NL1009541C2 - A method of manufacturing a film of arylalkyl modified polyacetylene, the polyacetylene obtained, and the use thereof. - Google Patents

Description

P HP / BM / K-47

A method of manufacturing a film of arylalkyl modified polyacetylene, the polyacetylene obtained, and the use thereof.

The present invention relates to the manufacture of a film of arylalkyl modified polyacetylene. In particular arylalkyl modified polyacetylene, and polydiacetylene, including 1,2- and 1,4-polydiacetylene.

Arylalkyl modified polyacetylene is a conjugated polymer that is electrically conductive after doping or photochemical treatment. Such polymers can be used in photovoltaic elements, photodiodes, photoconductors, and conductors in microelectronic devices, among others. For example, such a film can be used as an antenna layer in a so-called organic solar cell based on dye molecules and such a conjugated electrically conductive polymer. The conjugated polymer basically consists of a sequence of saturated and unsaturated bonds. Electrons and especially holes can move along the polyacetylene chain. Due to the high degree of order, few defects occur during the polymerization, so that optimum charge transport is possible. In fact, a so-called topo-chemical polymerization is usually carried out in which the arrangement is obtained by at least the aryl group of the arylalkyl-modified polyacetylene. In principle, the alkyl group acts as a spacer between the conjugated polyacetylene chain through which electrons / holes move and the stacked aryl groups. When these aryl groups are 30 dye groups, light absorption and excitation energy transport is possible. Two situations can be distinguished here. First, light absorption by the dye, followed by energy transfer and electron transfer by the dye, regeneration of the dye and removal of holes through the conjugate chain. Second, light absorption by the conjugate chain and electron transfer followed by hole transport and electron transport.

It has hitherto been impossible to apply chemically highly ordered arylalkyl-modified polyacetylenes on a support via a more or less topochemical polymerization, because such polyacetylenes are in principle unmanageable due to very poor solubility in solvents.

The present invention therefore provides a method by which it is possible to form on a support a film of an arylalkyl modified polyacetylene.

The invention is based on the insight that it is possible to form a well-ordered arylalkyl modified polyacetylene on a support by first applying or forming on the support the monomer intended for the polymerization in an adjustable and controlled layer thickness and then conduct the polymerization.

Thus, the present invention provides a method of manufacturing a film of arylalkyl modified polyacetylene, wherein a layer of an arylalkyl diacetylene compound of the formula (I) X (N) -L-CsC-GsC-L- ( N) X (I) wherein X (N) is a nitrogen-containing, planar aromatic group L a linear aliphatic group 1009541 3 - <CHa) n- with 1 sns 22, preferably 1 sns 9, more preferably 1 sns 6, 5 or a linear group - (CHa) pY- (CHa), -, 10 with 1 sp + qs 22, wherein preferably 1 sp or qs 9, more preferably 1 sp or qs 6, and Y a para-substituted aromatic group , 15 is formed and polymerized to the arylalkyl modified polyacetylene.

In the arylalkyl diacetylene compound of formula I, the groups X provide for the mutual orientation, arrangement and stacking of the compounds of formula I. To that end, it is necessary that the compound X (N) has a flat aromatic structure. The nitrogen atom provides the coupling of the group X to the group L. The group L serves as a spacer, ie determines the distance between the ordering group X on the one hand and the two conjugated acetylene bonds on the other.

The arylalkyl diacetylene compound of formula I can be applied directly to the support. For this purpose, the arylalkyl diacetylene compound has been chemically dissolved in advance. According to a first exemplary embodiment, the arylalkyl diacetylene compound of the formula I is chemically manufactured by an oxidative coupling of the compound of the formula II 35 X (N) -L-CsC-H (II) 1009541 4

This coupling can take place, for example, by thermal depletion. Here, the compound of formula II is heated to a temperature of generally 250-370 ° C, preferably 270-350 ° C, such as 320 ° C. It will be clear that the desired heating temperature to be selected will depend, inter alia, on the number of methylene groups in the group L.

The arylalkyl diacetylene compound of formula I can also be formed by a reaction between X (0) with 10 h2n-1-c = c-oc-1-nh2.

