especially those which have the indicated preferred meanings for D, D ¹ , B, B ', B ² , G ¹ , G ² , L, R' and R ² .

D-Phe, - means preferably

NR _n -

OR ^J

R ¹ O

-YO-

Phe "-B preferably signifies - (C JyNO ₂ '~ \ C y / ^{CN /}

CN

shark

COOR

shark

shark

shark

shark

-Ö- ^cN

shark

where Hal is F or Cl.

Of the NLO chromophores according to formula III, in particular those are preferred in which all radicals D ¹ , B 'and B ² H

mean or one of these radicals is different from H.

The compounds of formula III can be prepared by standard methods of organic chemistry. The reaction conditions can be taken from the standard works of Preparative Organic Chemistry, eg. B. 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 C = C double bonds can be prepared by reacting alkyl compounds with

corresponding aldehydes or ketones are condensed in a conventional manner. The condensation is advantageously carried out with the addition of a dehydrating agent such as AcetanhyJi iu, a base such as ammonia,

Ethylamine, piperidine, pyridine or a salt such as ammonium acetate or piperidinium acetate performed. As appropriate

also proves the addition of an inert solvent such. For example, hydrocarbons such as hexane, cyclohexane, benzene, toluene or xylene. The reaction temperature is usually between J ⁰ C and 25O ⁰ C, preferably between + 2O ⁰ C and 15O ⁰ C. At these temperatures, the reactions are usually completed after 15 minutes to 48 hours. Stilbenderivate can z. B.

by Wittig reaction or also by Wittig-Horner reaction of corresponding aromatic aldehydes and corresponding arylmethylphosphonium salts or phosphonates.

C = N or N = N double bonds can be obtained by analogous condensation reactions of aldehydes and primary amines, or nitroso compounds and primary amines, in a manner known to the person skilled in the art. In a further process for the preparation of said compounds, a (hetero) aryl halide is reacted with an olefin in the presence of a tertiary amine and a palladium catalyst (see RF Heck, Acc. Chem. Res. 1211979) 146). Suitable (hetero) aryl halides are, for example, chlorides, bromides and iodides, in particular bromides. The required for the success of the coupling reaction tertiary amines such. As triethylamine, are also suitable as a solvent. Suitable palladium catalysts are, for example, its salts, in particular Pd (II) acetate, together with organic phosphorus (III) compounds, for example triarylphosphanes. One possible emperaturen in the presence or absence of an inert solvent at ^T between about ⁰ ° C and 150 ° C, preferably between about 20 ° C and 100 ⁰ C, work; Suitable solvents are, for example, nitriles such as acetonitrile or hydrocarbons such as benzene or toluene. The (hetero) aryl halides used as starting materials and olefins are widely available commercially or can be prepared by literature methods, for example by halogenation of corresponding parent compounds or by elimination reactions of corresponding alcohols or halides.

Wei'erhin can be implemented for coupling of (hetero) aromatics (Hotero) arylhalogonide with (hetero) aryltin compounds or (hetero) arylboronic acids. These reactions are preferred with the addition of a catalyst such as. B. a palladium (O) complex in inert solvents such as hydrocarbons at high temperatures, eg. B. in boiling xylene, carried out under inert gas.

The vicinal position of electron donors and electron acceptors in multiple substitution may already be present at the stage of the starting compounds. First, a number of vicinal substituted starting compounds are already commercially available, such as. As phthalonitrile, o-dinitrobenzene, 3,4-dinitrotoluene, 3,4-dinitrobenzyl alcohol, 3-fluoro-4-nitrotoluene, o-phenylenediamine and o-dihalogenoaromatic and other unspecified vicinal here by electron donors or acceptors substituted aromatics (Merck, Darmstadt). On the other hand, they can be prepared by suitable substitution reactions from lower-substituted precursors, for example by nitration of 3-cyanotoluene, the S-cyano-nitrotoluene, optionally conversion of the nitro group via the amine with subsequent diazotization in the nitrile. O-phenylenediamine can be alkylated and converted into the benzaldehyde derivative by Vilsmeier's formylation. The reactions described are but a small selection of a wide variety of possible variations. The preparation methods are known in the art and in common textbooks, as well as in standard works of preparative organic chemistry, e.g. HOUBEN-WEYL, Methods of Organic Chemistry, Georg Thieme-Verlag Stuttgart. The starting compounds themselves are known or can be prepared analogously to known methods.

