POLYTHIOPHENES IN ORGANIC SOLVENTS

Abstract

The present invention relates to a composition comprising i) at least one polythiophene comprising monomer units of structure (Ia) or (Ib)

##STR00001## in which *, X, Z, R, and R.sup.1-R.sup.6 are as defined herein; ii) at least one organic compound carrying one or two inorganic acid group(s), preferably one or two sulfonic acid group(s), one or two sulfuric acid group(s), one or two phosphonic acid group(s) or one or two phosphoric acid group(s), or a salt of said organic compound, wherein the molecular weight of the organic compound or the salt thereof is less than 1,000 g/mol; and iii) at least one organic solvent. A method of preparing such compounds is also provided.

Claims

1. A composition comprising i) at least one polythiophene comprising monomer units of structure (IA) or (Ib) ##STR00028## in which * indicates the bond to the neighboring monomer units, X,Z represent O or S, R.sup.1-R.sup.6 independently from each other represent a hydrogen atom or an organic residue R, with the proviso that at least one of residues R.sup.1 to R.sup.4 and one of residues R.sup.5 and R.sup.6 represents an organic residue R; ii) at least one organic compound carrying one or two inorganic acid group(s) selected from the group consisting of one or two sulfonic acid group(s), one or two sulfuric acid group(s), one or two phosphonic acid group(s), one or two phosphoric acid group(s), and a salt of said organic compound, wherein the molecular weight of the organic compound or the salt thereof is less than 1,000 g/mol; and iii) at least one organic solvent.

2. The composition according to claim 1, wherein the composition is a dispersion, wherein the polythiophene i) and the organic compound ii) form a complex that is homogeneously dispersed in the organic solvent iii).

3. The composition according to claim 1, wherein the organic residue R does not carry anionic groups.

4. The composition according to claim 1, wherein the polythiophene is a homopolymer or copolymer comprising monomer units of structure (Ia) in which X and Z represent O, and wherein three of the residues selected from the group consisting of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 represent a hydrogen atom and the remaining residue represents an ether group having the structural formula (IIa)
—(CR.sup.7R.sup.8).sub.n—O—R.sup.9   (IIa) wherein R.sup.7 is H, a C.sub.1-C.sub.10-alkyl group or a C.sub.1-C.sub.10-alkoxy group, preferably H; R.sup.8 is H, a C.sub.1-C.sub.10-alkyl group or a C.sub.1-C.sub.10-alkoxy group, preferably H; n is an integer in the range from 0 to 10; and R.sup.9 is a C.sub.1-C.sub.30 alkyl group, an alkoxy group, an aryl group, an ether group or an ester group.

5. The composition according to claim 1, wherein the polythiophene is a homopolymer or copolymer comprising monomer units of structure (Ia) in which X and Z represent O, and wherein three of the residues selected from the group consisting of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 represent a hydrogen atom and the remaining residue represents an alkyl group having formula (IIb)
—C.sub.nH.sub.2n+1   (IIb) wherein n is an integer in the range from 1 to 20.

6. The composition according to claim 1, wherein the polythiophene is a homopolymer or copolymer comprising monomer units of structure (Ia) in which X and Z represent O, and wherein three of the residues selected from the group consisting of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 represent a hydrogen atom and the remaining residue represents a branched alkyl group or a branched ether group.

7. The composition according to claim 6, wherein the remaining residue represents a branched ether group having the structural formula (IIc)
—(CR.sup.10 R.sup.11).sub.n—O—R.sup.12   (IIc) wherein R.sup.10 is H, a C.sub.1-C.sub.10-alkyl group or a C.sub.1-C.sub.10-alkoxy group; R.sup.11 is H, a C.sub.1-C.sub.10-alkyl group or a C.sub.1-C.sub.10-alkoxy group; n is an integer in the range from 0 to 10; and R.sup.12 is a branched alkyl group or a branched arylalkyl group, wherein neither the branched alkyl group nor the branched arylalkyl group comprise an unsaturated C═C-bond in the alkyl chain.

8. The composition according to claim 7, wherein R.sup.12 is an organic residue having formula (IId)
—(CHR.sup.13).sub.m—R.sup.14   (IId) wherein m is 1, 2 or 3, R.sup.13 is H or a C.sub.1-C.sub.12 alkyl group, with the provisio that in only one of the structural units —CHR.sup.13— residue R.sup.13 is a C.sub.1-C.sub.12 alkyl group; R.sup.14 is a C.sub.1-C.sub.10-alkyl group or a aryl group.

9. The composition according to claim 1, wherein the composition further comprises iv) at least one non-conductive oligomeric or polymeric binder, preferably a poly(meth)acrylate and/or a polysilicone.

10. The composition according to claim 1, wherein the organic compound ii) is an anionic surfactant.

11. The composition according to claim 1, wherein the at least one organic solvent iii) is selected from the group consisting of toluene, xylene, anisole, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, octyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, 1-methoxy-2-propylacetat, 1-methoxy-2-propanol, butanol, 2-propanol, ethanol and mixtures thereof or mixtures of one or two of these aprotic solvents with one or two further solvents.

12. The composition according to claim 1, wherein the composition has an iron content of less than 30 ppm, based on the total weight of the composition.

13. A process for preparing a composition, the process comprising the steps of I) providing a reaction mixture comprising i) thiophene monomers of structure (VIa) or (VIb) ##STR00029## in which X,Z represent O or S, R.sup.1-R.sup.6 independently from each other represent a hydrogen atom or an organic residue R, with the proviso that at least one of residues R.sup.1 to R.sup.4 and one of residues R.sup.5 and R.sup.6 represents an organic residue R; ii) at least one organic compound carrying one or two inorganic acid group(s), preferably one or two sulfonic acid group(s), one or two sulfuric acid group(s), one or two phosphonic acid group(s) or one or two phosphoric acid group(s), or a salt of said organic compound, wherein the molecular weight of the organic compound or the salt thereof is less than 1,000 g/mol; iii) at least one organic solvent; and iv) at least one oxidizing agent, preferably at least one organic peroxide; II) oxidatively polymerizing the thiophene monomers for the formation a polythiophene.