The product of this reaction obtained can then be polymerized by the aforementioned thermal conditions or UV or gamma irradiation.

The polymerization to arylalkyl modified polyacetylene can in principle take place according to two different types of polymerizations, namely a 1,4 polymerization or a 1,2 polymerization. The notation mentioned here indicates that in the 1,4 polymerization the first C atom of the conjugated acetylene groups will react with the fourth C atom of the two conjugated acetylene groups of the adjacent arylalkyl diacetylene compound with formula I.

In a 1,2 polymerization, 25 adjacent arylalkyl diacetylene compounds react.

first C atom of one compound with the second C atom of the adjacent compound.

In principle, it is optionally adjustable (by the choice of the compound) whether a 1.4 polymerization or a 1.2 polymerization takes place. The criteria for allowing a 1,4 polymerization to take place are known from the literature (Langmuir 12 (1996) 6065, (T.

Kim, Q. Ye, L. Sun, K.C. Chan, R.M. Crooks).

The criteria are as follows. The perpendicular distance s2 should be between 3.4-4.0 A. The distance between the consecutive fourth carbon atoms of the conjugated two acetylene compounds (d2) should be between 4.7-5.2 A. The angle enclosed between the 1 00954 t 5 conjugated diacetylene groups and the distance d: should preferably be about 45 ° so that s ^ dl sin a. Furthermore, in the 1,4-polymerized polydiacetylene, the distance between two consecutive C1 atoms should be about 4 .93 5 A.

In a first embodiment, the nitrogen-containing planar aromatic group X (N) is the compound of formula III

0 10 xfi \ X [l ^ / N in 15 This ring structure has a flat shape due to the carbonyl groups at the 1 and 4 position of the imide five-membered ring. Furthermore, the bond between the carbon atoms at the 2 and 3 positions is also part of either a benzene ring or fused benzene rings. In the case of a benzene ring, the group X (N) is a phthalimide group. Such a group is known.

The compound of formula III can be obtained quantitatively with the following reaction equation: P o 25 γ-Λ r-Λ

X-j-O + H2N-L-C ^ CH -x-i-N-L-C = CH

O O

30

This known reaction is performed in the solvent N-methylpyrrolidone (NMP) under inert atmosphere (nitrogen, argon). The reaction time is generally 1 to 5 hours, and the reaction temperature is generally between 60 - 70 ° C (J. Chem. Soc., Chem. Commun. (1987) 390, N. Kobayashi, Y. Nishiyama, T. Ohya, M. Sato; Makromol Chem. 194 (1993) 2789, G. Karayanidis, D. Stamelos, D. Bikiaris).

1009541 6

In the publication of E. Clar, M. Zander: J. Chem. Soc. (1957) 4616 describes the synthesis of the following three compounds a, b, c with six, seven or nine fused benzene rings.

ShR dSö dSfcP

"Qf ΟΡάψ

° o ° O ^ -o- ^ O

15 2 b C

1009541 7

Starting from phthalic anhydride (X = 1 benzene ring), all other randomly fused benzene ring structures can be made. Examples of such starting materials are the following: 5 C | = $ 2> 0-8 0 0 0 0 * 0 ^ ° J \ o ^ o ^ o d & h

NpF Η n 0 o 0 ° ^ 0> 0 ο ^ οΛ0 g h cfp cfp <0 0 · ^ ° 0 οΛο O ^ Aq j k i 1009541 8

The H2N-L-CsC-H used in this reaction is in principle commercially available. If in the spacer group L the linear aliphatic group consists of CH2 (n = 1), this is the commercially available propargylamine. Furthermore, for example, there are possibilities to convert a terminal hydroxyl group (OH), a terminal acid group (COOH) or terminal halogens (F, Cl, Br, I) into a primary amino group (NH2) (Tetrahedron 53 (1997) 1505, GT Crisp, J. Gore; Tetrahedron 50 10 (1994) 2533, EM Campi, JM Chong, WR Jackson, M. van der Schoot; Tetrahedron 49 (1993) 4439, GL L'abbé, S. Leurs, I. Sannen, W Dehaen; Synthesis (1979) 161, N. Blazevic, D. Kolbah, B. Belin, V. Sunjic, F. Jajfez; Bulletin de la Société Chemique de France (1958) 490, A.