The polymers according to the invention are advantageously prepared so that the NLO chromophores are already covalently bound in a starting component, a tetracarboxylic dianhydride or a diamine. For the preparation of these starting components, the corresponding compounds, for example the preferred compounds of formula III are substituted accordingly. For example, the amino group -NR ' ₂ (D) in one or both R ^{1 is} monosubstituted in the ω-position by -OH or a halogen, such as Cl or Br, depending on whether the starting component comprises structural units of formula (f) or (g ) contains. Analogously, in order to prepare starting components which contain the NLO chromophore in the manner of a main chain (eg according to Scheme e), a compound functionalized in the donor and acceptor moiety is required. The polymers of the invention can be prepared by conventional methods. It is possible, for example, to react a corresponding tetracarboxylic acid or its dianhydride with a corresponding diamine to give the novel polyamic acids, as described, for example, in EP 0249881, EP 0231781, EP 0219336. Alternatively, a corresponding tetracarboxylic dianhydride can first be converted into a dicarboxylic acid diester, which is then reacted with a corresponding diamine Diamine further reacted to polyamide acid according to the invention (US 4,467,000).

The polyamic acid derivatives according to the invention can be prepared, for example, by first allowing the abovementioned dicarboxylic acid diesters to react first with their free COO (H) group under mild conditions. Usually they are converted into carboxylic acid halides, preferably in-chlorides with thionyl chloride. Subsequently, it is also reacted with a corresponding diamine, preferably under mild conditions, to form the polyamide ester according to the invention. Alternatively, the tetracarboxylic diester can also be polycondensed directly with the corresponding diamine corresponding to the polyamide ester according to the invention. Preferably, a carbodiimide, for example dicyclohexylcarbodiimide (DCC) is used as condensing agent, such as. B. described in DE 3411660.

From the polyamic acids or esters according to the invention, the polyimides according to the invention can be prepared by heating with elimination of water or alcohol. In particular, the imidization can be carried out at low temperatures (<200 ° C) when alcohol is split off instead of water. The degree of imidization is generally about 95 ° and more, i. it is also possible for acid or ester groups to be present in the polyimide according to the invention. The nonlinear optical arrangements according to the invention can be produced in various ways. For example, they can be prepared by first producing an inventive polyamic acid or its esters in an inert solvent, these by spin coating. Spread, print or dip, on a substrate surface, such as glass, applying and then aligns dipolar. The polyamide ester or the polyamic acid can also be imidized before the dipolar orientation.

The alignment is more conveniently carried out at a temperature close to the glass transition temperature of the polyimide, preferably by means of an electric field. The temperature can be both above and below the glass transition temperature. Subsequently, it is cooled in the electric field.

The polyimides according to the invention are distinguished by their generally very high glass transition temperatures and by their solvent resistance of the final polymer layer. The precursors, the polyamic acids or esters according to the invention are readily soluble. They can be applied, for example, by means of spin coating in a simple manner on substrate surfaces. All these advantages are for example in conventional NLO polymers, the poly (meth) acrylates, not given.

The polyimides according to the invention are thus suitable, for example, for use in optical components. By using the electro-optical effect or for frequency doubling and frequency mixing, they can thus in bulk

Materials and on the other hand be used in waveguide structures. The eriinclungsgomäßon polyimides may optionally act as a waveguide itself.

They are thus suitable for example in components in the field of integrated optics, sensor and telecommunications technology, for frequency doubling of laser light, for the production of Hichtkopplern, switching elements, modulators, parametric amplifiers, waveguide structures, light valves and other, known in the art, optical components. Optical components are described for example in EP 0218938.

The following examples serve to explain the invention.

