DD211798A1 - METHOD FOR THE PRODUCTION OF HIGH-MOLECULAR POLY (RADICAL CELLS) - Google Patents

Abstract

The invention relates to a process for the preparation of soluble high molecular weight poly (radical cations) with structural members which open up new technical solutions as film-forming polymer dyes, polymeric redox reagents, cationic polyelectrolytes and filiform semiconductors. The process according to the invention is characterized in that high molecular weight soluble epoxide-arylamine addition polymers or corresponding copolymers are converted to poly (radical cations) of the abovementioned types by oxidation processes in solution, as a solid, film or in solid-state surfaces. The oxidation can be chemical, e.g. by elemental halogens, tetracyanoethylene, chloranil or anitone pentachloride; photochemically, for example in the presence of oxygen or alkyl halides, if appropriate in the presence of sensitizers, or else electrochemically in the presence of conductive salts.

Description

Process for the preparation of high molecular weight poly (radical cations)

Field of application of the invention

The invention relates to a process for the preparation of high molecular weight poly (radical cations) carrying arylamine radical: cation groups A or B in a macromolecular chain:

- R

Φ © -] -NR ¹¹ U -... B

aryl

High molecular weight poly (radical cations) of this type are more or less dependent on the aryl radical and its substitution. less stable radical cations possessing a low energy excitable yC electron system, where the radical ion function is associated with the advantageous mechanical , technological, and structure-specific properties of film-forming macromolecules. Technically valuable properties of the radical cations of the invention include: the light absorption in the visible loading * rich, the increased electronic conductivity of combinations of Radikalkstionen Rait suitable counter-ions, the photoconductivity in the visible range, the Paramagnetissius, the ability to represent one-electron reduction or oxidation,

the possibility given by the Polykation character of the combination with the most diverse anions by ion exchange or in the course of the production. The poly (radical cations) according to the invention can therefore serve as intermediates for the production of optical, 'photoelectric, electronic and chemical components or large-area layer elements', The production process can also be used as a chemical process step in the construction of such devices.

Characteristic of the known technical solutions

Epoxide-amine addition polyesters are described in DDR patents 154985 and 149534-and in the publications of Hörhold and Mitarb. Makromol. Chemistry, Rapid Commun. 2 (1981) 113 and Z. Chem. 2 (1982) 166.

So far, only by the publication of co-inventors Hörhold and Klee in Z. Chem. 22 (1982) 166 the radical cation formation of DGEBA addition polymers has been reported.

In the GDR patent WP 232300/3 are. Wurster-type poly (radical cations), but based on N ₈ N ¹ -disubstituted p-phenylenediamines and diepoxides, so that the specific epoxide-arylamine addition polymers underlying the invention were not the basis of the oxidation reaction.

Object of the invention

The object of the invention is to find a generally applicable process for the preparation of high molecular weight poly (radical cations). In order to enable the use for the production of large-area layer elements, it should be striven that the new polycations or their chemical precursors are soluble or thermoplastic deformable and can beforested to layers alone or with binders.

Explanation of the essence of the invention

According to the invention, the process for the preparation of high molecular weight poly (radical cations) is characterized in that soluble fumbildende epoxide-arylamine addition polymers, which have arisen from the polyaddition of diepoxides with an aryl compound having a primary amino group, preferably those of the structure! _ Or 2_ and copolymers with corresponding structural members:

1-N-CH ₀ CHCh ₀ -R-CH ₀ CHCH ₀ -I-1

iLιtL άιd. \ -

OH

-N-CH CHCH _{O O O} R-CH CHCH _O -2, 2 2t 2

by an oxidation process on several (m) structural members (2 - m - n) to poly (radical cations) of type 3 or, are used

Fri.

I i

OH

OH

-N-R ^f -N-CH ₀ CHCH ₀ -R-Ch ₀ CHCH ₀

OH

OH

1, 2, 3 and 4, the radicals Z, R and R ⁹ preferably have the following meaning:

Z * H, halogen (F, Cl, Br, D), R "0-, R" S-, R "N-, CH ₃ , R-CC-, R-OOC-, (R" = alkyl, aryl radicals ²

R * - aliphatic, araliphatic cycloaliphatiseher di ~ functional radical or a substituted radical derived therefrom, such as -CH ₂ CH ₂ -, -CH ₂ C ₆ H ₄ CH ₂ - / "* ^C 5 ^H io

R = difunctional radical / which can connect two glycidyl groups, preferably -OC ₃ H ₄ C (CH ₃ J ₂ CgH ₄ O-, -OC ₆ H ₄ CH ₂ C ₆ H ₄ O-, -OC ₆ H ₄ O-, -0OC-R ^ COO.

However, the oxidation process of this invention into poly (arylamine radical cations) can be applied to other aryl arene addition polymers, such as those bearing other arylamine groups derived from mono- or polynuclear, mono- or poly-substituted primary arylamines.

