DE4312243A1 - Polymeric cpd. with nonlinear optical properties for holography etc. - contains imide-, iso:imide- or amide-type bound chromophores, used for waveguide - Google Patents

Abstract

A polymeric organic cpd. container imide, isoimide or amide type bound chromophones with non-linear optical properties, where the bridge between the polymer chain (a) and chromophore (b) consists of C and N atoms and in the case of an amide type cpd. has only one CO member. Also claimed are (i) the prepn. of the cpd. by forming a homo, co or terpolymer from monomers contg. functional gps. capable of undergoing condensn. and/or polymerisation and reacting with a chromophone having a gp. capable of condensn. or addn.; and (ii) a waveguide of three layers of polymer film in which the middle film comprises the above cpd. and has a higher refractive index than the other two layers. USE - Used for holographic devices, modulators, waveguides, sensors, etc. and either (inert) optical and electrooptical devices.

Description

The invention relates to polymeric organic compounds which in Molecular imide, isoimide or amide-like chromophores not bound contain linear optical properties, their manufacture and their Use, especially for optical, integrated optical, electro optical, photorefractive or holographic functional elements (Devi ces), as modulators, switches, directional couplers, amplifiers, waveguides, Sensors etc. as well as for frequency conversion, in particular frequency ver duplication.

The new compounds are a) polymer chains to which b) chromophores nonlinear optical properties (NLO chromophores) amide, imide or are bound isoimide-like, the bridge between polymer chain (a) and chromophore (b) consists only of nitrogen and carbon atoms and where in the case of the amide-like bond said bridge is only one -CO- Member (a carbonyl group) contains. It doesn't matter which one other atoms / atom groups / substituents on the nitrogen and carbon atoms are bound. Preferably the bridge contains no urea grouping between chromophore and polymer chain (interm member of the formula -NH-CO-NH-).

The polymer chains (a) (before the reaction with the chromophores) are uni- (= Homo-), copolymers or terpolymers made from monomeric compounds with several functional group capable of condensation and / or polymerization pen, generally compounds from the group of aliphatic and cycli shear anhydrides and imides, e.g. B. maleic anhydride, maleimide, Methacrylic anhydride, itaconic anhydride, citraconic anhydride and Compounds of formulas 1 to 6

formula 1

wherein the two R ₁ a independently of one another hydrogen, chlorine, C _1-5 alkyl, or a R₁a also phenyl, C _1-5 alkoxy, C _1-5 alkylcarbonyloxy, C _1-5 alkoxymethyl, C _1-5 -Alkylcarbonyl oxymethyl, allyloxycarbonyl or a radical of the formula

and R _{11 is} hydrogen or C _1-5 alkyl;

Formula 2

wherein all R ₁₂ , independently of hydrogen or methyl,
R _{13 is} a bridge member of the formula -O-, -S-, -SO ₂ - -CH ₂ O-, -CH ₂ OCH ₂ -, -CO-, - (C (R ₁₄ ) ₂ ) - or - (Si ( R ₁₄ ) ₂ ) -
and all R _{14 are} independently hydrogen, methyl or C _4-6 cycloalkyl or together ω-C _4-6 alkylene;

Formula 3

Furan, thiophene, 2,3- or 3,4-dihydrofuran, 2,3-dihydropyran, cyclo hexene, indene, indole or NC _1-3 alkyl indole;

Formula 4

wherein a) R _{15 is} a -CH ₂ bridge
one R ₁₆ and one R _{17 are} hydrogen, the remaining R ₁₆ and R _{17 are} the direct bond
or b) R _{15 is} a -CH ₂ - or -O bridge,
all R ₁₆ and R ₁₇ independently of one another are hydrogen or a radical of the formula -CH = CH ₂ , -CH = CH-CH ₃ , -C (CH ₃ ) = CH ₂ , -CHO or -COCH ₃ or
the two R ₁₆ together are a radical of the formula = CH ₂ or = CH-CH ₃ and the two R _{17 are} each hydrogen, or an R ₁₆ with an R _{17 is} a bridge of the formula -CH ₂ -CH = CH- or -CO- O-CO- and the remaining R ₁₆ and R _{17 are} hydrogen;

Formula 5

wherein R ₁₈ (in ortho, meta or para position) hydroxyl, carboxyl, formyl or a radical of the formula

R _{18a is} hydrogen, fluorine or chlorine,
R₁₉ is hydrogen, C _1-2 alkyl or cyan and
R₂₀ is hydrogen, hydroxyl or C _1-3 alkoxy.

Formula 6

wherein the two R _{21 are} independently halogen, especially chlorine or bromine, or C _1-4 alkyl and
R _{22 is} vinyl or allyl.

The composition of the copolymers of the cyclic anhydrides with the Compounds of formulas 1, 3, 4, 5 and 6 is generally 1:10 to 10: 1, preferably 1: 1, that of cyclic anhydrides with compounds of  Formula 2 is preferably 2: 1. These "base polymers" (polymer chains a) and their manufacture are largely known from the literature (e.g. G. Sackmann: "Polymerization of unsaturated polycarboxylic acids and their Derivatives ", in" Methods of org. Chemistry ", Houben-Weyl, 4th Edition, Vol. E20 / 3, pp. 1234 ff., Europ. 0324547 A2; Kwang-Duk Ahn et al. "Synthesis and polymerization of N- (tert-butyloxycarbonyl) maleimide and facile de protection of polymer side-chain t-BOC groups ", published in" Polymer ", 1992, Vol 33, No. 22, pp 4851-56, see also Examples 1 to 15 below), the unknown polymers can be the skilled person easy to produce in analogy to known methods.

The monomeric chromophores b) with non-linear optical properties contain one for reaction with the polymer chains a) preferably with an acid derivative (anhydride, acid chloride), for imide, isoimide or Amide-forming group, they correspond to formulas I to V

where in these formulas R _{1 is} hydrogen, halogen, carboxyl, cyan or rhodan,
R _{2 is} hydrogen, halogen, cyan, carboxyl or nitro,
R _{3 is} hydrogen, C _1-2 -alkyl, C _1-2 -alkoxy, amino-C _1-2 -alkyl or C _1-2 -alkylcarbonylamino,
R _{3 ′ is} hydrogen, C _1-2 alkyl or C _1-2 alkoxy,
R _{4 is} hydrogen or C _1-2 alkoxy,
R _{4 ′ is} hydrogen or C _1-2 alkoxy,
R _{5 is} a group of the formula

or if R₃ is amino-C _1-2 -alkyl, also di- (C _1-4 -alkyl) -amino,
R ₆ cyan, nitro, C _1-2 alkylsulfonyl, aminosulfonyl, dicyanovinyl, tricyanovinyl, di- (C _1-4 -alkoxycarbonyl) -vinyl or a group of the formula -CH = CH-NO ₂ , -C (C _{1- 4} -alkyl) = C (CN) ₂ ,