14. The process according to claim 13, wherein the reaction mixtures provided in process step I) comprises thiophene monomers of structure (VIa) in which X and Z represent O, and wherein three of the residues selected from the group consisting of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 represent a hydrogen atom and the remaining residue represents an ether group having the structural formula (IIa)
—(CR.sup.7R.sup.8).sub.n—O—R.sup.9   (IIa) wherein R.sup.7 is H, a C.sub.1-C.sub.10-alkyl group or a C.sub.1-C.sub.10-alkoxy group; R.sup.8 is H, a C.sub.1-C.sub.10-alkyl group or a C.sub.1-C.sub.10-alkoxy group; n is an integer in the range from 0 to 10; and R.sup.9 is an alkyl group, an alkoxy group, an aryl group, an ether group or an ester group, preferably a C.sub.1-C.sub.30 alkyl group.

15. The process according to claim 13, wherein the reaction mixtures provided in process step I) comprises thiophene monomers of structure (VIa) in which X and Z represent O, and wherein three of the residues selected from the group consisting of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 represent a hydrogen atom and the remaining residue represents an alkyl group having formula (IIb)
—C.sub.nH.sub.2n+1   (IIb) wherein n is an integer in the range from 1 to 20.

16. The process according to claim 13, wherein the reaction mixtures provided in process step I) comprises thiophene monomers of structure (VIa) in which X and Z represent O, and wherein three of the residues selected from the group consisting of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 represent a hydrogen atom and the remaining residue represents a branched alkyl group or a branched ether group.

17. The process according to claim 16, wherein the remaining residue represents a branched ether group having the structural formula (IIc)
—(CR.sup.10R.sup.11).sub.n—OR.sup.12   (IIc) wherein R.sup.10 is H, a C.sub.1-C.sub.10-alkyl group or a C.sub.1-C.sub.10-alkoxy group; R.sup.11 is H, a C.sub.1-C.sub.10-alkyl group or a C.sub.1-C.sub.10-alkoxy group; n is an integer in the range from 0 to 10; and R.sup.12 is a branched alkyl group or a branched arylalkyl group, wherein neither the branched alkyl group nor the branched arylalkyl group comprise an unsaturated C═C-bond in the alkyl chain.

18. The process according to claim 17, wherein R.sup.12 is an organic residue having formula (IId)
—(CHR.sup.13).sub.m—R.sup.14   (IId) wherein m is 1, 2 or 3, R.sup.13 is H or a C.sub.1-C.sub.12 alkyl group, with the provisio that in only one of the structural units —CHR.sup.13— residue R.sup.13 is a C.sub.1-C.sub.12 alkyl group; R.sup.14 is a C.sub.1-C.sub.10-alkyl group or a aryl group.

19. A layer structure comprising a substrate and an electrically conductive layer applied onto the substrate, wherein the electrically conductive layer comprises a polythiophene i) as defined in in claim 1 and at least one organic compound ii) carrying one or two inorganic acid group(s), preferably one or two sulfonic acid group(s), one or two sulfuric acid group(s), one or two phosphonic acid group(s) or one or two phosphoric acid group(s), or a salt of said organic compound, as defined in claim 1.

20. A process for the preparation of a layer structure, comprising the process steps of A) provision of a substrate; B) coating a substrate (with a composition according to claim 1 C) at least partial removal of the organic solvent iii) for the formation of an electrically conductive layer.

21. An electronic component comprising a layer structure according to claim 19.

22. (canceled)

Description

EXAMPLES

Example 1

Reference Example for the Synthesis of 2-[(decyloxy)methyl]-2,3-dihydrothieno[3,4-b]-1,4-dioxin

[0257] ##STR00023##

[0258] The synthesis is conducted under dry and inert conditions.

[0259] THF (6.6 L) and 18-Crown-6 (22.0 g, 88 mmol) are added to the reaction vessel. NaH (166.4 g, 4.15 mol) as 60% suspension in oil is added under stirring, the mixture is stirred at room temperature. At 0° C. a EDOT-MeOH (551 g, 3.2 mol) solution in THF are added to the NaH solution. After addition of the solution the reaction mixture is stirred for 1.5 h at room temperature, subsequently 1 h at 50° C. Reaction mixture is cooled to 0° C. and a 1-bromo-decane (936.7 g, 4.2 mol) solution, stirred for 1 h at room temperature and 15 h at 50° C. The reaction mixture is cooled to room temperature and quenched with a mixture of isopropanol/water 70:30 (v/v). The crude product was purified by column chromatography.

[0260] The reaction product (2-[(decyloxy)methyl]-2,3-dihydro-thieno[3,4-b]-1,4-dioxin, CAS: 210476-55-4) is obtained as a yellow oil in a yield of 74-80%.

Example 2

Comparative Example According to the Teaching of WO-A-2012/059215

[0261] A 1 L three-necked round-bottom flask equipped with mechanical stirrer was charged with 294 g anisole (Aldrich), 9.4 g of dibenzoyl peroxide (39 mmol; Aldrich), 8.25 g of a sulfonated block-copolymer (Kraton Nexar® MD) and 7.2 g of para-toluene sulfonic acid (38 mmol, Aldrich). After heating to 60° C. 4.95 g of 3,4-ethylenedioxythiophene (35 mmol; Clevios M V2; Heraeus Deutschland GmbH & Co KG, Germany) dissolved in 20 g of anisole were added over 40 min. The dispersion was stirred for another 3 h at 60° C. and then cooled to room temperature. This dispersion is called dispersion 2A.