15 Marszak-Fleury; Bulletin de la Société Chemique de France (1971) 1468, Y. Besace, A. Marszak-Fleury, I. Marszak; Archive der Pharmazie 290 (1957) 118, K.-E. Schulte, M. Goes. For example, an acetylene terminal group can be synthesized from an olefin terminal group (Vogel's Textbook of Practical Organic Chemistry, Fifth Edition, B.S. Fumiss, A.J. Hannaford, P.W.G. Smith, A.R. Tatchell, Etc.)

In another embodiment, the nitrogen-containing planar aromatic groups X (N)

25 represented by the compound of formula IV

X.

<rY

30 x (IV)

The X group in this case may represent a benzene ring or fused benzene rings. For the synthesis of such compounds, reference is further made to the following literature: 1009541 9 J. Polym. Sci .: Polym. Phys. Ed. 16 (1978) 431 (K.C. Yee, R.R. Chance) J. Am. Chem. Soc. 109 (1987) 761 (H. Eckert, J.P. Yesinowski, D.J.Sandman, Ch.S.Velazquez) 5 - Macromolecules 28 (1995) 8142 (D.J.Sandman, C.S.

Velazquez, S.H.W. Hankin, B.M. Foxman)

Macromolecules 29 (1996) 568 (J. Liao, D.C. Martin) In a third embodiment, the nitrogen-containing planar aromatic ring X (N) is formed by the compound of formula III

"Λ

Ky 15 (III)

O

wherein X (N) is a phthalocyanine derivative of the formula V.

R R

N = NS r-N n N-M-N N-

25 N == P-N

Q <vi

R R

Precursor phthalocyanine X (O) can be synthesized according to known reaction procedures.

Compound VI is prepared in a four-step process starting from 1,2-dihydroxybenzene

HN

n / Tjf 35 fj V (VI)

HN

1009541 10

This synthesis is described in the thesis "Columnar Aggregates Based on Phtalocyanine" written by J.F. van der Pol in Synthesis (1993) 377 (M. Hanack, P.

Haisch, H. Lehmann, L.R. Subramanian).

The compound VI is then reacted

with connection to VII

HN

hn I

V ^^ CN (VII)

HN

in a molar mass ratio of 3: 1. The preparation of compound VI and the precursor phthalocyanine is described in J. Chem. Soc., Chem. Commun. (1985) 259 (Ch.

Piechocki, J. Simon).

The precursor phthalocyanine (VII) formed has six aliphatic side groups and two cyano groups.

N

tu 2 ° R? 25 f ^ 4y „R '(VIII) R *

The conversion of the two cyano groups into carboxyl groups is described in Makromol. Chem. 181, 30 (1980) 2127 (D. Wóhrle, G. Meyer). Then both carboxylic acid groups are converted into an acid anhydride group by refluxing in benzene acetyl chloride (1: 1 v / v). In J. Chem. Soc. Chem. Commun. (1987) 390 (N. Kobayashi, Y. Nishiyama, T. Ohya, M. Sato).

The group L may be a linear aliphatic group which may optionally be interrupted by a para-substituted aromatic group, for example a benzene ring. As the number of the metylene groups 1009541 11 increases, the solubility of the diacetylene compound in the solvent will also increase.

The application of the arylalkyldiacetylene compound with (I) or the reactants from which this compound can be formed on the support can be carried out by various known coating techniques, such as chemical vapor deposition (CVD), dip coating by dipping the support in a solvent in which the compounds are dissolved, or, for example, by spin coating. It is thus possible to apply thin layers in a controllable manner. The layers have a thickness generally between 100 and 1000 nanometers. 100 nanometers is usually a lower limit because below this layer thickness there is a risk of forming so-called pin-holes. Above a layer thickness of generally 1000 nanometers, the layer becomes so thick that, for example, no additional contribution is made; light absorption and ohmic losses can occur during electron passage and / or hole conduction. The 20 layer thicknesses are generally between 400 and 600 nanometers.