R _{7 is} hydrogen or nitro,
R _{8 is} hydrogen, C _1-4 alkyl, benzyl or C ₁ - ₂ alkylcarbonyloxy-C ₂ - ₃ alkyl,
n is zero or a number from 1 to 9,
p zero, 1 or 2
A _{1 is} the direct bond or a bridge member of the formula -CH = CH-, -N = CH- or -CH = N-,
A ₂ oxygen or sulfur,
B is a group of the formula

W ₁ tricyanovinyl, nitro or a group of the formula -CHO, -CH = C (CN) ₂ , -C (C _1-4 alkyl) = C (CN) ₂,

or -CH = C (COO-C _1-4 alkyl) ₂,

W _{2 is} hydrogen, chlorine, C _1-4 alkyl or phenyl,
Y nitro, formyl, cyano, C _1-2 alkylsulfonyl, dicyanovinyl or tricyanovinyl,
Z ₁ = N-, = CH- or = C (NO ₂ ) - and
Z ₂ = N-, = CH- or = C (NO ₂ ) - mean
where halogen is preferably chlorine and bromine.

In formulas I to V preferably mean independently of one another

R _{1 is} hydrogen, chlorine or bromine,
R _{2 is} hydrogen, chlorine, bromine, cyan or nitro,
R _{3 is} hydrogen, methyl or C _1-2 alkylcarbonylamino,
R _{3 ′ is} hydrogen or methyl,
R _{4 is} hydrogen or C _1-2 alkoxy,
R ₅ (NC _1-2 alkyl-N-ω-C _1-3 alkyl) amino, (N-benzyl-N-γ-aminopropyl) amino or N-piperazyl,
R _{4 ′ is} hydrogen,
R ₆ cyan, nitro, dicyanovinyl or C _1-2 alkylsulfonyl, R ₇ nitro,
R _{8 is} C _1-4 alkyl or benzyl,
n 1, 2 or 3, preferably 2 or 3,
p zero or 1, preferably zero,
A ₂ sulfur,
B is a group of the formula b or c (above),
W ₁ dicyanvinyl, tricianvinyl, formyl or di- (C _1-2 -alkoxycarbonyl) -vinyl,
W _{2 is} hydrogen, chlorine, methyl or phenyl,
Y nitro or cyan,
Z ₁ = CH-, = N- or = C (NO ₂ ) - and
Z ₂ = CH-, = N- or = C (NO ₂ ) -.

The chromophores are bonded to the polymer chain (a) via the amino or imino nitrogen atom of the substituent R ₅ or R ₃ , preferably via R _{5, in the} manner of an imide, isoimide or amide.

The chromophores b) with non-linear optical properties and their Manufacture are partly (as dyes, brighteners or intermediate products for dyes). If they are not known, this is done their preparation in analogy to the synthesis of similar, known verb  fertilize; see also Examples 17, 18, 71, 85 below.

The compounds of the invention are prepared by, in in any order, the uni-, co- or terpolymers (= polymer chains a) from the monomeric compounds with several for the polymerization and / or condensation capable functional groups and with the Chromophores (b), which is a group capable of condensation or addition contained, brings to reaction.

The monomeric compounds with which the uni, Co or optionally terpolymer chains (a) are built up, one or two, in particular a group capable of polymerization and one for Condensation with the chromophore (b) functional group (the are z. B. the compounds from the alipha group mentioned above table and cyclic anhydrides and optionally amides, which, as Copolymers which contain reaction products of the formulas 1 to 6). Chromophores (b) include those of the formulas I to V, with a Amino or imino group, preferably also as salts, e.g. B. as a hydro chloride, hydrosulfate or sulfate or with a protected amino group can be present. These chromophores react with the condensate functional groups (only) with the formation of an amide and can then be cyclized to the isoimide and / or the imide.

In the case of the polymeric organic compounds in which the polymer chains (a) Unipolymerisate contain the corresponding monomeric compounds several for condensation and / or polymerization, preferably one each for condensation and a functional group capable of polymerization. Unipolymeric compounds preferably contain acrylic acid anhydride, Methacrylic anhydride, citraconic anhydride or itaconic anhydride derived polymer components.

The groups of the polymers capable of amide, isoimide or imide formation Links are generally functional carboxylic acid derivatives, in particular their carboxylic anhydrides. Carboxylic acid halides can also be used in this Case to be considered. The reaction conditions for production these new compounds are known to the person skilled in the art.

In the following examples, u. a. the reactions more polymer-bound cyclic carboxylic anhydrides (as mentioned at the beginning) with chromo phores containing an amino group (compounds of the formulas I to V), and subsequent cyclization (with elimination of water) with Cycli sation reagents (compounds promoting the elimination of water, esp special acetic anhydride). Similar reactions are also known from the literature, e.g. B. J.A. Moore et al. Tetrahedron Lett. 32, 3449, (1991): Reaction of activated polymer-bound cyclic carbon acid anhydrides or carboxylic acid chlorides with dye-containing amines (Ammonium salts or N-protected amines); or Europ. Patent application 0 324 547. Both the first amides formed with a free carboxylic acid group, or the isoimides (see e.g. Ver publication of F.W. Haris et al. "Polyimides containing oxyethylene units, III. Isoimide Precursor to semicrystalline Polyimides " in Polymer Preprints 26, (1985), pp. 287/8) as well as that in further step reaction obtained imides to the verbin according to the invention counting.

Chromophores with a secondary amino were used as the starting substance group, especially with a terminal piperazyl group, lead in this case to amide acids (Examples 118 to 122, 127 and 128) with a free carboxylic acid group per chromophore residue.

The NLO polymers according to the invention can also polymerize by reaction bound cyclic carboxylic acid anhydrides with isocyanate groups ent holding chromophores (R.A. Meyers, J. Polym. Sci., Part A1, 7, (1969), p. 2757), the intermediate Ver Bindings with 7-membered ring structure the subject of the present Er are.

Compounds according to the invention can also be obtained by free radicals Copolymerization of chromophore-functionalized maleimides (from Maleic anhydride and a chromophore with an amino group) with vinyl connections (e.g. of formulas 1 to 6, above).

Furthermore, compounds according to the invention can also be polymerized by reaction bonded cyclic carboximides (especially maleimides)  with chromophores containing a primary hydroxyl group (Mitsunobu reaction, see also I. Cabrera et al. Angew. Chemie, 103, (1991), p. 106-8).

Compounds according to the invention with a dicyanovinyl or dicyanovinyl ester group can also (standard method, see eg the book "Organi kum ", organic, basic chemical internship, 15th edition, VEB, German Verlag der Wissenschaften, Berlin 1977, pages 571 ff.) By reaction a polymer containing chromophore (prepared as described above) aromatic aldehyde group, with malononitrile or cyanmalonic acid esters to be manufactured.

As can also be seen from the examples, there are those according to the invention Polymers not (only) from compounds in which each is repetitive Polymer unit carries a residue with chromophoric properties.