N-Ar (aryl radical, mononuclear or polynuclear, on or

multiply substituted aryl radical, for example naphthyl or 2,4-dimethoxyphenyl)

High-molecular-weight film-forming epoxide-arylamine addition polymers can be obtained by addition polymerization of diglycidyl compounds and primary aromatic monoarenes to N, N-diaryldiamines by known processes (DD 154985 / DO 149534, also see publications by Hörhold and Mitarb, Makromol Cotnmun., 2 (1981) 113 / Z., ex 22 (1982) 156).

These epoxide arylamxn addition polyraers are soluble in organic solvents such as THF / dioxane and pyridine and in the solution medium mixture CHCl ₃ ZCH ₃ OH (4: 1) and can be cast from these solutions into films and layers.

The oxidation of the epoxide-arylamine addition polymers according to the invention can be carried out with various oxidizing agents. As chemical oxidizing agents are for the purposes of the invention particularly elemental halogens, antimony pentachloride; Chioranil, tetracyanoethylene and lead tetraacetate suitable.

The oxidation to poly (arylamine radical cations) can also be pho-

tocherisch, for example by oxygen (0 _p ) or alkyl halides, optionally in the presence of sensitizers.

The oxidation of the epoxide-arylamine addition polymers can also be carried out electrochemically according to the invention. In this case, the oxidation takes place, for example, at the anode of a provided with a diaphragm electrolysis cell in the presence of a suitable conductive salt, such as. As Tetraethylararaoniumperchlorat, Tetrabutylaramoniumperchlorat or Lithiuraperchlorat. If the oxidation is not in solution but in solid phase, for. Example, applied to the anode thin films of the addition polymers, so the use of a diaphragm is not required.

It has also been found that the epoxide-arylamine addition polymers can be converted both in solution and as a solid, preferably in the form of thin layers, to the poly (radical cations) according to the invention.

Further, the oxidation process may also be carried out by vapor deposition of corresponding epoxy-arylamine polymer layers with the oxidizing agent, e.g. B »Dod, or by contact of the surfaces of addition polymer layers with gaseous, liquid, dissolved or solid oxidizing agents.

For example, to carry out the process according to the invention, the polymer layer of an epoxide-arylamine addition polymer of p-anisidine and bisphenol A diglycidyl ether is oxidized by placing the layer in a vessel saturated with bread vapor for a short time (1-10 s). The result is a red poly (radical cation) containing the following structural elements:

O ρ LJ

r Qa ^B / 7 ~ a ι ³ / r ^,

+ -N - CH ₀ CHCH ₀ CK '\ y CK ⁷ V-OCH ₀ CHCH ₀ -I. RK-I

ii έ \ t. V- / i \ - / ^ i ^

^^ OH CH OH

- b

Furthermore, the oxidation of the epoxy-arylamine addition poly kidneys can be carried out in solution. So z. For example, an addition polymer of N, N-diethyl-p-phenylenediamine and bisphenol A diglycidyl ether in CHCl ₃ ZCH ₃ OH (4: 1) and reacted by adding bromine at room temperature. The result is a blue poly (radical cation) with absorption maxima at 635 and 585 nm, which contains the following structural units:

I 3 r ~ -OCH ₂ CHCH ₂ - C - <j f / \ - OH J CH ₃ Y Z - \ IJ

N - CH _o CHCH _o 0 - <f> C -f ^ V-OCH ^ CHCH ^ - \ RK-2 2i 2 \ _

example 1

50 mg of an addition polymer of p-anisidine and bisphenol A diglycidyl ether (M 12 000) prepared according to DD 154985 Example 3 are dissolved in 1 ml CHCl ₃ ZCH ₃ OH. The solution is placed on a quartz plate and the solvent evaporated. The resulting layer is bromine vapor for 1 - 10 seconds at room temperature; by placing the layer in a vessel containing a few grams of elemental bromine at the bottom and in which the equilibrium vapor pressure has settled.

The result is a red poly (radical cation) containing structural elements RK-I (see Fig. 1)

Example 2

50 mg of an addition polymer of N / N-diethyl-p-phenylendiarain and bisphenol A diglycidyl ether (M _n 10 800) are dissolved ₃ ZCH ₃ OH in 1 ml CHCl. This solution is applied to a quartz plate and the solvent is evaporated off. Thereafter, the layer is irradiated in the air with a high-pressure mercury vapor lamp (HBO 200). This results in a hlaue layer containing a poly (radical cation) having structural members RK-2. (Fig. 2)

Example 3

0.281 g (0.46 raraol WSE) of an addition polymer of N, N'-di (p-methoxyphenyl) ethylandiamine and bisphenol A diglycidyl ether (M 6600) are dissolved in 20 ml CHClo / CH 2 OH (4: 1) While stirring, 73.27 mg (0.46 mbar) of bromine are slowly added dropwise, and the resulting red solution is immediately poured into a red film.

