DD231079A1 - METHOD FOR PRODUCING HIGH-MOLECULAR POLYCANES OF TRIPHENYLMETHANE-TARGET-TYPE - Google Patents

Abstract

The invention relates to a process for the preparation of soluble, high molecular weight triphenylmethane dye-type polycations which contain the following structural members: and, owing to this structure, to open up new technical solutions as film-forming dyes, cationic polyelectrolytes, film-forming semiconductors and photo-semiconductors. The process according to the invention is characterized in that per se known linear epoxide-amine addition polymers, which are leuco forms of the polycation, by oxidation processes in solution, as a solid, film or in Festkoerperoberflaechen be implemented. The oxidation to the polycations according to the invention can be effected both by chemical oxidants and also photochemically or electrochemically.

Description

Process for the preparation of high molecular weight triphenylmethane dye-type polycations

Field of application of the invention

The invention relates to a process for preparing triphenylmethane dye-type soluble high molecular weight polycations containing moieties of structure I ₁ as part of a macromolecular chain:

R = chain module ·

R * = N-substituent which is not part of the macromolecular chain

2 ^ ι 'i η S = H or substituent

High molecular weight polycations of this type have a low energy excitable W electron system located in the backbone, linking the triphenylmethane dye moiety to the advantageous mechanical, technological, and structure-specific properties of thermoplastic macromolecules.

Λ Ί

Among the technically interesting properties of such cyanine dyes are highlighted: the light absorption in the visible range, the possibility of orientation of the color centers, the increased electrical conductivity of combinations of Cyaninkationen with suitable counterions, the photoconductivity in the visible range, the ability to reductive transition in, corresponding Leuko Compounds, the possibility given by the polycation character of the combination with the various anions by ion exchange or in the course of production

The triphenylmethane dye-f-type polycations according to the invention can therefore serve as intermediates for the production of optical, electronic photoelectronic and electrochemical components or large-area layer elements.

The manufacturing process can also be used as a chemical process step in the construction of such devices.

Characteristic of the known technical solutions

Soluble and at the same time high molecular weight triphenylmethane dye-type polycations have not hitherto been known.

Object of the invention

The object of the invention is to find a generally applicable process for the preparation of high molecular weight triphenylacrylate dye-type polycations. In order to enable the use for the production of large area laminates, it is desirable that the novel polymers or their precursors be soluble and alone or can be formed into layers with binders.

Explanation of the essence of the invention

According to the Triphenylmethanfarbstoff- type high molecular weight polycations are prepared by oxidation of thermoplastic, soluble addition polymers AP containing a Ν, Ν'-disubstituted phenyl-bis (aminophenyl) methane block and a connecting block, which is derived from a diglycidyl compound.

OH

OH

the oxidation being conducted in such a way that, on average, chains with two or more (2-rm (= n) cation members of the structure TM are formed:

N-CH-CH _O CH _O R ^II ~ -CH -CH-CH _C> -

Il

R · OH OH

In this case, R 'is an araliphatic cycloaliphatic or aliphatic radical, preferably the senzyl, cyclohexyl or methyl radical, R "represents a group which can connect two glycidyl radicals (CH ₂ -CH-CH ₂ -), preferably

wise

ΠΡ U Cf PH λ P 1-1 Pi-DP U PU P Ul Π

UUgH ₄ U (UI ₃ J ₂ U ₆ H ₄ U, Uu ₆ H ₄ -GH ₂ -CgH ₄ U -OOC-R ^tt -COO-, -OOC-C ₆ H ₄ -COO-NC ₆ H ₄ -CH ₂ -C ₆ H ₄ -N-,> -C ₆ H ₅ , -00c

R ·

R *

COO,

-A-

and S is a substituent, preferably H, Cl, Br, OR ,. OCH ₃ , SR ¹ NR ' ₂ , N (CH ₂ ) ₂ ,' N (C ₂ H ₅ J ₂ , COOR ', SO ₃₁ R. It is advantageous to use addition polymers of the structures AP-1, AP-2 and AP- third

High molecular weight thermoplastic addition polymers AP are accessible by addition polymerization (polyaddition) of N, N * -disubstituted phenyl-bis (aminophenyl) methanes by known methods.

For example, according to DO 141677 or US 4308085 and DD 211799, a high molecular weight, soluble addition polymer AP can be obtained from phenylbis (4-methylaminophenyl) methane and a diglycidyl compound, which can serve as starting material for the preparation process according to the invention.

CH,

N - // \\ - CH - // VS-N-CH ₀ CH-CH ₀ O - // \\ - C- / 7 \\ - OCH ₀ CH-CH.