Ausführungsbelsplele

Example 1 3,3 '- [N- (4'-nitrostilbenyl) -imino) -bis-4- (propyloxycarbonyl) phthalic anhydride

a) 4- (N, N-bis (3-hydroxypropyl) amino) -4'-nltrostilbene

To a solution of 20.0 g (83.2 mmol) 4-amino-4'-nitrostilbene (obtainable by reaction of 4-acetamidobenzaldehyde of 4-nitrophenylacetic acid in piperidine / pyridine and subsequent release of the amine) and 34.0 g (183 mmol) 3 -Oldpropanol in 120 ml of N-methyl'pyrimidin-2-one (NMP) are added 15.4 g (183 mmol) of sodium bicarbonate and the mixture is heated to 100 ⁰ C for 4 h. The mixture is poured into water, the precipitate is filtered off and recrystallized from ethanol. This gives deep red crystals

 Analog is produced:

4- (N, N-bis (3-hydroxypropyl amino) -3'-cyano-4'-nitrostilbene Violette, shimmering green crystals having a melting point of:. 168 ⁰ C.

b) 3,3 '- [N- (4'-nitrostilbenyl) -imino | -bls-4- (propyloxycarbonyl) phthalic anhydride

A solution of 6.45 g (18.1 mmol) of 4- (N, N-bis (3-hydroxypropyl) -amino-4'-nitrostilbene, 7.62 g (36.2 mmol) of 1,2,4-benzenetricarboxylic anhydride chlorio and 2.68 g (36.2 mmol) of pyridine in 50 ml of tetrahydrofuran (THF) is stirred at room temperature for 18 h, the mixture is poured into 25% hydrochloric acid and the precipitate is filtered off with suction, and the precipitate is purified by extraction with hot acetic acid (containing 5% of acetic anhydride). A red powder is obtained.

S ^ '- IN-O'-cyano ^' - nitrostilbenyD-iminoJ-up ^ -lpropoxycarbonyD-phthalic anhydride. A dark red powder is obtained.

Example 2 N, N-bis-S-acetamidobenzylM-amino-S'-cyano-1'-nitrostilbene

a) N.N-tBis-S-acetamidobenzyO ^ -amino-S'-cyano ^ '- nitrostilbene

To a solution of 50.0 g (189 mmol) of 4-amino-3'-cyano-4'-nitrostilbon (obtainable by reacting 2-nitro-5-methylbenzonitrile and 4-acetamidobenzaldehyde analogously to Example 1 a) and 86.5 g (471 mmol) 4-acetamidobenzyl chloride (prepared according to H. Piieninger, Chem. Ber. 87,22811954]) in 500 ml of NMP, 39.6 g (471 mmol) of sodium bicarbonate and 28.3 g of sodium iodide and the mixture heated to 100 ⁰ C for 4 h. It is allowed to cool, poured onto water and filtered from the precipitate. You get red crystals.

b) N, N- (bis-3-aminobenzyl) -4-amino-3'-cyano-4'-nitrostilbene

A suspension of 90.0 g (161 mmol) of N.N-IBis-S-acetamidobenzylM-amino-S'-cyano-1'-nitrostilbon in 2 l of ethanol and 400 ml of 37% hydrochloric acid is heated to boiling for 3 h. The mixture is concentrated to half the original volume and poured into dilute sodium hydroxide solution. The precipitate is filtered off with suction and on a silica gel column with dichloromethane / methanol 95: 5 chromatographies. This gives deep red crystals.

Example 3

A solution of 20 mmol of tetracarboxylic dianhydride and 20 mmol of diamine in 15 ml of NMP is stirred for 18 h at room temperature. Dilute with 20 ml of NMP and precipitate the polymer from ethanol.