While it is generally desirable, for obvious reasons, the Number of chromophores with non-linear optical properties (b) in To have molecule as high as possible, however this is from reaction kinetic reasons not always possible. As can be seen from the examples are chromophore contents of 98% (chromophore residues per themselves fetching polymer unit, see example 122) in practice the maximum achievable concentration (except when the chromophores start with the polymerizable compounds are implemented).

The molecular weight of the polymer chains (without chromophores) for the compounds according to the invention is generally between 2 · 10 ³ to 5 · 10 ⁶ , in particular between 1 · 10 ⁴ to 3 · 10 ⁵ . In order to obtain the corresponding desired molecular weights, the initiator concentration (initiator is preferably azoisobutyronitrile), the monomer concentration and / or the reaction temperature can be varied in a manner known to the person skilled in the art. Furthermore, the average molecular weights can be controlled by regulator additives (known to the person skilled in the art) (for example a mercaptan).

The polymeric compounds of the invention are mainly in Form of thin films, or for coating optical, or  electro-optical components, for the production of non-linear optical Effects, e.g. B. as modulators, electro-optical switches, for frequency conversion, or frequency doubling, etc. used. The polymers are readily soluble in organic solvents, making it easy to process (Spin coating, dip coating). The high glass tempera is also worth mentioning copolymers, their long-term durability and their high not linear coefficients for electro-optical and non-linear optical Effects. The polymer films made with the new compounds show also very good waveguide properties (low attenuation).

Compared to the previously known compounds, which are used for the same purpose, and production methods for those compounds, the compounds according to the invention have the following advantages: high molecular weight (up to 5 · 10 ⁶ ), good solubility in organic solvents, very good processability, simple synthesis and above all also a high glass transition temperature with high non-linearity and long-term stability of the high non-linearity, this particularly in the case of the compounds which contain a radical of the formula 4.

According to the invention are also one or more polymer layers existing polymer films for laser light of different wavelengths have good waveguiding properties. Wavelength is preferred ter arrangements of three layers in which both the top and the lower layer has a smaller refractive index than that middle layer, and the glass temperature Tg of both the top and the lower layer is larger or at least as large as that of the middle layer. Generally, the top layer (Top Buffer) from polymer chains (a) without chromophore, with very little NLO chro mophor (b) or with non-NLO active chromophore (c), the middle Layer (EO, Main Layer) of polymer chains (a) with a maximum con concentration on NLO chromophore and the bottom layer (bottom buffer) again like the top layer, but regardless, from polymer chains (a) without chromophore, with very little NLO chromophore (b) or with non- NLO-active chromophore (c).  

Preferred examples of non-NLO chromophores (c) correspond to those Formulas VI and VII

wherein the symbols A ₂ , R ₃ , R ₄ and R _{5 have} the meanings given above
and Y ₂ and Y ₃ independently of one another are hydrogen, fluorine, chlorine, bromine, methyl or methoxy and the cores A and B are further substituents from the group chlorine, bromine, amino, mono- or di-C _1-3 -alkylamino, C Can carry _1-3 alkoxy or hydroxyl.

Examples 109 to 114 describe such chromophores.

EXAMPLES

Unless otherwise stated, the parts mean parts by weight and Percentages by weight. The temperatures are in degrees Celsius understand.

In Examples 1 to 6 and 13 to 16 is the production of poly Merketten (a), in Examples 7 to 12 the production multifunction neller compounds of the formulas 1 to 6, in Examples 17 to 114 die Production of chromophores, in Examples 115 to 204 is the Her Position of the chromophoric polymers described. The example le 205 to 211 are application examples.  

example 1

Poly- (styrene-co-maleic anhydride) is based on D. Braun, H. Cherdron, W. Kern, Internship in Macromolecular Organic Chemistry, 2nd ed., P. 220, Dr. A. Hüthig Verlag, Heidelberg 1971, manufactured; toluene is used as the solvent and azo-bis-isobutyronitrile as Initiator used.

Copolymers of different molecular weights are made by changing the Monomer and the initiator concentration according to those skilled in the art Methods made.

Extremely high molecular weight poly (styrene-co-maleic anhydride) is, according to G. Sackmann in Houben-Weyl, Methods of Organic Chemistry E20, Part 3, 4. Ed. P. 1243, H. Bartel, J. Falbe (Eds.), T. Thieme Verlag.

Analogous to the above regulations, poly- (α-methylstyrene-co- Maleic anhydride) and poly (norbornadiene-co-maleic anhydride) produced.

Example 2

Poly (ethylene-co-maleic anhydride) is based on G. Sackmann in Houben-Weyl, Methods of Organic Chemistry, E20, Part 3, 4th ed. P. 1242, H. Bartel, J. Falbe (Eds.), G. Thieme Verlag. Here is toluene as a solvent and azo-bis-isobutyronitrile as an initiator used.

Analogous to the above procedure, poly- (propen-co-maleic acid anhydride) and poly (isobutene-co-maleic anhydride).

Example 3 Poly (ethyl vinyl ether-co-maleic anhydride)

A solution of 14.71 g maleic anhydride, 14.4 ml ethyl vinyl ether and 123 mg azoisobutyronitrile in 200 ml toluene is 5 minutes with nitrogen rinsed and the solution was then stirred at 60 ° for 1 hour. The The copolymer precipitated during the reaction is filtered off with 200 ml Washed toluene and dried at 50 ° / 33 hPa.  

Example 4

Poly (furan-co-maleic anhydride) is, according to N.G. Gaylord, M. Martan, FROM. Deshpande, J. Polym. Sci., Polym. Chem. Ed., 16, 1527 (1978) posed.

The Diels-Alder product is made from furan and Polymerized maleic anhydride.

Example 5

Poly (divinyl sulfone-co-maleic anhydride) is made according to G.B. Butler, J. Macromol. Sci. Chem., AS, 219 (1971).

Example 6

Poly (methacrylic anhydride) is described by A. Crawshaw, G.B. Butler, J.Am. Chem. Soc., 80, 5464 (1958).