[0262] 20 g of the dispersion obtained after filtration and 20 g of butyl acetate were mixed in a 50 ml glass bottle and subjected to 2 min or ultrasound treatment (Hielscher UP 200 S, cycle 1, amplitude 100%). This sample is called dispersion 2B.

[0263] Analysis of Dispersion 2B:

[0264] Solids content: 2.5% (gravimetric)

[0265] Using a wire-bar a 12 μm wet film was deposited of dispersion 2B on a substrate and dried for 15 min at 130° C. in an oven. The conductive layer was characterized by the following properties:

[0266] Conductivity (on glass): 7.7 S/cm

[0267] Sheet resistance (12 μm on PET): 17,000 Ohm/sq

Example 3

According to the Present Invention

[0268] In Example 3 the following complex is prepared:

##STR00024##

[0269] Dispersion A:

[0270] A 100 ml three-necked round-bottom flask equipped with mechanical stirrer, condenser and nitrogen inlet was charged with 29.7 g anisole (Aldrich), 2.7 g of dibenzoyl peroxide (11.1 mmol; Aldrich) and 3.7 g dodecylbenzene sulfonic acid (11.5 mmol; Aldrich). After heating to 60° C. 0.705 g of 3,4-ethylenedioxythiophene (5 mmol; Clevios M V2; Heraeus Deutschland GmbH & Co KG, Germany) and 1.55 g of the EDOT-derivative obtained in the Example 1(5 mmol) were added. The dispersion was stirred for another 3 h at 60° C. under nitrogen. Then 35 g of anisole were added. After cooling to room temperature, the dispersion was let to stand overnight. This dispersion is called dispersion 3A.

[0271] Dispersion 3B:

[0272] 5 g of dispersion 3A and 5 g butyl acetate were mixed in a 20 ml glass bottle and subjected to 1 min of ultrasound treatment (Hielscher UP 200 S, cycle 1, amplitude 100%). This material is called dispersion 3B.

[0273] Analysis of Dispersion 3B:

[0274] Solids content: 2.4% (gravimetric)

[0275] Using a wire-bar a 12 um wet film was deposited on a PET substrate and dried for 15 min at 130° C. in an oven. The film was characterized by the following properties:

[0276] Sheet resistance (12 μm on PET) 20,000 Ohm/sq

[0277] Dispersion 3C:

[0278] 2.5 g of dispersion+3A, 2.5 g anisole and 5 g butyl acetate were mixed in a 20 ml glass bottle and subjected to 1 min of ultrasound treatment (Hielscher UP 200 S, cycle 1, amplitude 100%). This material is called dispersion 3C.

[0279] Analysis of Dispersion 3C:

[0280] Solids content: 1.2% (gravimetric)

[0281] Water content: 0.04%

[0282] Ion-content was measured by inductively coupled plasma optical emission spectrometry:

[0283] Na content: 24 ppm

[0284] Ca content: 0.6 ppm

[0285] Mg content: 0.06 ppm

[0286] K, Fe, Cu, Pb, Al, Cr, Co, Mn, Ni, V, Zn and Cd were below the detection limit of 0.025 ppm.

[0287] Using a wire-bar a 12 μm wet film was deposited on a PET substrate and dried for 15 min at 130° C. in an oven. The film was characterized by the following properties:

[0288] Sheet resistance (12 μm on PET) 16,000 Ohm/sq

[0289] Transmission (including PET) 83.3%

[0290] Haze (including PET) 0.58

[0291] Dispersion 3C was deposited on glass by spin-coating and dried for 10 min at 130° C. on a hot plat. The conductivity was measured according to the Test method described above.

[0292] The film was characterized by the following property

[0293] Conductivity 9.4 S/cm

Example 4

According to the Present Invention

[0294] (in Example 4 the concentration of dodecylbenzenesulfonic acid is reduced)

[0295] A 100 ml three-necked round-bottom flask equipped with mechanical stirrer, condenser and nitrogen inlet was charged with 29.7 g anisole (Aldrich), 2.7 g of dibenzoyl peroxide (11.1 mmol; Aldrich) and 3.08 g dodecylbenzene sulfonic acid (9.6 mmol; Aldrich). After heating to 60° C. 0.705 g of 3,4-ethylenedioxythiophene (5 mmol; Clevios M V2; Heraeus Deutschland GmbH & Co KG, Germany) and 1.55 g of the EDOT-derivative obtained in the Example 1 (5 mmol) were added. The dispersion was stirred for another 3 h at 60° C. under nitrogen. Then 35 g of anisole were added. After cooling to room temperature, the dispersion was let to stand overnight. This dispersion is called dispersion 4A.

[0296] 5 g of dispersion 4A, and 5 g butyl acetate were mixed in a 20 ml glass bottle and subjected to 1 min of ultrasound treatment (Hielscher UP 200 S, cycle 1, amplitude 100%). This material is called dispersion 4C.

[0297] Analysis of dispersion 4C:

[0298] Solids content: 2.1% (gravimetric)

[0299] Using a wire-bar a 12 μm wet film was deposited on a PET substrate and dried for 15 min at 130° C. in an oven. The film was characterized by the following properties:

[0300] Sheet resistance (12 μm on PET): 12,000 Ohm/sq

Example 5

According to the Present Invention

[0301] (in Example 5 the concentration of dodecylbenzenesulfonic acid is reduced further)

[0302] A 100 ml three-necked round-bottom flask equipped with mechanical stirrer, condenser and nitrogen inlet was charged with 29.7 g anisole (Aldrich), 2.7 g of dibenzoyl peroxide (11.1 mmol; Aldrich) and 2.2 g dodecylbenzene sulfonic acid (6.8 mmol; Aldrich). After heating to 60° C. 0.705 g of 3,4-ethylenedioxythiophene (5 mmol; Clevios M V2; Heraeus Deutschland GmbH & Co KG, Germany) and 1.55 g of the EDOT-derivative obtained in the Example 1 (5 mmol) were added. The dispersion was stirred for another 3 h at 60° C. under nitrogen. Then 35 g of anisole were added. After cooling to room temperature, the dispersion was let to stand overnight. This dispersion is called dispersion 5A.