According to this regulation are produced:

a) polyamic acid from 3,3 '- [N- (4'-nitrostilbenyl) -imino] -bis-4- (propyloxycarbonyl) phthalic anhydride (1 b) and m-phenylenediamine,

b) polyamic acid from S '' - IN-O'-cyano ^ '- nitrostilbenyD-iminoJ-bis ^ -propyloxycarbonyD-phthalic anhydride (1 b) and m-phenylenediamine,

c) polyamide acid from N.N-IBis-S-aminobenzyl-amino-S'-cyano-1'-nitrostilbene (2 b) and pyromellitic dianhydride,

d) polyamic acid from S.S'-IN-O-cyano ^ '- nitrostilbenyl-1-iminol-bis ^' - ipropyloxycarbonyD-phthalic anhydride (1b) and NN-IBis-S-aminobenzylM-amino-S'-cyano ^ ' nitrostilbene (2 b).

Example 4

In a modification of Example 3, polyimides 4 a, b, c and d are prepared according to 3a, b, c and d by adding the components

Stirred at 200 ⁰ C in NMP for 3 h.

Example 5

A solution of the polyamic acid of Example 3a (0.6 g) in 3.5 g NMP is prepared. The solution is filtered (filter with pore diameter 2 μ) to remove dust particles.

A glass plate coated with ITO (indium tin oxide) (4 cm χ 4 cm, thickness: 1.1 mm) is dissolved in neutral soap solution (Extran, Fa.

Merck) in the ultrasound for 10 minutes, then rinsed in double distilled water and rinsed with isopropanol. The polymer solution is spun on this glass plate (1000 U / min), then in vacuo at 100 ⁰ C for

Dried for 4 hours. On this film, a semitransparent gold electrode is evaporated.

The film is heated to 10 ° C in a vacuum oven; then a DC voltage of 100 V for 10 minutes at 13O ⁰ C is applied. In the electric field, the sample is cooled to room temperature at 2 ° C / min, then the field is switched off. The film is placed in the Sirahlengang of a Nd: YAG laser (λ = 1.06mm, pulse duration 7 nsec, Pulorgorgie 0.5mJ, 50 ° angle to the film surface). The incident light is partially frequency doubled.

Analogously, films of the polyamic acids of Examples 3b and c are prepared and tested. It is also observed frequency doubling.

Example β

It will be a film, prepared as described in Example 5, but wherein heated before the vapor deposition of the gold electrode in a vacuum oven for 2 h at 220 ⁰ C (imidization). After the vapor deposition, a DC voltage of 100V for 10 minutes at 200 ⁰ C is applied. Subsequently, the sample is cooled at 5 ° C / min to room temperature and proceeded to Example B. From the polyamic acids of Examples 3 b and c also polyimide films are prepared, oriented and examined. All films partially double the frequency of the irradiated light.

Example 7 Analogously to Example 5, a solution of the polyimide of Example 4a and by spin coating a film thereof is prepared. After this Vapor deposition of the gold electrode is continued according to Example 6. Similarly, polyimide films are prepared from the polyimides 4b and c, oriented and examined. All movies show good up

excellent frequency doubling efficiency.

Example 8 It becomes an optical device as described by R. Lytel et al. in proc. SPIE, Vol.824, p. 152 (1988), with the polymer Example 4a prepared. The material shows excellent waveguiding properties.

Claims (8)

1. polyamic acids and their reactive derivatives with chemically bonded nonlinear optically active chromophores, which can be converted by cyclization in polyimides, characterized in that the nonlinear optically active chromophores have a positive value for the quadratic hyperpolarizability (ß). 2. polyamic acids and their reactive derivatives according to claim 1, characterized in that the non-linear optically active chromophores consist of Elßktronendonor-Aakzeptor-substituted conjugated π-systems. 3. Polymer materials based on polyimides, obtainable by cyclization of polymers according to claim 1 or 2. 4. Non-linear optical arrangements, characterized in that they contain polymers according to claim 1 or 2 or polymer materials according to claim 3. 5. A process for the preparation of nonlinear optical arrangements according to claim 4, characterized in that applying polymers according to claim 1 or 2 or polymer materials according to claim 3 on a substrate and aligns dipolar. 6. A process for the preparation of nonlinear optical arrangements according to claim 4, characterized in that applying polymers according to claim 1 or 2 on a substrate, imidized and optionally aligned dipolar. 7. Use of non-linear optical arrangements according to claim 4 in optical components. 8. An optical component containing nonlinear optical arrangements according to claim 4.