Example 7

The literature-known m-formyl styrene is made from m-bromobenzaldehyde and Ethylene analogous to a regulation by W. Heitz et. al., Makromol. Chem. 189, 119 (1988). Kp .: 121 ° / 28 mbar

Example 8

The literature-known m-bromocinnamic acid is made by Knoevenagelreaktion m-bromobenzaldehyde and malonic acid according to: author collective, organic, Organic chemical internship, VEB German Publishing House of Sciences, Berlin 1977, p. 572, variant B, manufactured. Mp .: 180 °  

Example 9

m-Vinyl cinnamic acid is converted from m-vinyl benzaldehyde by Knoevenagel reaction and malonic acid analogous to the procedure in Example 8 (Lit .: authors collective, organic, organic-chemical internship, VEB German Verlag der Wissenschaften, Berlin 1977, p. 572, variant B.) or from m-bromocinnamic acid and ethylene analogous to a regulation by W. Heitz et al., Macromol. Chem. 189, 119 (1988):

A reaction mixture of 63.7 g m-bromocinnamic acid, 1.75 g tri-o-tolyl phosphine and 0.63 g palladium acetate in 280 ml acetonitrile and 220 ml tri ethylamine in an autoclave is initially 2 minutes with nitrogen rinsed and then pressed 15 bar ethylene at room temperature. The temperature is increased to 125 ° with a heating rate of 2 ° / minute and held at 125 ° for 20 hours; the pressure rises 35 bar. The reaction mixture is allowed to cool to room temperature and gives the filtered mixture to a mixture of 165 ml conc. hydrochloric acid and 450 ml of ice water. The brown mixture obtained is 3 times with each 400 ml of diethyl ether extracted, the combined ether phases filtered and Extracted twice with 300 ml of 20% sodium carbonate solution. The watery Phase is slowly concentrated to a mixture of 260 ml. Hydrochloric acid and 500 ml Given ice water. The white product which has precipitated is filtered off and dried in vacuo at room temperature. Mp: 152-155 ° C.

Example 10

The m-vinyl cinnamic acid methyl ester known from the literature is obtained from m-vinyl cinnamic acid by reaction with thionyl chloride and subsequent esterification with methanol according to a standard method (Lit .: authors collective, organic, organic chemical internship, VEB Deutscher Verlag der Wissenschaften, Berlin 1977, p. 505) . R _f (silica gel / toluene) = 0.41

Example 11

m-Vinyl-α-cyano-cinnamic acid methyl ester is obtained by Knoevenagel reaction from m-vinylbenzaldehyde and methyl cyanoacetate according to: Autorenkollek tiv, organic, organic-chemical internship, VEB German publisher of Sciences, Berlin 1977, p. 572, variant A:

A mixture of 61 g of m-vinylbenzaldehyde, 41 ml of methyl cyanoacetate, 4.1 g of β-alanine, 0.5 g of hydroquinone and 5.3 ml of glacial acetic acid in 250 ml of toluene are boiled under reflux in a water separator until no more water is separated off ( 1.5 h). After cooling, the mixture is extracted 3 times with 350 ml of approximately 4% sodium carbonate solution and once with 400 ml of water. The organic phase is diluted with 400 ml of methylene chloride and dried over sodium sulfate. After the solvent has been distilled off, the product is recrystallized from toluene / hexane.
R _f (silica gel / toluene) = 0.43
IR (KBr): 2225 cm ^-1 , m, CN; 1724 cm ^-1 , s, methyl ester; 1608 cm ^-1 , s, C = C.

Example 12

N-Allyl-2,3-dimethyl-maleimide is made from 2,3-dimethyl-maleic anhydride and allylamine according to the Ciba-Geigy patent, DE 29 34 550. Kp .: 98 ° / 1 mbar.  

Example 13 Poly (maleic anhydride-co-allyl-2,3-dimethylmaleimide)

A solution of 30.79 g allyl-2,3-dimethylmaleimide, 17.36 g maleic anhydride and 581 mg azo-bisisobutyronitrile in 40 ml toluene is gassed with oxygen-free nitrogen for 5 minutes and then in a gas-tight flask for 24 hours 70 ° tempered. The reaction mixture is diluted with 120 ml of tetrahydrofuran and slowly added dropwise to 1.9 liters of methanol with stirring. The precipitated copolymer is filtered off through a glass frit and dried to constant weight.
IR (KB1): 1701 cm ^-1 , s, C = O maleimide; 1784 cm ^-1 , s, 1860 cm ^-1 , w, C = O anhydride
Elemental analysis: C: 58.2%, H: 5.2%, N: 5.3%, O: 31.3%

Example 14 Poly (maleic anhydride-co-m-vinyl-α-cyano-cinnamic acid methyl ester)

A filtered solution of 1 g of m-vinyl-α-cyano-cinnamic acid methyl ester, 460 mg of maleic anhydride and 15.5 mg of azo-bis-isobutyronitrile in 15 ml of toluene is gassed with oxygen-free nitrogen for 3 minutes and then in a gas-tight flask for 17 hours tempered at 60 °. The precipitated copolymer is filtered off through a glass frit, washed with toluene and dried to constant weight.
UV (CH ₂ Cl ₂ ): 302 nm, methyl cyanocinnamate
IR (KBr): 2225 cm ^-1 , w, CN; 1782, s, 1859 cm ^-1 , w, C = O anhydride; 1733 cm ^-1 , C = O methyl ester; 1610 cm ^-1 , m, C = C.

Analogous to the above procedure:
Poly (m-vinyl cinnamic acid methyl ester-co-maleic anhydride),
IR (KBr): 1781, s, 1859 cm ^-1 , w, C = O anhydride; 1717 cm ^-1 , C = O methyl ester; 1639 cm ^-1 , m, C = C
Poly- (m-vinyl cinnamic acid-co-citraconic anhydride) and poly- (m-vinyl cinnamic acid-co-itaconic anhydride).

Example 15

Poly (m-formylstyrene-co-maleic anhydride) is prepared following the procedure in Example 1; the crude product is dissolved in dimethylformamide and reprecipitated in methanol.
IR (KBr): 1858 cm ^-1 , w, 1780 cm ^-1 , s, C = O anhydride; 1699 cm ^-1 , s, CHO.

Example 16

p-Hydroxystyrene is produced according to DOS 22 48 525 (1973), Example 5, Mp: 69-71 ° C.

Poly (p-hydroxystyrene-co-maleic anhydride) is prepared following the procedure in Example 1; a mixture of toluene / acetone 1/1 is used as solvent and the copolymer is then precipitated in diethyl ether.
IR (KBr): 3447 cm ^-1 , b, OH; 1856 cm ^-1 , m, 1772 cm ^-1 , s, C = O anhydride.

Manufacture of chromophores Example 17 Preparation of 4-nitro-4 ′ - (N-ethyl-N-β-aminoethyl) -1,1′-azobenzene, Hydrochloride N-ethyl-N-cyanomethyl aniline

A mixture of 1051 g of N-ethyl is in a 10-liter flask aniline, 1060 ml dimethylformamide, 206 g magnesium oxide and 22.5 potassium iodide submitted. It is heated to 100 ° and within about 90 min 569 ml of chloroacetonitrile were added dropwise. The mixture is left at 120 ° for about 2 hours stir and then add 340 ml of acetic anhydride at 100 °, one brown solution arises. After 30 minutes, 3200 ml of toluene are added at about 75 ° and 3200 ml of water and after cooling, the reaction mixture is in filled a separatory funnel. The aqueous phase is separated off and extracted twice with 500 ml of toluene. The united organic Phases are washed twice with 500 ml of water each time, it is over Dried overnight over magnesium sulfate and then the solution medium removed in a rotary evaporator. 1484.5 g of crude product are obtained as a brown oil that is processed directly.  