Generally, the carriers are formed by oxidic materials, glass, metal surfaces, semiconductor materials, and the like. Known support materials to be used include silicon dioxide, glass, platinum, gold, silver, tin dioxide, titanium dioxide, and indium tin dioxide (ITO).

As indicated above, it is possible for the diacetylene compound to be formed either by a thermally induced coupling or by a chemical coupling. Subsequently, the final polymerization usually takes place by thermal heating at a temperature between generally 350 ° C and 500 ° C. In order to avoid the volatile reactants from disappearing as much as possible in both these reactions, it is preferred to carry out these reactions on the support in a closed system, for example in a pressure vessel. However, if the layer is subsequently used in a 1009541 12 electrical device and the layer is to be provided on both sides with a conductive material, it is preferable to include the layer to be polymerized at least between a metal coating which is then electrode will form. Thus, at least the layer to be polymerized is interposed between the top layer and the support and evaporation is suppressed for that reason as well. In order to avoid side reactions as much as possible, it is further preferred to carry out the reaction under inert conditions.

Mentioned and other features of the method, the obtained layer of arylalkyl modified polyacetylene on the support and the use thereof, will be elucidated hereinafter on the basis of a number of exemplary embodiments.

Example 1

A solution of monomer diacetylene A in chloroform (concentration 15-100 mM., In particular 25 mM.) Is dripped onto a flat substrate consisting of titanium dioxide (TiO2), which is kept for 5 sec. rotating at a speed of 500 rpm and then 5 sec. spins at a speed of 2000 rpm (This procedure is called spin coating). The solution is spread over the TiO2 surface, the solvent chloroform evaporates, and a thin layer of monomer A remains. This monomer is then polymerized with 254 nm UV light (mercury lamp) for 0.5 to 5 hours. The film generally has a thickness of 100-1000 nm, in particular 200-500 nm. An electrical back contact is then applied to this polymerized film by means of a mercury drop. The contact area of the mercury droplet ret the polymer is 0.78 mm 2.

35, 1009541 °.

13 5 I Jn- (ch2) 9 - = - * = - (CH2) 9 —n 1/1 o A 0

Under conditions in which there is no exposure, the material behaves like a diode. That is, under conditions of a positive bias (mercury drop 10 more positive potential), no current flows; under conditions of a negative bias of -0.8 Volt an anodic current (to the Ti2 electrode) of 10'6 Ampere flows.

15 Example 2

As example 1, but now examined under lighting conditions:

Under conditions in which the cell is illuminated with a xenon lamp with a light intensity of 1000 mW / cm2, a photocurrent will flow. Under conditions of a positive bias of +0.8 Volt a cathodic current of 4 * 10'4 Ampere is running. Under conditions of a negative bias of -0.8 Volt an anodic current of 10 "3 Ampere is running.

25

Example 3

As example 2, but now tested with indium tin dioxide.

No photocurrent is observed.

30

Example 4

Diacetylene compound A can also be formed from the acetylene precursor B

35 1009541 14

O

(CH2) 9 - = —H

5 O

B

Compound B is spin-coated on a support material. For conditions see example 1. The B film is then heat treated. The compound melts at 56 ° C. Heating to 342 ° C leads to an exothermic reaction in which the compound A (the diacetylene) is simultaneously formed first, which reacts directly to polydiacetylene. In a separate experiment it has been determined that A thermally polymerizes to polydiacetylene at a temperature of 324 ° C.

Example 5

Compound C is spin-coated on a support material. For conditions see example 1.

(CH2) 9 s = —H

The C film is then heat treated. The compound melts at 195 ° C.

Heating to 344 ° C leads to an exothermic reaction in which the diacetylene is first formed, which reacts directly to the polydiacetylene.

Example 6 Compound D is spin-coated on a support material. For conditions see example 1.

i 1009541 15

CH2 - = - H

D

The film consisting of D is heat treated. This compound melts at 323 ° C. Further heating leads to two exothermic processes: one at 328 10 ° C and one at 335 ° C. At the first temperature, the diacetylene is formed, which crystallizes at the second temperature. Further heating to 500 ° C for 2 hours leads to the polydiacetylene.