Example 6

[0303] Dispersion 2A and dispersion 5A were compared with respect to their solvent compatibility. Samples were mixed with additional solvent as shown in Table 1 and then subjected to ultrasound for 1 min.

[0304] Using a wire-bar a 12 μm wet film was deposited on a PET substrate and dried for 15 min at 130° C. in an oven. The sheet resistance was determined.

TABLE-US-00001 TABLE 1 Dilution of inventive dispersion 5A and reference dispersion 2A with different solvents and sheet resistance of the respective films. polythiophene Example dispersion added solvent SR (Ohm/sq) 6A (inventive) 5 g dispersion 5A 5 g DMSO 1.5 × 10.sup.5  6B (inventive) 5 g dispersion 5A 5 g n-butanol 2.2 × 10.sup.4  6C (reference) 5 g dispersion 2A 5 g DMSO 1.8 × 10.sup.11 6D (reference) 5 g dispersion 2A 5 g n-butanol 6.9 × 10.sup.10

[0305] Table 1 shows that the inventive dispersion 5A gives low sheet resistance values of less 1.5×10.sup.5 Ohm/sq with various solvents whilst dispersion 2A gives values of up to 10.sup.11 Ohm/sq.

Example 7

[0306] A 2.5% solution of poly(isobutyl methacrylate) in an anisole/butyl acetate mixture (50%/50% w/w) was prepared. This solution was mixed in different ratios with dispersion 2B. Since both solutions have the same solids content, the ratio of the solution/dispersion corresponds to the ratio of solids in the resulting film.

[0307] Additionally, a 2.4% solution of poly(isobutyl methacrylate) in an anisole/butyl acetate mixture (50%/50% w/w) was prepared. This solution was mixed in different ratios with dispersion 3B. Since both solutions have the same solids content, the ratio of the solution/dispersion corresponds to the ratio of solids in the resulting film.

[0308] Using a wire-bar 12 μm wet films of all eight mixtures were deposited on PET substrates and dried for 15 min at 130° C. in an oven.

TABLE-US-00002 TABLE 2 Sheet resistance and haze of polythiophene/poly(isobutyl methacrylate) coatings on PET films ratio of polythio- phene complex solids and poly(isobutyl content sheet methacrylate) in of mixture resistance dispersion dried film (w:w) [%] (Ohm/sq) haze (%) 2B (reference) 1:9 2.5 6.3 × 10.sup.7 1.2 2B (reference) 1:4 2.5 5.0 × 10.sup.6 6.7 2B (reference) 1:2 2.5 6.6 × 10.sup.5 13.3 2B (reference) 1:1 2.5 1.3 × 10.sup.5 17.5 3B (inventive) 1:9 2.4 1.6 × 10.sup.6 0.42 3B (inventive) 1:4 2.4 1.7 × 10.sup.5 0.49 3B (inventive) 1:2 2.4 5.5 × 10.sup.4 0.55 3B (inventive) 1:1 2.4 2.6 × 10.sup.4 0.8

[0309] Table 2 shows that the inventive dispersion 3B results in lower sheet resistance and lower haze when blended with poly(isobutyl methacrylate) compared to reference dispersion 2B.

Example 8

According to the Present Invention

[0310] In Example 8 the following complex is prepared:

##STR00025##

[0311] Dispersion 8A:

[0312] A 100 ml three-necked round-bottom flask equipped with mechanical stirrer, condenser and nitrogen inlet was charged with 29.7 g anisole (Aldrich), 2.7 g of dibenzoyl peroxide (11.1 mmol; Aldrich) and 3.0 g dodecylbenzene sulfonic acid (9.3 mmol; DBSA; Aldrich). After heating to 60° C. 0.42 g of 3,4-ethylenedioxythiophene (3 mmol; Clevios M V2; Heraeus Deutschland GmbH & Co KG, Germany) and 1.38 g of 2-butyl-2,3-dihydrothieno[3,4b][1,4]dioxine (7 mmol; ButylEDOT; CAS 552857-06-4, Synmax Biochemical, Taiwan) are added. The dispersion was stirred for another 3 h at 60° C. under nitrogen. Then 35 g of anisole were added. After cooling to room temperature, the dispersion was let to stand overnight. This dispersion is called dispersion 8A.

[0313] Dispersion 8B:

[0314] 5 g of dispersion 6A, 3 g anisole and 2 g butanol were mixed in a 20 ml glass bottle and subjected to 1 min of ultrasound treatment (Hielscher UP 200 S, cycle 1, amplitude 100%). This material is called dispersion 8B.

[0315] Using a wire-bar a 12 μm wet film was deposited on a PET substrate and dried for 15 min at 130° C. in an oven. The film was characterized by the following properties:

[0316] Sheet resistance (12 μm on PET) 17,400 Ohm/sq

[0317] Haze (12 μm on PET) 0.7

Example 9

According to the Present Invention

[0318] The synthesis of example 8 was repeated using 0.846 g of 3,4-ethylenedioxythiophene (6 mmol) and 0.79 g of 2-butyl-2,3-dihydrothieno[3,4b][1,4]dioxine (4 mmol). All other parameters remained unchanged. The final material obtained after ultrasound treatment is called dispersion 9B.

Example 10

According to the Present Invention

[0319] The synthesis of example 8 was repeated using 0.705 g of 3,4-ethylenedioxythiophene (5 mmol) and 0.98 g of 2-butyl-2,3-dihydrothieno[3,4b][1,4]dioxine (5 mmol). All other parameters remained unchanged. The final material obtained after ultrasound treatment is called dispersion 10B.