N-ethyl-N- (β-aminoaethyl) aniline

In a 5 l steel autoclave, a mixture of 3000 ml isopropanol, 350 ml of liquid ammonia, 742 g of N-ethyl-N-cyanomethyl-aniline and 74 g Nickel catalyst H1-50 from BASF presented. At 90 ° and 10 bar Pressure is hydrogenated for 2.5 hours. The consumption of hydrogen is thereby 190 l. The light brown solution is at 50 ° and initially 500 mbar, then concentrated to 20 mbar in a rotary evaporator, about 730 g of one light brown oil can be obtained. Distillation at 96-98 ° and 0.02 mbar provides 587.3 g (84.1% of theory) of product as a colorless liquid.

Coupling with 4-nitroaniline

1650 ml of water, 528 g of 30% hydrochloric acid are placed in a 3 l sulfonation flask and 174 g of 4-nitroaniline (95.5%) for about 2 hours at room temperature stirs. By external cooling and adding 200 g ice to the reaction mixture is cooled to 0 °. 250 ml of a 33% sodium nitrite Solution and allowed to stir at 0-5 ° for 2 h. Then you destroy the Excess nitrite with sulfamic acid and filtered through a glass sinter nutsche G1.

The filtrate is placed in a 10 liter sulfonation flask at 0 ° and it is a solution was added dropwise at 0 ° within one hour, by mixing of 205.3 g of N-ethyl-N- (β-aminoaethyl) aniline and 300 g of water as well dropwise addition of 30% hydrochloric acid up to pH 1 was put. The mixture is stirred at 0 ° for 2 hours and then opened overnight Warm RT. 2 l of water are added and the pH is increased to 2 Add 30% sodium hydroxide solution, which causes dense precipitation. To 2 hours stirring is filtered off with a glass sintered filter G3 and in Vacuum dried at approx. 80 °. 500 g of a red dye are obtained.

For cleaning, the product in 200 ml of dimethylformamide at 100 ° warms, insoluble components are filtered off, the warm filtrate becomes mixed with 4000 ml of chloroform and allowed to crystallize. It is filtered off, washed with 2000 ml of chloroform, dried in vacuo and receives 258 g of dye of the following formula in the hydrochloride form:

Rf value = 0.43:
Thin layer chromatography with finished films POLYGRAM SIL G / UV 254 from Macherey-Nagel, eluent: mixture of 50 parts toluene, 20 parts ethanol, 10 parts triethylamine, 10 parts dioxane and 2.5 parts water.

Example 18 N-methyl-N- (γ-aminopropyl) aniline

A mixture of 4300 ml of isopropanol, 185 ml of liquid ammonia, 494 g of N-methyl-N-cyanaethyl-aniline and 50 g of nickel catalyst H1-50 from BASF is placed in a 5-liter steel autoclave. The mixture is hydrogenated for 2 hours at 90 ° and 5 bar pressure. The consumption of hydrogen is 141 l. The light brown solution is concentrated at 45 ° and 135 mbar in a rotary evaporator, giving 656.6 g of a light brown oil. Distillation at 83 ° and 0.015 mbar gives 479.4 g (94.7% of theory) of product as a colorless liquid.
Coupling with 2-chloro-4-nitroaniline:

170 g of ice water are stirred into 270 ml of ice water in a 1.5 l sulfonation flask 95% sulfuric acid dropped. At room temperature, 96 g of 2-chloro-4- nitroaniline is added and the mixture is stirred for about 1 h. It gets to 0 °. cooled, 113 g of a 33% sodium nitrite solution are added and lets stir for 3 h. Then you destroy the excess nitrite with Amidosulfonic acid.

89 g of N-methyl-N- (γ-aminopropyl) - are placed in a 3.5 l sulfonation flask. aniline from 1a) in 200 ml of DMF at 0 °. Within about 1-2 hours the yellow-brown diazonium salt suspension with a peristaltic pump added, with simultaneous dropwise addition of 30% sodium hydroxide solution a pH of 1.5 is maintained and the temperature of the reaction mixture is always approx. 0-5 °. The mixture is allowed to stir for 3 hours, then the pH to approx. 5, filtered off after a further 2 h and dried in a vacuum at approx. 60-80 °. About 178 g of a red dye are obtained.

For cleaning, the dye is about 3-4 times in a 2.5 l sulfonation flask suspended in 2 l of toluene, the mixture is heated to reflux for 2 h in each case and  then filtered off. Then the product is made with a mixture 2 l of methanol and 200 ml of 10% sodium hydroxide solution at room temperature tur stirred, it is filtered off and dried in vacuo at about 60 °. About 149 g of the dye of the formula are obtained:

Rf value = 0.31:
Thin layer chromatography with finished films POLYGRAM SIL G / UV 254 from Macherey-Nagel, eluent: mixture of 50 parts toluene, 20 parts ethanol, 10 parts triethylamine, 10 parts dioxane and 2.5 parts water.

The chromophores given in Table 1 below correspond to Formula Ia;

and are known by diazotization of the corresponding starting materials Methods and coupling in analogy to the information in Example 17 as corresponding ammonium salt or Example 18 as "free amine" herge poses.  

Table 1

The chromophores in Table 2 below correspond to the formula

and are known by diazotization of the corresponding starting materials Methods and coupling in analogy to the information in Examples 17 and 18 produced.

Table 2

Example 71 5-nitro-2-piperazino-pyrimidine

A mixture of 1000 ml of water, 5.47 g of thiourea, 6.2 g of piperazine and 10 g of the sodium salt of nitromalonaldehyde (produced according to Organic Synthesis, Coll. Vol. IV, page 844) is placed in a 2.5 l sulfonation flask. heated to 70 ° and stirred for 15 min at this temperature. The mixture is allowed to cool and the reaction mixture is concentrated in a rotary evaporator under vacuum until crystallization occurs. The mixture is left to stand overnight, filtered off and dried in vacuo. 2.3 g of product are obtained.
Rf value = 0.69:
Thin layer chromatography with finished films POLYGRAM SIL G / UV254 from Macherey-Nagel, eluent: mixture of 30 parts of ethyl methyl ketone, 10 parts of diethylamine and 12 parts of a 25% ammonia solution.

The chromophores known from the literature correspond to Table 3 below of the formula

they are manufactured according to known methods.  

Table 3

Example 79a

The compound of the formula 3b is made by the known methods on the following Made way:

The chromophores in Table 4 below correspond to the formula

they are known by diazotization of the corresponding educts Methods and coupling in analogy to the information in Examples 17 and 18 produced.

Example 85

In a 0.5 l sulfonation flask with stirrer, thermometer and external cooling 158 g of 98% sulfuric acid) are introduced. 31.5 g of 2-amino-4-chloro-5- dicyanovinyl-thiazole (made from 2-amino-4-chloro-5-formyl-thiazole and malononitrile in analogy to DOS 31 08 077, Example 101c) added with good stirring within about 30 min at 0-5 °. At 0-3 ° become 48 g of a 40% solution of nitrosylsulfuric acid within 1 h added dropwise in sulfuric acid (98%) and it is replenished at 0-3 ° for 3 h stirs.