1009541

Claims (15)

A process for manufacturing a film of arylalkyl modified polyacetylene, wherein a layer of an arylalkyl diacetylene compound of the formula (I) 5 X (N) -LC = CC = CL- (N) X (I) is supported wherein X (N) is a nitrogen-containing, flat aromatic group 10 L a linear aliphatic group - <CIVn- 15 with 1 sns 22, preferably 1 sns 9, more preferably 1 sns 6, or a linear group - (CH2) pY - (CH2) q-, 20 with 1 sp + qs 22, wherein preferably: sp or qs 9, more preferably 1 sp or qs 6, and Y represents a para-substituted aromatic group 25 is formed and polymerized to the arylalkyl modified polyacetylene. 2. Process according to claim 1, wherein the arylalkyldiacetylene compound is formed on the support from the compound of the formula (II) X (N) -LC = CH (II) f00954 ί or from X (0) with H2N-L- CsC-C = CL-NH2 wherein X (N) and L each have the meanings indicated above, and X (0) is an oxygen-containing planar aromatic group. 3. A method according to claim 1 or 2, wherein the polymerization is a 1,4 polymerization and the arylalkyl modified polydiacetylene is formed. The method of claim 1 or 2, wherein the polymerization is a 1,2 polymerization and the arylalkyl modified polyacetylene is formed. 5. Process according to claims 1-4, wherein the nitrogen-containing planar aromatic group X (N) is a compound of the formula III O, Λ-IL / 20 (III) O wherein X represents a benzene ring, or fused benzene rings. 6. Process according to claims 1-4, wherein the nitrogen-containing planar aromatic group X (N) is a compound of the formula IV 30 \ N- / (IV) X '' wherein X represents a benzene ring, or fused benzene rings . 1009541 A method according to claim 5 or 6, wherein X represents 2-9 fused benzene rings. 8. Process according to claims 1-4, wherein the nitrogen-containing planar aromatic group X (N) is the compound of formula III. O wherein X (N) is a phthalocyanine derivative of the formula IV. Ir N = ^} -N 15. JVvC N = ^ ^ -N 20. m R R where R = OCmH2m + 1 with m is 1-20 and M = 2H, Mg, Zn, Co, Fe, AlCl, TiO, SnO. 9. A method according to claim 8, wherein a = S-18, preferably 12. A method according to claims 1-9, wherein the polymerization to arylalkyl modified polyacetylene is carried out by heating, photochemical and / or ionizing radiation. The method of claims 1-10, wherein the polymerization is performed in a closed system. 12. A method according to claims 1-11, wherein a coating is applied to the layer of the arylalkyl diacetylene compound prior to the polymerization. A method according to claims 1-12, wherein the carrier comprises a (semi-) conductive material. 1009541 A supported layer of arylalkyl modified polyacetylene available by the method of claims 1-13. The use of a layer of arylalkyl modified polyacetylene applied on a support 5 obtained by the method according to claim 1-13 or claim 14 as an electrically conductive polymer for instance in a photovoltaic element, photodiode, photoconductor. 10 1009541 COOPERATION TREATY (PCT) REPORT ON INTERNATIONAL TYPE STANDARD RESEARCH RESEARCH> IDENTIFICATION OF THE NATIONAL APPLICATION Characteristic of the applicant or of the authorized representative P HP / SvW / K-47 Dutch application no. Filing date 1009541 Claimed priority date NV KEMA Date of the request for an examination of international type Awarded by the International Research Authority (ISA) to the request for an examination of international type No SN 31747 EN I. CLASSIFICATION OF THE SUBJECT (where different classifications apply, all classify symbols) According to International Classification (IRC) Int.Cl.6: C 08 F 38/00, C 08 J 5/18, H 01 L 31/0246 II. FIELDS OF TECHNIQUE EXAMINED Minimum documentation examined Classification system I _ Classification symbols Int.Cl.6: C 08 F, C 09 D Documentation examined other than minimum documentation insofar as such documents have been examined in the areas examined «Hl · 1 1 NO RESEARCH POSSIBLE FOR CERTAIN CONCLUSIONS (Comments on Supplementary Sheet), IV- 1 1 LACK OF UNITY OF INVENTION (Comments on Supplementary Sheet)? -----— Porm RCT / ISA / 701 (as of 07.1979