Example 11

According to the Present Invention

[0320] The synthesis of example 8 was repeated using 0.56 g of 3,4-ethylenedioxythiophene (4 mmol) and 1.18 g of 2-butyl-2,3-dihydrothieno[3,4b][1,4]dioxine (6 mmol). All other parameters remained unchanged. The final material obtained after ultrasound treatment is called dispersion 11B.

Example 12

According to the Present Invention

[0321] The synthesis of example 8 was repeated using 2-butyl-2,3-dihydrothieno-[3,4b][1,4]dioxine in an amount of 10 mmol. No 3,4-ethylenedioxythiophene was used. All other parameters remained unchanged. The dispersion that is obtained after cooling to room temperature and standing overnight is called dispersion 12A. The final material obtained after ultrasound treatment is called dispersion 12B.

[0322] Using a wire-bar 12 μm wet films were deposited from dispersions 9B to 12B pursuant to Example 8 on a PET substrate and dried for 15 min at 130° C. in an oven. The films were characterized by their sheet resistance and haze.

[0323] Ion-content of 12 B was measured by inductively coupled plasma optical emission spectrometry:

TABLE-US-00003 Na content:  1.4 ppm Ca content:  2.8 ppm Mg content: 0.02 ppm

[0324] K, Fe, Cu, Pb, Al, Cr, Co, Mn, Ni, V, Zn and Cd were below the detection limit of 0.025 ppm.

[0325] Table 3 summarizes the results of Dispersions 2B and 8B to 12B with respect to sheet resistance and haze.

TABLE-US-00004 TABLE 3 Sheet resistance and Haze of films prepared with dispersions 2B and 8B-12B amount side chain of EDT- amount sheet re- disper- in EDT- derivative of EDT count- sistance haze sion derivative [mmol] [mmol] erion (Ohm/sq) (%)  2B none — 35 Nexar ® 17,000 0.6 MD  9B n-butyl  4  6 DBSA  4,100 6.1 10B n-butyl  5  5 DBSA  7,300 3.1 11B n-butyl  6  4 DBSA 14,400 0.7  8B n-butyl  7  3 DBSA 17,400 0.7 12B n-butyl 10  0 DBSA 80,000 0.5

Example 13

According to the Present Invention

[0326] A solution of poly(isobutylmethacrylate) (PIBM) was prepared. For that purpose, 13.6 g poly(isobutyl methacrylate) were dissolved in a mixture of 220 g anisole, 132 g butyl acetate and 88 g butanol. [0327] Series 1 of blends: [0328] A series of blends of PIBM solution with dispersions 2B and 8B-12B were prepared. 9 g of the PIBM solution were mixed with 0.34 g of dispersion 12B and 0.55 g anisole, 0.33 g butyl acetate and 0.22 g of butanol. The mass ratio of the non-conductive PIBM and the polythiophene/DBSA complex is 36:1. In the same way 0.34 g of dispersions 2B and 8B to 11B were blended with 9 g of PIBM solution and additional solvents. [0329] Series 2 of blends: [0330] A second series of blends was prepared. 4 g of the PIBM solution were mixed with 0.29 g of dispersion 12B and 0.35 g anisole, 0.21 g butyl acetate and 0.14 g butanol. The mass ratio of the non-conductive PIBM and the polythiophene/DBSA complex is 19:1. In the same way 0.29 g of dispersions 2B and 8B to 11B were blende with 4 g of PIBM solution and additional solvents.

[0331] Using a wire-bar a 12 um wet film of the dispersions in series 1 and 2 was deposited on PET substrates and dried for 15 min at 130° C. in an oven. The films were characterized by their sheet resistance. Table 4 summarizes the results.

TABLE-US-00005 TABLE 4 Sheet resistance of films prepared with dispersions 2B and 8B-12B into which PIBM has been added sheet re- sheet re- sistance sistance in blend in blend amount with with side chain of EDT- amount PIBM PIBM disper- in EDT- derivative of EDT counter 1:19 1:36 sion derivative [mmol] [mmol] ion (Ω/sq) (Ω/sq) .sup.  2B.sup.1) none — 35  Nexar ® 2 × 10.sup.11 2 × 10.sup.11 MD  9B n-butyl 4 6 DBSA 4 × 10.sup.10 2 × 10.sup.11 10B n-butyl 5 5 DBSA 3 × 10.sup.9  1 × 10.sup.10 11B n-butyl 6 4 DBSA 4 × 10.sup.7  1 × 10.sup.10  8B n-butyl 7 3 DBSA 1 × 10.sup.7  2 × 10.sup.7  12B n-butyl 10  0 DBSA 1 × 10.sup.7  1 × 10.sup.7  (.sup.1)not according to the present invention)

[0332] Table 4 clearly shows the advantage of polythiophenes comprising alkyl-EDOT.

Example 14

According to the Present Invention

[0333] The dispersion obtained in Example 12A was diluted with a range of solvents. Table 5 shows solvent mixtures.

Example 14B

[0334] 5 g of Dispersion 12 B were mixed with 3 g anisole and 2 g n-butanol. The resulting solvent mixture contained 80% anisole (w/w) and 20% n-butanol (w/w). Using a wire-bar a 12 μm wet films of dispersions was deposited on PET substrates and dried for 15 min at 130° C. in an oven. The solids content was 2.2%. The sheet resistance was 8×10.sup.4 Ohm/sq

Example 14C

[0335] 5 g dispersion were mixed with 10 g anisole and 5 g n-butanol. The resulting solvent mixture contained 75% anisole and 25% n-butanol. The solids content was 1.1%. Using a wire-bar a 12 μm wet films of dispersions was deposited on PET substrates and dried for 15 min at 130° C. in an oven. The sheet resistance was 16×10.sup.4 Ohm/sq.

[0336] Examples 14D, 14 E, 14F and 14 G are prepared accordingly.