In a 2.5 l sulfonation flask with stirrer, thermometer and external cooling 150 g of ice are first mixed with 17 g of sulfuric acid (98%). Then 29 g of N-ethyl-N- (γ-aminopropyl) -m-toluidine (prepared from N- Aethyl-N- (β-cyano-ethyl) -m-toluidine in analogy to Example 18) added ben, the resulting solution is cooled to 0 ° and there are still 1-2 g Amidosulfonic acid added. The above "diazonium salt solution" becomes internal pumped in half an hour, with external cooling and portions wise addition of a total of 500-800 g of ice at a temperature of 0-5 °  is held. The mixture is stirred for about 1-2 hours and filtered with a Glass internal chute G3. The residue is suspended in about 4 l of water and stirred for 30 min, it is filtered off and dried in vacuo. For The crude product is cleaned at room temperature with 400 ml of dimethyl Formamide added, insoluble components are filtered off and it 2.5 l of chloroform are added. The dye so precipitated is removed filtered, the cleaning operation is repeated again, and it is then washed with 1000 ml of chloroform and dried in vacuo. About 15 g of chromophore of the following structure are obtained in the corresponding manner the "ammonium salt form":

Rf value = 0.14:
Thin layer chromatography with finished films POLYGRAM SIL G / UV 254 from Macherey-Nagel, eluent: mixture of 50 parts toluene, 20 parts ethanol, 10 parts triethylamine, 10 parts dioxane and 2.5 parts water.

Table 5

The chromophores given in the following table correspond to the formula

they are known by diazotization of the corresponding educts Methods and coupling in analogy to the information in Example 85 posed.  

The chromophores given in Table 6 below correspond to formula

they are obtained by diazotizing and coupling the corresponding starting materials known methods, in analogy to the information in Example 85 poses.  

Table 6

The chromophores given in Table 7 below correspond to formula

and are also by diazotizing and coupling the corresponding Educts, prepared by known methods.

Example 114

The literature-known dye of the following structure is by Desul Formation of the corresponding 2-sulfonic acid derivative according to known Methods shown:

Example 115 Reaction of poly (styrene-co-maleic anhydride) according to Example 1 with the chromophore according to Example 18

To a solution of 1.17 g of poly (styrene-co-maleic anhydride) in 15 ml Dimethylformamide becomes a filtered solution from 2.01 g of the chromophore 18 dropwise in 50 ml of dimethylformamide and the solution at 2 h Room temperature stirred. The mixture is filtered and slowly to 650 ml Methanol (that's 10 times the amount of precipitant), which  precipitated product filtered off, washed with methanol and at 50 ° / 33 mbar dried.

According to the above procedure, the reaction can also be carried out in a whole amount of solvent of 20 ml of dimethylformamide are carried out; in front the polymer solution is precipitated with 20 ml of dimethylformamide, Diluted N-methylpyrrolidone or tetrahydrofuran.

According to the above procedure, the precipitation of the polymer can also be carried out in Ethyl acetate are carried out.

According to the above procedure, the reaction can also be carried out in N-methyl pyrrolidone can be carried out.

According to the above procedure, the reaction can also with the ammonium salt of the dye with the addition of 2.5 ml of triethylamine in dimethyl formamide or N-methylpyrrolidone can be carried out.

According to the above procedure, the reaction can also be carried out at temperatures from RT to 120 °.

According to the above procedure, the reaction can also take place Catalytic amounts of pyridine (1-20 mol%) are carried out.

Analogous to the mode of operation of example 115, the parameters shown in FIG polymers of formula 8 given in Table 8:

Formula 8

Table 8

Analogous to the way in which Example 115 works, the ones shown in fol polymers shown in Tables 9-12 of the general formulas 9-14 produced:

Formula 9

Table 9

Deviating from the general rule according to Example 115, the Reaction for the preparation of the compounds of Table 10, according to the formula 10 with the insoluble poly (methacrylic anhydride) according to Example 6 first started in suspension. With further progress a homogeneous solution is formed.

Formula 10

Table 10

Formula 11

Table 11

Formula 12

Formula 13

Formula 14

Table 12

Example 136 Reaction of the polyamic acid according to Example 115 and ring closure to give the imide

0.66 ml of acetic anhydride and. Are added to the reaction solution from Example 115 the mixture is stirred at 120 ° for 2 hours. After cooling, the Filter the solution and slowly to a mixture of 700 ml of methanol and Dropped 70 ml of water. The precipitated product is filtered off and at 50 ° / 33 hPa dried.

According to the above procedure, the precipitation of the polymer can also with reduced (six times) the amount of precipitant.  

According to the above procedure, the reaction can also be carried out by adding Oxalyl chloride can be carried out in tetrahydrofuran as a solvent.

According to the above procedure, the reaction can also be carried out by adding Trimethylchlorosilane can be performed.

Following the procedure in Examples 115 and 136, the reaction also by adding trimethylchlorosilane and triethylamine to the dye and then dropping this mixture into a solution of the Polymers are carried out.

Analogous to the working methods of Examples 115 and 136, the in polymers of formula 15 given in Table 13 below. The reaction can both with the isolated polyamic acid form can also be carried out in a one-pot reaction:

Formula 15

Table 13

Analogous to the working methods of Examples 115 and 136, those in FIGS The following tables 14-17 indicated polymers of the general formulas 16-24 manufactured:

Formula 16

Formula 17

Table 14

Formula 18

Table 15

Formula 19

Table 16

Formula 20

Formula 21

Formula 22

Formula 23

Formula 24

Table 17

Analogous to the working methods of Examples 115 and 136, the in polymers of formula 25 given in Table 18 below; deviating from the above procedure, two equi are used per repeating unit valent chromophore and 2 equivalents of acetic anhydride in the reaction puts.

Formula 25

Table 18

Example 204

Formula 26

0.15 g of tetracyanethylene is added to a solution of 0.42 g of the copolymer according to Example 171 in 5 ml of N-methylpyrrolidone. The dark red reaction solution is stirred for 5 hours at room temperature, diluted with 2 ml of N-methylpyrrolidone, filtered and slowly added dropwise to 200 ml of ethyl acetate. The precipitated copolymer is filtered off and dried at 33 hPa / 30 °. UV: λ _max = 527 nm (NMP).

Example 205 (Application example)

1 g of the polymer from Example 141 is in about 4 h at room temperature in 9 g of a mixture of 8.1 g of cyclohexanone and 0.9 g N-methylpyrrolidone dissolved. To remove dust particles, the Solution through a Teflon filter with a pore diameter of 0.2 µm filtered.