If the red solution is kept at room temperature for a longer time (2 hours), a color change to green occurs. The polymer solution is then dropped into 200 ml of hexane, the precipitated poly (cation) is separated and dried for 12 hours at 80 C and 0.01 Torr.

Yield: 0.130 g (37 % of theory )

(° 37 ^H 44 ^Br 2} Be r. C (772.6) - 5 , 74 br 20 , 69 H 3 , 53 Gef. C 57.52 H 6 , 07 br 20 , 83 N 3 , 32 57.95 H example 4

0.955 g (2.08 mmol VVSE) of an addition polymer of p-anisidine and bisphenol A diglycidyl ether (M _n 12 000) are dissolved in 20 ml CHCl ₃ / CH ₃ OH and mixed with 52.83 mg (0.21 mmol) God in 5.283 ml CHGl _{3 added} dropwise with stirring. The resulting red solution is immediately shed into a red film.

If the red solution is kept at room temperature for a longer time (2 hours), a color change to green occurs. The polymer solution is added dropwise in 200 ml of hexane, the precipitated poly (cation) is separated and dried at 0.01 torr and 80 ⁰ C for 8 hours.

Yield: 0.76 g (75 % of theory )

(° 28 ^Η 33 ^α 0,2 ^ΝΟ 5>< ⁴⁸⁹ '°)

8er. C 68,78 H 5,80 3 5,19 N 2,86 Gef. C 53,56 H 6,90 0 5,60 N 2,71

Example 5

1.043 g (2.25 mmol WSE) of an addition polymer of p-anisidine and bisphenol A diglycidyl ether (M 12 000) are dissolved in 20 ml CHCl ₃ / CH ₃ OH and treated with 142.75 rag (0.56 mmol) Dod in 14.28 ml of CHCl _{3 added} dropwise with stirring. The red polymer solution is then added dropwise in 200 ml of hexane, the precipitated poly (radical cation) is separated and dried for 8 hours at Ο, ΌΙ Torr and 80 ⁰ C. The poly (radical cation) has a broad unresolved signal in the ESR spectrum (Figure 3) and absorption at 450 na (Figure 4).

Yield: 0.92 g (78% of theory). It shows the following analytical composition.

( ^C 28 ^H 33 ^a 0.5 ^N0 5> (527.0) "

Ber. C 63.81 H 6.31 O 12; 04 N 2.66 C, C, 63.50, H, 6.54, 3, 12.45, N, 2.28

Example 6

0.488 g (1.02 mmol WSE) of an addition polymer of N, N "diethyl-p-phenylenediamine and bisphenol F diglycidyl ether (M 5200) are dissolved in 40 ml OHCl ₃ ZCH ₃ OH (4: 1) and stirred 81.80 mg (0.51 mmol) of bromine added. The blue poly (radical cation) is precipitated in 200 ml of hexane and dried for 8 hours at 80 ^° C. and 0.01 torr.

Yield: 0.342 g (60 % of theory )

( ^C 29 ^H 36 ^N 2 ° 4 ^8r) "~ (556.5) -

Ber. C 52.59 H 6.52 Br 14.35 N 5.03 Gef. C 62.52 H 6.45 Br 14.15 N 4.97

Example 7

0.360 g (0.713 mmol WSE) of an addition of M, N-diethyl-p-phenylenediamine and bisphenol A diglyeidyl ether (Fi 10 800) are dissolved in 25 ml of CHCl ₃ ZCH ₃ OH and with

»- 9 -

14.25 mg (0.089 mmol) of bromine are added dropwise and with stirring. The polymer solution is dripped into 200 ml of hexane and the precipitated poly (radical cation) is separated and dried in vacuo. The blue poly (radical cation) shows absorption maxima at 585 nm and 635 nm in the UV spectrum.

Yield: 0.281 g (75 % of theory )

< ^C 31 ^H 40 ^Br O , 25 ^Ν 2 ° 4 ) C 70 (524, .5) 7 , 69 br 3 , 31 N 5 , 34 Ber. C 69 97 H 7 , 89 br 3 , 78 N 5 , 78 Ge f. , 86 H example 8th

15 mg of an addition polymer of p-anisidine and bisphenol A ~ diglycidyl ether (M 12 000) are dissolved together with 250 mg of tetraethylammonium perchlorate in 25 ml CHCl ~ / 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 raA. In a short time, the solution in the anode compartment turns red and shows in the spectrum the absorption of the poly (radical cation) ,: with a broad absorption maximum at 450 nm.