[0337] Table 5 shows the compositions and resulting sheet resistances:

TABLE-US-00006 TABLE 5 Blends of dispersion 12A with various solvents dis- concen- sheet re- per- tration butyl ethyl n- iso- sistance sion [wt.-%] anisole acetate toluene acetate butanol propanol PGME (S)/sq) 14B 2.2 80 20  8 × 10.sup.4 14C 1.1 75 25 16 × 10.sup.4 14D 1.1 50 50 16 × 10.sup.4 14E 1.1 25 25 50 11 × 10.sup.4 14F 2.2 50 30 20  8 × 10.sup.4 14G 1.1 40 10 25 25 25 × 10.sup.4

[0338] In all six cases uniform dispersions were obtained that do not form particles or precipitates. Table 5 also clearly shows the advantage of polythiophenes comprising alkyl-EDOT.

Example 15

According to the Present Invention

[0339] A 100 ml three-necked round-bottom flask equipped with mechanical stirrer, condenser and nitrogen inlet was charged with 29.7 g anisole (Aldrich), 2.7 g of dibenzoyl peroxide (11.1 mmol; Aldrich) and 3.0 g dodecylbenzene sulfonic acid (9.3 mmol; DBSA; Aldrich). After heating to 60° C. 0.56 g of 2-decyl-2,3-dihydrothieno[3,4b][1,4]dioxine (2 mmol; DecylEDOT; CAS 126213-55-6) and 1.58 g of 2-butyl-2,3-dihydrothieno[3,4b][1,4]dioxine (8 mmol; ButylEDOT; CAS 552857-06-4) are added. The dispersion was stirred for another 3 h at 60° C. under nitrogen. Then 35 g of anisole were added. After cooling to room temperature, the dispersion was let to stand overnight. This dispersion is called dispersion 15A.

[0340] Dispersion 15B:

[0341] 5 g of dispersion 15A, 3 g anisole and 2 g butanol were mixed in a 20 ml glass bottle and subjected to 1 min of ultrasound treatment (Hielscher UP 200 S, cycle 1, amplitude 100%). This material is called dispersion 15B.

[0342] Solids content: 2.4%

[0343] Using a wire-bar a 12 μm wet film was deposited on a PET substrate and dried for 15 min at 130° C. in an oven. The film was characterized by the following properties:

[0344] Sheet resistance (12 μm on PET) 64,000 Ohm/sq

[0345] Haze (12 μm on PET) 0.8

Example 16

According to the Present Invention

[0346] Poly(n-butylacrylate) is an example of a polyacrylate with a low glass-transition temperature (Tg=−54° C.). Poly(n-butylacrylate) in toluene (CAS 9003-49-0; 25 wt % in toluene, M.sub.w 99000 g/mol; Sigma Aldrich product 181404) was blended with Dispersion 15B. Table 6 shows the blending ratio of three mixtures.

[0347] Using a wire-bar a 12 μm wet film was deposited on a PET substrate for each mixture and dried for 15 min at 130° C. in an oven. The sheet resistance was measured.

TABLE-US-00007 TABLE 6 Blends of Dispersion 15 B with poly(n-butylacrylate) and their sheet resistance mass of ratio of poly Polybutyl- butylacrylate: acrylate mass of polythiophene solution Dispersion mass of complex Sheet (25%) in 15 B Added in dried resistance Sample toluene (2.4%) Toluene film [Ohm/sq] 16A 5 g 5.2 g   0 g  90:10 5.5 × 10.sup.7 16B 5 g 4.0 g 1.2 g 92.5:7.5 8.2 × 10.sup.8 16C 5 g 2.0 g 3.2 g 97.5:3.7 6.6 × 10.sup.9

Example 17

Reference Example for the Synthesis of 3-(2-ethylhexoxymethyl)-2,3-dihydrothieno[3,4-b][1,4]dioxine

[0348] ##STR00026##

[0349] The synthesis is conducted under dry and inert conditions.

[0350] THF (60 mL) and 18-Crown-6 (0.200 g, 0.8 mmol) are added to the reaction vessel. NaH (1.512 g, 37.8 mmol) as 60% suspension in oil is added under stirring, the mixture is stirred at room temperature. At 0° C. a EDOT-MeOH (5.00 g, 29.0 mmol) solution in 20 mL THF is added to the NaH solution. After addition of the solution the reaction mixture is stirred for 2.5 h at room temperature, subsequently 0.5 h at 55° C. Reaction mixture is cooled to 0° C. and a 2-ethylhexyl bromide (7.300 g, 37.8 mmol) solution in 20 mL THF is added. The reaction mixture is stirred for 1 h at room temperature and 40 h at 50° C. The reaction mixture is cooled to room temperature and quenched with a mixture of isopropanol/water 70:30 (v/v). The crude product was purified by column chromatography.

[0351] The reaction product (3-(2-ethylhexoxymethyl)-2,3-dihydrothieno[3,4-b][1,4]dioxine) is obtained as a yellow oil in a yield of 15%.

Example 18

Reference Example for the Synthesis of 3-(1-phenylethoxymethyl)-2,3-dihydrothieno[3,4-b][1,4]dioxine

[0352] ##STR00027##

[0353] The synthesis is conducted under dry and inert conditions.

[0354] DMSO (50 mL), KOH (3.254 g, 58 mmol), 1-bromoethyl)benzene (6.700 g, 37.8 mmol) , and EDOT-MeOH (5.00 g, 29.0 mmol) are added to the reaction vessel. The resulting reaction mixture is stirred at 20° C. for 24 h. After the reaction is completed, the reaction mixture is poured into deionized water (1000 mL) and stirred for 1 h. The volume of the resulting mixture is halved by vacuum distillation. The mixture is extracted three times with ethyl acetate (150 ml), the combined organic phases are washed with brine (150 ml), dried over MgSO.sub.4 and the solvent is removed in vacuo. The crude product is purified by column chromatography.