A 50 × 50 mm glass plate is cleaned as follows: Treatment with conc. Soap solution in an ultrasonic bath for approx. 1 hour, rinse one after the other with dist. Water, acetone and again with dist. Water, and then drying in a vacuum drying cabinet for approx. 12 hours 80 °.

In a dust-free atmosphere, the o.g. Polymer solution on this glass plate at 2400 rpm within 50 s hurled. Then one after the other in the vacuum drying cabinet each dried for 20 hours at 70 °, 150 ° and 170 °.

A homogeneous film of good optical quality is obtained. The Layer thickness is 0.4-0.5 µm (Alpha Step measuring device from Tencor, Rugnis, France).

The film is inside at 140-150 ° by Corona Poling at about 5 kVolt poled for approx. 30 min. The polarity is determined by SHG measurements after the "Maker-fringe" method followed at 1064 nm, cf. M.A. Mortazavi et al., J. Opt. Soc. At the. B, 6 (4) 741 (1989).  

After reaching the maximum SHG signal, the electr. Field slowly cooled to room temperature.

The following value for the NLO coefficient is obtained: d 31 = 360 pm / V (1064 nm, resonance increase).

Example 206-208 (Application examples)

Analogously to Example 205, the corresponding polymers are formed by spin coating the respective polymer films in layer thicknesses of approx. 0.4-0.5 µm receive. The appropriate polarization temperatures and the d31 obtained Values are summarized in Table 19 below.

Table 19

The listed polymer films show excellent polarity Long-term stability.  

Example 209 (Application example)

1.5 g of the polymer from Example 154 are in about 4 h at room temperature in 6 g of a mixture of 5.4 g of cyclohexanone and 0.6 g N-methylpyrrolidone dissolved. To remove dust particles, the Solution through a Teflon filter with a pore diameter of 0.2 µm filtered.

A glass plate from Balzers coated with indium tin oxide (ITO) (26 × 75 mm) is cleaned as follows: Treatment with conc. Soap solution in an ultrasonic bath for approx. 1 hour, rinsing in succession with dist. What water, acetone and again with dist. Water, followed by drying in a vacuum drying cabinet for approx. 12 hours at 80 °.

In a dust-free atmosphere, the o.g. Polymer solution on this glass plate at 3800 rpm within 50 seconds hurled. Then one after the other in the vacuum drying cabinet each dried for 20 hours at 70 °, 150 ° and 170 °.

A homogeneous film of good optical quality is obtained. The Layer thickness is 1.6-1.9 µm (Alpha Step measuring device from Tencor, Rugnis, France).

The film is inside at 170-180 ° by Corona Poling at about 5 kVolt poled for approx. 30 min. The polarity is determined by SHG measurements after the "Maker-fringe" method followed at 1313 nm, cf. M.A. Mortazavi et al., J. Opt. Soc. At the. B, 6 (4) 733-741 (1989).

After reaching the maximum SHG signal, the electr. Field slowly cooled to room temperature.

The following value is obtained for the NLO coefficient: d 33 = 78 pm / V (1313 nm).

The polymer film showed an excellent long-term in the poled state stability.  

Example 210 (Application example)

The following polymer solutions are produced:

• α) 1 g of polymer from Example 138 in a mixture of 3.6 g of cyclohexanone and 0.4 g of N-methylpyrrolidone,
• β) 2 g of polymer from Example 146 in a mixture of 5.4 g of cyclohexanone and 0.6 g of N-methylpyrrolidone,
• γ) 2 g of polymer from Example 1 in a mixture of 7.2 g of cyclohexanone and 0.8 g of N-methylpyrrolidone.

The solutions are removed by Teflon filters to remove dust particles filtered with a pore diameter of 0.2 microns.

Polymer film α

A silicon waver is cut to a size of approx. 20 × 20 mm, cleaning is carried out as described in example 205 for glass plates. In a dust-free atmosphere in a spin coating plant 3800 rpm, the polymer solution α on this silicon within 50 s thrown waver. Then is in the vacuum drying cabinet dried each other for 20 hours at 70 °, 150 ° and 170 °. The Layer thickness α is approximately 1.65 µm.

Polymer films α + β

The polymer is applied to the polymer film α at 3400 rpm within 50 seconds spin-on solution β. It is again in the vacuum drying cabinet each dried for 20 hours at 70 °, 150 ° and 170 °. The thickness of the Double layer α + β is approximately 4.45 µm.

Polymer films α + β + γ

The poly is applied to the double layer α + β at 5700 rpm within 50 s spin solution γ spun on. It is again in the vacuum drying cabinet successively dried for 20 hours at 70 °, 150 ° and 170 °. The fat the triple layer α + β + γ is approximately 6.45 µm.  

On the silicon wafer coated with the polymer films α + β + γ Distance of about 1 cm creates two parallel breaking edges. On one Break edge is cut into the laser beam with a wavelength of 1064 nm middle polymer layer β coupled in, on the opposite edge will exit with an IR camera and a connected monitor de light detected. The polymer arrangement shows excellent waves line properties.

Example 211 (Application example)

Based on a suitable three-layer polymer film arrangement as in Example 210 can be electro-optical devices (modulators, switches etc.) produce, as already published in principle, e.g. B. in SPIE Proceedings 1337, 215 (1990).

Claims (13)