OH

CH,

1 OH

AP-I

-N-CH ₀ CH-CH ₀ O-CO I ² I ² CH ₃ OH

AP-2

CO-OCH-CH ₀ CH ^_0/2 I ² OH

OH

N-CH ₀ CH-CH ₀ -N - // \\ - CH - // \\ -N-CH ₀ CH-CH ₀ 2i 2i \ / i \ / ι 2. 2

= N =

CH

CH ₃ OH

AP-3

These polymers are in different solvents, z.3. in a mixture of chloroform and methanol (vol. ratio 4: 1), THF, methylene chloride, dichloroethane and the like. Soluble and can be cast from solution to transparent films by conventional casting technologies. They can also be used in solution for the production process according to the invention.

The oxidation according to the invention of the AP polymers to the polyisocyanates of the triphenylmethane dye type can be carried out with various oxidizing agents. As chemical oxidants are particularly suitable for the purposes of the invention:

Elemental halogens (iodine, bromine, chlorine), antimony pentachloride (SbCl ₅ ), arsenic pentafluoride (AsF ₅ ), chloranil (CgO ₂ Cl ₄ ), tetracyanoethylene (CgN ₄ ), PbO ₂ / HCl and other oxidants as described in Beilstein's Handbook of Organic Chemie Hauptwerk Bd. 13, p. 275, Springer-Verlag Berlin 1930 and second supplementary work Bd. 13, p. 135, Springer-Verlag Berlin, Gottingen, Heidelberg 1950. '

Depending on the oxidizing agent, various anions occur as a counterion, eg, I ₃ , Br, Cl ", SbCl ₆ ". For example, a solution of the addition polymer of phenylbis (4-methylarainophenyl) methane and DGEBA (AP-I), which was prepared according to DD 211 799, dissolved in chloroform / methanol (4: 1) and with an iodine solution in Chloroform added. If the amount of iodine is such that 2.0 mol of I ₂ is reacted per mol of repeat structural unit of AP-I, then an oxidative addition is formally carried out in accordance with Eq. 1

( ^C 42 ^H 46 ^N 2 ° 4> n ^{+ 2} '° » ^Σ 2 ->« MZ ^ aWη ^G1 ' ¹

The empirical formula ( ^C 42 ^H 46 ^isl 2 ⁰ 4 ^I 4 ^, however, represents an average formula which is presumably based on the following distribution:

(C ₄₂ H ₄₆ N ₂ 0 ₄ I ₃ ) _2/3

According to this, 2/3 of the repeat structural units are oxidized to the triphenylmethane dye cationic TM and combined with I ₃ counterions.

The formation of the triphenylmethane dye is confirmed by the absorption spectrum of the resulting oxidation products (Figure 1). The spectrum has the absorption bands typical of the triphenylmethane dye system. The existence of the I ₃ "* ions is evidenced by the absorption band at 365 nm, and other unoxidized structural members remain in the polymer chain, which, however, are involved in salt formation with the hydrogen iodide or HG ₃ formed during the oxidation In accordance with the invention it has been found that the epoxy-amine addition polymers of structure AP are oxidized not only in solution but also as a solid, preferably in the form of thin layers or cantilevered films, by immersion in solutions of the oxidizing agents to the triphenylmethane dye-type polycations of the invention It is expedient to choose those solvents which do not dissolve the polymer film or the polymer layer or at least do not dissolve in the brief immersion time (seconds to minutes).

Further, the process of oxidation may also be accomplished by vapor deposition of AP layers or films with the oxidizing agent, e.g. Iodine or by contact of the surface of AP layers with gaseous oxidizing agents.

For example, an AP layer in an atmosphere of bromine vapor is rapidly oxidized to the triphenylmethane dye-type polycations. The oxidation to polycations can also be carried out photochemically, for example in the presence of oxygen (Op) or alkyl halides, if appropriate in the presence of sensitizers.

An advantageous embodiment of the method according to the invention is the electrochemical oxidation. The oxidation of the dissolved polymer takes place, for example, at the anode of an electrolytic cell provided with a diaphragm in the presence of a suitable electrolyte, preferably in the presence of alkali metal or tetraalkylammonium salts with the anions ClO ₄ "," BF ₄ "", PPg ", ³ ^ g"'Sb-Clg"ASFG", RSO ₃ ", RCOO". particularly advantageous is the use of tetraethylammonium _f tetrabutylammonium perchlorate or lithium perchlorate. If the electrochemical oxidation is not in solution but on the fixed body, for example on a on the anode applied thin layer of the polymers of the invention, the use of a diaphragm is not required.