[0355] The reaction product 3-(1-phenylethoxymethyl)-2,3-dihydrothieno[3,4-b][1,4]dioxine) is obtained as a yellow oil in a yield of 49%.

Example 19

[0356] A 250 mL three-necked round-bottom flask equipped with mechanical stirrer was charged with 65 g anisole (Aldrich), 2.699 g of dibenzoyl peroxide (11.1 mmol; Aldrich), and 2.981 g 4-dodecylbenzenesulfonic acid (9.3 mmol, Aldrich). After heating to 60° C. 1.185 g of 3-butyl-2,3-dihydrothieno[3,4-b][1,4]dioxine (6 mmol; ButylEDOT; CAS 552857-06-4, Synmax Biochemical, Taiwan) and 1.134 g product obtained from the reaction in Example 17 (4 mmol) dissolved in 20 g of anisole were added over 40 min. The dispersion was stirred for another 3 h at 60° C. and then cooled to room temperature.

[0357] 50 g of the dispersion, 30 g anisole, and 20 g of n-butanol are added to a 100 mL flask and mixed via gentle stirring of the resulting dispersion.

[0358] This is called dispersion 19.

[0359] Analysis of dispersion 19:

[0360] Solids content: 2.4% (gravimetric)

[0361] Sheet resistance (12 μm on PET): 210000 Ohm/sq

[0362] The ion-content of dispersion 19 was measured by inductively coupled plasma optical emission spectrometry:

[0363] Na 0.324 ppm

[0364] Fe 0.043 ppm

[0365] Cu 0.000 ppm

[0366] Pb 0.000 ppm

[0367] B 0.010 ppm

[0368] Mo 0.370 ppm

[0369] Al 0.000 ppm

[0370] Cr 0.028 ppm

[0371] Co 0.000 ppm

[0372] Mn 0.000 ppm

[0373] Ni 0.000 ppm

[0374] V 0.000 ppm

[0375] Zn 0.514 ppm

[0376] Ca 0.172 ppm

[0377] K 0.000 ppm

[0378] Mg 0.077 ppm

[0379] Cd 0.012 ppm

Example 20

[0380] A 250 mL three-necked round-bottom flask equipped with mechanical stirrer was charged with 65 g anisole (Aldrich), 2.699 g of dibenzoyl peroxide (11.1 mmol; Aldrich), and 2.981 g 4-dodecylbenzenesulfonic acid (9.3 mmol, Aldrich). After heating to 60° C. 1.185 g of 3-butyl-2,3-dihydrothieno[3,4-b][1,4]dioxine (10 mmol; ButylEDOT; CAS 552857-06-4, Synmax Biochemical, Taiwan) dissolved in 20 g of anisole were added over 40 min. The dispersion was stirred for another 3 h at 60° C. and then cooled to room temperature.

[0381] 50 g of the dispersion, 30 g anisole, and 20 g of n-butanol are added to a 100 mL flask and mixed via gentle stirring of the resulting dispersion.

[0382] This is called dispersion 20.

[0383] Analysis of dispersion 20:

[0384] Solids content: 2.2% (gravimetric)

[0385] Sheet resistance (12 μm on PET): 70000 Ohm/sq

Example 21

[0386] Dispersion 19 and dispersion 20 were tested with respect to their solvent compatibility. 1 g of the named dispersion is mixed by gentle stirring and shaking with 9 g of the additional solvent as shown in Table 7.

[0387] Using a wire-bar a 12 μm wet film was deposited on a PET substrate and dried for 15 min at 130° C. in an oven. The surface resistivity was determined.

[0388] A blank PET substrate yields the following baseline values upon measurement:

[0389] Surface resistivity: 1.8×10.sup.11 Ohm/sq

[0390] Transmission: 91%

TABLE-US-00008 TABLE 7 Dilution of dispersion 19 and dispersion 20 with various solvents. surface trans- resistivity mission Example dispersion solvent solubility [Ohm/sq] [%] 21A 19 1-Methoxy- + 1.1 × 10.sup.7 89 2-propanol 21B 19 isopropanol + 1.6 × 10.sup.7 89 21C 19 toluene + 1.2 × 10.sup.7 89 21D 19 butyl acetate + 1.8 × 10.sup.7 89 21E 19 butyl benzoate + 1.0 × 10.sup.7 89 21F 19 1-methoxy-2- + 1.2 × 10.sup.7 89 propylacetat 21G 19 ethyl acetate + 1.4 × 10.sup.7 89 21H 19 anisole + 6.7 × 10.sup.6 89 21I 20 1-Methoxy- + 1.7 × 10.sup.6 89 2-propanol 21J 20 ethanol + 3.9 × 10.sup.7 90 21K 20 butyl acetate + 1.0 × 10.sup.6 89 21L 20 anisole + 7.8 × 10.sup.5 89

[0391] Table 7 shows that the dispersion from the inventive example 19 and 20 are demonstrating a good surface resistivity and forms stable dispersions in a variety of common organic solvents.

Example 22

[0392] A 250 mL three-necked round-bottom flask equipped with mechanical stirrer was charged with 65 g anisole (Aldrich), 2.699 g of dibenzoyl peroxide (11.1 mmol; Aldrich), and 2.981 g 4-dodecylbenzenesulfonic acid (9.3 mmol, Aldrich). After heating to 60° C. 1.565 g of 3-butyl-2,3-dihydrothieno[3,4-b][1,4]dioxine (8 mmol; ButylEDOT; CAS 552857-06-4, Synmax Biochemical, Taiwan) and 0.565 g of 3-decyl-2,3-dihydrothieno[3,4-b][1,4]dioxine (2 mmol; CAS: 210476-55-4) dissolved in 20 g of anisole were added over 40 min. The dispersion was stirred for another 3 h at 60° C. and then cooled to room temperature.