1. Polymeric organic compounds in the molecule imide, isoimide or amide-like bound chromophores with non-linear optical properties contain shafts, the bridge between polymer chain (a) and Chromophore (b) consists only of carbon and nitrogen atoms and in the case of the amide-like bond said bridge only one -CO member contains. 2. Polymeric organic compounds according to claim 1, wherein the poly Merketten (a) Unipolymerisate from monomeric compounds with several for condensation and / or polymerization, preferably one for poly merisation and a functional group capable of condensation are. 3. Polymeric organic compounds according to claim 2, wherein the polymer chain unipolymerizates from acrylic acid anhydride, methacrylic acid anhydride, Citraconic anhydride or itaconic anhydride. 4. Polymeric organic compounds according to claim 1, wherein the polymer chains (a) copolymers or terpolymers, preferably copolymers of aliphatic or cyclic anhydrides or imides with compounds of the formulas 1 to 6 are formula 1 wherein the two R ₁ a independently of one another hydrogen, chlorine, C _1-5 alkyl, or an R ₁ a also phenyl, C _1-5 alkoxy, C _1-5 alkyl carbonyloxy, C _1-5 alkoxymethyl, C _1-5 alkylcarbonyloxymethyl, allyloxycarbonyl or a radical of the formula and R _{11 is} hydrogen or C _1-5 alkyl; formula 2 wherein all R ₁₂ , independently of hydrogen or methyl,
R _{13 is} a bridge member of the formula -O-, -S-, -SO ₂ - -CH ₂ O-, -CH ₂ OCH ₂ -, -CO-, - (C (R ₁₄ ) ₂ ) - or - (Si ( R ₁₄ ) ₂ ) - and all R ₁₄ independently of one another are hydrogen, methyl or C _4-6 -cycloalkyl or together ω-C _4-6 -alkylene; formula 3Furan, thiophene, 2,3- or 3,4-dihydrofuran , 2,3-dihydropyran, cyclo hexene, indene, indole or NC _1-3 alkyl indole; formula 4 wherein a) R _{15 is} a -CH ₂ bridge
one R ₁₆ and one R _{17 are} hydrogen, the remaining R ₁₆ and R _{17 are} the direct bond
or b) R _{15 is} a -CH ₂ - or -O bridge,
all R ₁₆ and R ₁₇ independently of one another are hydrogen or a radical of the formula -CH = CH ₂ , -CH = C-CH ₃ , -C (CH ₃ ) = CH ₂ , -CHO or -COCH ₃ or
the two R ₁₆ together are a radical of the formula = CH ₂ or = CH-CH ₃ and the two R _{17 are} each hydrogen, or an R ₁₆ with an R _{17 is} a bridge of the formula -CH ₂ -CH = CH- or -CO- O-CO- and the remaining R ₁₆ and R _{17 are} hydrogen; formula 5 wherein R ₁₈ (in ortho, meta or para position) hydroxyl, carboxyl, formyl or a radical of the formula R _{18a is} hydrogen, fluorine or chlorine,
R _{19 is} hydrogen, C _1-2 alkyl or cyan
and R _{20 is} hydrogen, hydroxyl or C _1-3 alkoxy. Formula 6 wherein the two R _{21 are} independently halogen, especially chlorine or bromine, or C _1-4 alkyl and
R _{22 is} vinyl or allyl. 5. Polymeric organic compounds according to any one of the preceding claims, wherein the chromophores correspond to formulas I to V. where in these formulas R _{1 is} hydrogen, halogen, carboxyl, cyan or rhodan,
R _{2 is} hydrogen, halogen, cyan, carboxyl or nitro,
R _{3 is} hydrogen, C _1-2 -alkyl, C _1-2 -alkoxy, amino-C _1-2 -alkyl or C ₁ - ₂ -alkylcarbonylamino,
R _{3 ′ is} hydrogen, C _1-2 alkyl or C _1-2 alkoxy,
R _{4 is} hydrogen or C _1-2 alkoxy,
R _{4 ′ is} hydrogen or C _1-2 alkoxy,
R _{5 is} a group of the formula or if R₃ is amino-C _1-2 -alkyl, also di- (C _1-4 -alkyl) -amino,
R ₆ cyan, nitro, C _1-2 alkylsulfonyl, aminosulfonyl, dicyanovinyl, tricyanovinyl, di- (C _1-4 -alkoxycarbonyl) -vinyl or a group of the formula -CH = CH-NO ₂ , -C (C _{1- 4} -alkyl) = (CN) ₂ , R _{7 is} hydrogen or nitro,
R _{8 is} hydrogen, C _1-4 alkyl, benzyl or C ₁ - ₂ alkylcarbonyloxy-C ₂ - ₃ alkyl,
n is zero or a number from 1 to 9,
p zero, 1 or 2,
A _{1 is} the direct bond or a bridge member of the formula -CH = CH-, -N = CH- or -CH = N-,
A ₂ oxygen or sulfur,
B is a group of the formula W ₁ tricyanovinyl, nitro or a group of the formula -CHO, -CH = C (CN) ₂ , -C (C _1-4 alkyl) = C (CN) ₂ or -CH = C (COO-C _1-4 alkyl) ₂,
W _{2 is} hydrogen, chlorine, C _1-4 alkyl or phenyl,
Y nitro, formyl, cyano, C _1-2 alkylsulfonyl, dicyanovinyl or tricyanovinyl,
Z ₁ = N-, = CH- or = C (NO ₂ ) - and
Z ₂ = N-, = CH- or = C (NO ₂ ) - mean
where halogen is preferably chlorine and bromine. 6. Polymeric organic compounds according to claim 5, wherein in the formulas I to V, the substituents
R _{1 is} hydrogen, chlorine or bromine,
R _{2 is} hydrogen, chlorine, bromine, cyan or nitro,
R _{3 is} hydrogen, methyl or C _1-2 alkylcarbonylamino,
R _{3 ′ is} hydrogen or methyl,
R _{4 is} hydrogen or C _1-2 alkoxy,
R _{4 ′ is} hydrogen,
R ₅ (NC _1-2 alkyl-N-ω-C _1-3 alkyl) amino, (N-benzyl-N-γ-aminopropyl) amino or N-piperazyl,
R _{6 is} cyan, nitro, dicyanovinyl or C _1-2 alkylsulfonyl,
R ₇ nitro,
R _{8 is} C _1-4 alkyl or benzyl,
n 1, 2 or 3, preferably 2 or 3,
p zero or 1, preferably zero,
A ₂ sulfur,
B is a group of the formula b or c (claim 5),
W ₁ dicyanvinyl, tricianvinyl, formyl or di- (C _1-2 -alkoxycarbonyl) -vinyl,
W _{2 is} hydrogen, chlorine, methyl or phenyl,
Y nitro or cyan,
Z ₁ = CH-, = N- or = C (NO ₂ ) - and
Z ₂ = CH-, = N- or = C (NO ₂ ) - mean. 7. Process for the preparation of the polymeric organic compounds, according to one of the preceding claims, characterized in that one, in any order, the uni-, co- or terpolymer chains (a) with the one or more for condensation and / or poly merizable functional groups containing monomeric Ver builds up bonds with the chromophores (b), one of which is condensed containation or addition capable group, brings to reaction. 8. The method according to claim 7, characterized in that as monomeric compounds with which the polymer chains are built, selects one or two, preferably one for polymerization capable group and one capable of condensation with the chromophore functional group included. 9. The method according to claim 6 or 7, characterized in that one Unipolymer chains from aliphatic or cyclic anhydrides, be or copolymer chains of aliphatic or cyclic Anhydrides and compounds of the formulas 1 to 6, according to claim 4, builds up and with chromophores that ent an amino or ammonium group hold, condensed. 10. Use of the compounds according to one of claims 1 to 6 for Production of polymer films with nonlinear optical properties shafts that consist of one or more polymer layers. 11. Use of the compounds according to one of claims 1 to 6 in the manufacture of the middle layer be one of three layers standing polymer film system in which both the lower and the upper layer have a smaller refractive index than the middle right layer and the glass transition temperature Tg of both the lower and the upper layer is larger or at least as large as that of the middle layer.   12. Use of the products according to one of claims 10 and 11, in which Production of films from one or more polymer layers for Modulators, electro-optical switches and switch systems and in Devices for frequency conversion, frequency doubling and others nonlinear optical effects. 13. waveguide arrangements of three layers of a polymer film system, in which the middle layer of compounds according to one of the An claims 1 to 6 and has a larger refractive index than the other two layers and the glass temperature Tg of the middle layer is smaller or at most the same size as that of the two other layers.