He Example Ie Example 1

0.2085 g (3.24 χ 10 ~ ⁴ mol) addition polymer AP-I, M _n (VPO) 10970, T 114 ⁰ C produced according to DD 211 799 (Example l) _f in 50 ml of chloroform / methanol (4: 1) and added dropwise with stirring 6.87 ml of an iodine solution (11.9 g / l). The solution turns dark green. From hexane, a dark green solid falls at 80 ⁰ C in a vacuum

(10 'Torr ) dried becomes. 2 H 5 17 N 3, 10 I 28 30 Yield: 0 , 21 g , 05 H 5 , 28 N 2, 91 I 28 , 66 (c ₄₂ l · I A I_) _n 8s. : C 56 (396, Ge f. : C 56 I ₄₆ N ₂ O < ⁶ > n

Example 2

1.0 g (1.71 χ 10 ^"3 mol) of AP-2, M _n (Vpq) 7000, are dissolved in 40 ml CHClVGH-OH (4: 1) and treated with stirring with 4.35 troofenweise lö χ" ~ ml Br_ offset. From hexane falls a turquoise solid which is dried at 80 C in a vacuum

 Yield: 1.05 g.

Example 3

0.5 g of the polyadduct AP-I are dissolved in 10 ml of dichloroethane and poured into a layer (10 ^ m) on a quartz plate. By immersing this layer in a lproz. Iodine solution in benzene gives rise to a green polycation with absorption at K = 635 nm.

Example 4

A layer of AP-3M (VPO) 8380, T 116 ^Q C on a quartz plate prepared as in Example 3 is used for

about 10 sec. placed in a saturated with bromine vapor vessel. The layer immediately turns intensively green, forming the absorption band at 635 nm.

Example 5

15 mg of the addition polymer AP-I are dissolved together with 250 mg of tetraethylammonium perchlorate in 25 ml CHClo / CH OH. The solution is placed in an electrochemical cell containing a diaphragm to separate the anode and cathode compartments and exposed to a direct current of 1 mA. After just a short time, the solution turns green in the anodic space and shows in the spectrum the absorption of the polycation with an absorption maximum at 635 nm.

Claims (5)

invention claim 1. A process for the preparation of high molecular weight polycations of Triphenylmethanfarbstoff type, characterized in that high molecular weight, thermoplastic addition polymers of the structure AP- by an oxidation process to several (m) N- (/ Vy-CH- <v V> -N-CH ₂ CH-CH ₂ -R - CH ₂ CH-GH ₂ - L R * OH OH Structural members (2 h m * =. N) are converted so that 'chains with structure TM structure. N-CH ₂ CH-CH ₂ -R "-CH ₂ CH-CH ₂ - OH OH wherein R * is an araliphatic, cycloaliphatic or aliphatic radical, preferably the benzyl, cyclohexyl, methyl or ethyl radical, and R * represents a moiety capable of linking two glycidyl radicals, preferably -OC ₆ H ₄ C (CH ₃ J ₂ C ₆ H ₄ O-, ⁰ C ₅ H ₄ -CH ₂ -C ₆ H ₄ O- OC ₆ H ₄ O-, -00C-R ^nt -C 00 -,) NC ₆ H ₅ , -N-CgH ₄ -CH ₂ -C ₆ H ₄ -N- -00C-C ₆ H ₄ -COO- R 'R * -0OC COO-, and S is a phenyl substituent be indicated preferably H, Cl, Br, OR ', OCH ₃ , SR *, NR ₂ , N (C ₂ Hg) ₂ , COOR', SO ₃ R '. 2. The method according to item 1, characterized in that the oxidation is chemically, for example by elemental Halogens, preferably iodine, bromine or chlorine, by anti-monopentachloride, arsenic pentafluoride, lead dioxide / hydrochloric acid, parachloranil. Tetracyanoethylene or tetracyanoquinodimethane is made, 3. The method according to item 1, characterized in that the oxidation is carried out photochemically, for example in the presence of oxygen or alkyl halides, optionally in the presence of sensitizers. 4 «method according to item 1, characterized in that the oxidation electrochemically, for example in the presence of suitable electrolytes, preferably in the presence of alkali metal or tetraalkylammonium salts with the anions ClO ₄ ", BF ₄ ", PF ₆ ", AsF ₆ ", RSO" or RCOO "(R = alkyl, aryl). 5. The method according to item 1 to 4, characterized in that the oxidation of the addition polymers AP is carried out in solution or as a solid reaction on a thin AP film or an AP layer. For this ..AJkiten drawings