[0393] 50 g of the dispersion, 30 g anisole, and 20 g of n-butanol are added to a 100 mL flask and mixed via gentle stirring of the resulting dispersion.

[0394] This is called dispersion 22.

[0395] Analysis of dispersion 22:

[0396] Solids content: 2.3% (gravimetric)

[0397] Sheet resistance (12 μm on PET): 63000 Ohm/sq

Example 23

[0398] Dispersion 19 and dispersion 22 were tested with respect to their compatibility with acrylic resins. Table 8 shows the amounts of used dispersions, solvents, and dipentaerythritol penta-/hexa-acrylate (CAS 60506-81-2, Sigma Aldrich).

[0399] Using a wire-bar a 12 μm wet film was deposited on a PET substrate and dried for 15 min at 130° C. in an oven. The surface resistivity was determined.

TABLE-US-00009 TABLE 8 Surface resistivity of dispersion 19 and dispersion 22 in an acrylic resin. dipentaerythritol surface penta-/hexa-acry- resistivity Example dispersion solvent late [g] [Ohm/sq] 23A 0.6 g 8.4 g 1-methoxy-2- 1 6.1 × 10.sup.10 dispersion 19 propanol 23B 1.5 g 7.5 g 1-methoxy-2- 1 2.5 × 10.sup.9  dispersion 19 propanol 23C 2.4 g 6.6 g 1-methoxy-2- 1 6.1 × 10.sup.7  dispersion 19 propanol 23D 0.6 g 8.4 g ethyl acetate 1 1.1 × 10.sup.11 dispersion 19 23E 1.5 g 7.5 g ethyl acetate 1 5.5 × 10.sup.8  dispersion 19 23F 2.4 g 6.6 g ethyl acetate 1 7.7 × 10.sup.8  dispersion 19 23G 2.4 g 6.6 g ethyl acetate 1 7.0 × 10.sup.7  dispersion 22

[0400] Table 8 shows the compatibility of dispersions 19 and 22 with acrylic resins as demonstrated in the achieved surface resistivity values.

Example 24

[0401] Dispersion 19 and dispersion 2B were compared with respect to their compatibility with silicon release resins. Table shows the amounts of used dispersions, solvents, and KS 847-H (CAS: 63148-53-8; Shin-Etsu Silicone). As a solvent, a mixture of toluene, alkanes and ketones is used.

[0402] Using a wire-bar a 12 μm wet film was deposited on a PET substrate and dried for 15 min at 130° C. in an oven. The surface resistivity was determined.

TABLE-US-00010 TABLE 9 Surface resistivity of dispersion 19 and dispersion 24 in a silicone release resin. surface solvent KS 847-H resistivity Example dispersion [g] [g ] [Ohm/sq] 24A (inventive) 0.5 g dispersion 19 10 1.3 1.5 × 10.sup.11 24B (inventive)   1 g dispersion 19 10 1.3 1.3 × 10.sup.9  24C (inventive)   2 g dispersion 19 10 1.3 2.3 × 10.sup.7  24E (comparative) 0.5 g dispersion 2B 10 1.3 2.3 × 10.sup.11 24F (comparative)   1 g dispersion 2B 10 1.3 2.3 × 10.sup.11 24G (comparative)   2 g dispersion 2B 10 1.3 2.3 × 10.sup.11

[0403] Table 9 shows the superior compatibility of dispersion 19 with silicone release resins as demonstrated in the achieved surface resistivity values.

Example 25

[0404] Dispersion 19 and dispersion 22 were tested with respect to their compatibility with polyacrylic resins. Table 10 shows the amounts of used dispersions, solvents, and polybutylacrylate (CAS 9003-49-0, Sigma Aldrich).

[0405] Using a wire-bar a 12 μm wet film was deposited on a PET substrate and dried for 15 min at 130° C. in an oven. The surface resistivity was determined.

TABLE-US-00011 TABLE 10 Surface resistivity of dispersion 19 and dispersion 22 in a polyacrylic binder. surface polybutyl resistivity Example dispersion toluene [g] acrylate [g] [Ohm/sq] 25A 0.455 g dispersion 19 5.545 4 4.1 × 10.sup.10 25B 1.136 g dispersion 19 4.864 4 5.3 × 10.sup.9  25C 2.273 g dispersion 19 3.727 4 1.7 × 10.sup.9  25D 2.273 g dispersion 22 3.727 4 1.7 × 10.sup.9 

[0406] Table 10 shows the compatibility of the dispersion 19 and 22 with poly(meth)acrylate binders as demonstrated in the achieved surface resistivity.

Example 26

[0407] A 250 mL three-necked round-bottom flask equipped with mechanical stirrer was charged with 65 g anisole (Aldrich), 2.699 g of dibenzoyl peroxide (11.1 mmol; Aldrich), and 2.981 g 4-dodecylbenzenesulfonic acid (9.3 mmol, Aldrich). After heating to 60° C. 1.584 g of 3-butyl-2,3-dihydrothieno[3,4-b][1,4]dioxine (8 mmol; ButylEDOT; CAS 552857-06-4, Synmax Biochemical, Taiwan) and 0.553 g product obtained from the reaction in Example 18 (2 mmol) dissolved in 20 g of anisole were added over 40 min. The dispersion was stirred for another 3 h at 60° C. and then cooled to room temperature.

[0408] 5 g of the dispersion, 3 g anisole, and 2 g of n-butanol are mixed via gentle stirring and subjected to 1 min of ultrasound treatment (Hielscher UP 200 S, cycle 1, amplitude 100%) to yield the resulting dispersion.

[0409] This is called dispersion 26.

[0410] Analysis of dispersion 26:

[0411] Solids content: 2.4% (gravimetric)

[0412] Sheet resistance (12 μm on PET): 19000 Ohm/sq

LIST OF REFERENCE NUMERALS

[0413] 100 layer body

[0414] 101 substrate

[0415] 102 electrically conductive layer