Example 9

15 mg of an addition polymer of N / N-diethyl-p-phenylenediarine and bisphenol A diglycidyl ether (H 14 100) are dissolved together with 250 g of tetraethylammonium perchlorate in 25 ml of CHClo / Cf-LOH. It will continue to proceed as described in 3-game 8. After just a short reaction time, the solution in the anode compartment turns blue and shows in the spectrum the absorption of the poly (radical cation) with absorption maxima at 585 and 635 nm.

Example 10

20 mg of an addition polymer of p ~ anisidine and bisphenol A ~ diglycidyl ether are by solution casting a solution in as a thin film on a platinum electrode with

an area of 13 cm applied. Subsequently, the thus coated electrode is connected in a 0.2 molar solution of lithium perchlorate as an anode against a platinum cathode and exposed to a direct current of ImA »This turns the previously almost colorless film of the epoxy-arylamine addition polymer on the anode in a red Film of poly (radical cation).

Claims (10)

invention claim 1. A process for the preparation of high molecular weight poly (radical cations), characterized in that soluble, film-forming epoxide arylamine addition polyesters, preferably those of the structure! _ Or 2 ,, -JN-CH ₀ CKGH ₀ -R-CH ₀ CHCH ₀ ] 1 V 2 (2 21 2-f- - - Ö ^{0H 0H J} n 4-N - R ^f - N - CH ₀ CHCh ₀ - R - CH ₀ CHCH ₀ - L 2 QQ ^{0H 0H} η by an oxidation process on a plurality of (m) structural members (2 - ro - n) to corresponding poly (radical cations), preferably to those of the type 3> or »4, vice sets are r 3
| -N - CH ₂ CHCH ₂ -R-CH ₂ CHCh ₂ -J- B 4-N - R ^f --ΝΝ - CH ₀ CHCH ₀ -R-CH 1 CHCh, where in! _, 2_ _# 3_ and 4 the radicals Z, R and R * have the following meanings: Z = H, halogen (F, Cl, Br, G), R "O, R" S-: R " ₂ N-, CH ₃ , 'R''CO-, R ¹¹ OOC- (R''= alkyl, aryl) R * = aliphatic araliphatic cycloaliphatic difunctional radical or a substituted radical derived therefrom, such as -CHPCH ₀ -, -C ₆ H ₁₀ -, -CH ₂ CH ₂ OCH ₂ CH ₂ R = difunctional "radical, which can connect two glycidyl groups, preferably -OC ₅ H ₄ C (CH ₀ J ₂ C ₅ H ^ O-, -OC ₅ H ₄ Q-, -OOC-R'-CQG". 2. The method according to item 1, characterized in that the oxidation is carried out in solution. 3. Method according to item 1, characterized in that the oxidation is carried out on a corresponding polymer layer or a polymer film. 4. The method according to item 1 to 3, characterized in that ^: that the oxidation by elemental halogens, preferably by God, bromine or chlorine, by antimony pentachloride, "Parachloranil or tetracyanoethylene is made, 5. The method of item I ₁ '2 and 3 i characterized in that the oxidation is carried out photochemically, preferably by oxygen, optionally in the presence of sensitizers. S. Procedure according to item 1 ^,; 2 and 3, ^1, characterized in that the oxidation is carried out photochemically by alkyl halides, optionally in the presence of sensitizers. 7. The method according to item 1, 5 and 6 _4, characterized in that the oxidation is carried out by imagewise exposure of a thin layer of the epoxy-arylamine addition Polyraere 1_ or 2_, preferably in the presence of introduced into the layer alkyl halides such as Tetrabromkoblenstoff, chloroform and others. _O 8. The method according to item 1, 2 and 3, characterized in that the oxidation is carried out electrochemically in the presence of conductive salts, preferably in the presence of Bu ₄ NClO ₁ , LiClO ₄ . 9. The method according to item 1 to 8, characterized in that is set as a polyarylamine a polymer of the structure 5 *. • J - N - CH ₀ CHCH ₀ -R-CH ₀ CHCh ₀ - OH OK NO". R- = CH ₃ , C ₂ H- R = -OC ₆ H ₄ C (CH ₃ ) J ₂ C ₆ H ₄ O- 10. The method according to item 1 to 8, i, characterized in that a polymer of the structure 6> is used as the polyaryl amine. 4-N - CH ₀ CHCH ₀ -R-Ch ₀ CHCH ₀ - ^ OH OH OCH. , R = -OC ₆ H ₄ C (CH ₃ ) ₂ C ₆ H ₄ O- 11. The method according to item 1 to 8, characterized in that as polyarylamine a polymer of the structure 7, is usedc -UN - CH ₂ CH ₂ - N - CH ₂ CHCH ₂ -R-CH ₂ CHCH ₂ -L ι OCH. OH OH R = -0 C _s H ₄ C (CH ₃ ) ₂ C _s H ₄ O- WN