JPS6345276A - Polymerizable thiophene monomer, its production and polymer obtained - Google Patents

Abstract

(57) [Abstract] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a thiophene compound or derivative, which is a sulfur-containing multicyclic polymerizable monomer compound.

The present invention relates to a method for producing these novel monomeric compounds and a polymerization method.

(Prior art) 3-alkylthiophene U, e.g., tba 3-ethyl=
+ 3-n-buty-83-n-octyne- or 3.
Regarding homopolymers and copolymers of 4-dimethylthiophene, see "Journal of the Chemical Industry, Chemical Communications J 1346.
~1347 pages (1986) Kwan-Yue, G.G.
, Miller and Ronald L.

Described in Elsenpaumer's paper.

(Means for solving the problem) As a result of research, the present inventor succeeded in discovering a novel thiophene derivative that can be polymerized to produce a conductive polymer.

That is, according to the present invention of @l, the following general formula [in the formula +
R' is a group -(CH2)rnNHCOR.

Group -O(CH2)♂H-COR, Group -(CH2)rnC
ONHR1 group -O(CH2)rnC0NHR5, group -(
CH2)nO(CH2CH2), OR'.

), or an aryl group, an amino group, an aminoalkyl group, or a substituted aminoalkyl group, and the nitrogen atom of these groups is an alkyl group.

It may have at least one of an aryl group or a substituted aryl group as a substituent, R is an alkyl group having 1 to 1 g of carbon atoms, and R is the same as R, or R is a hydrogen atom. , a halogen atom or an amino group, R is a hydrogen atom or a methyl group, and R is an alkyl A- having 1 to 6 carbon atoms.
It is the basis.

R is an alkyl group having 1 to 1 g of carbon atoms, or some r is an aryl group which may be substituted with an alkyl group or an alkylaryl group, m is an integer of 1 to 6, and n is zero or 1 to 6.
un of 6, p is an integer of 1 to 6], and a compound is provided.

Among the compounds of the present invention represented by general formula (1), preferred compounds include groups in which the group R1 is -(CH2)nO(CH2CH2), 0R
4 (wherein n is O or 1, p and R have the same meanings as above), or R is a group -CH2N) lCOR
' (where R' is an alkyl group having carbon fi1 to fi12), or R is a group -O (CH2C! (2) NHC
OR' (wherein R is an alkyl group having 6 to 180 carbon atoms). Further, compounds in which R in the general formula (1) is a hydrogen atom are also preferred compounds of the present invention.

Particularly preferred examples of the compounds of the present invention represented by general formula (1) are as follows.

3-(Simete A-)thiophene.

3-(Methoxyethoxyethoxymethyl)thiofene! -15-(ptoxyethoxyethoxyethoxyethoxyethoxymethyl)thiophene, N-(3-thienylmethyl)acetamide, N-(3-thienylmethyl)-
octaneamide or N-(3-thienylmethyl)dodecanamide, 3-(Methin ShedΦshi)thiophene,
The compound of the present invention of the general formula (1) is 3-(methoxyethoxyethoxy)thiophene, or N-(3-O-thienylethoxy)octanamide or N-(3-o-thienylethoxy)dodecaneamide. Among them, al is the group -
The compound (CH2)no(cnn3cH2), oR' (wherein R5, RJ, n and p have the above-mentioned meanings) can be produced by the reaction shown in the first general reaction process diagram.

Other L R'=(C)IR'CH2)pOR' In the compound of the present invention of general formula (1), al is a group -(CH2)JHCOR (wherein R and m have the above meanings) The compound (with) can be produced by the method shown in the first-order general reaction process diagram.

Further, among the compounds of the present invention represented by the general formula (1), compounds in which al is a group -O(CHRCH2) or OR can be produced by the method shown in the first general reaction process diagram.

In the compound of the present invention of general formula (1), R is a group -O(
The compound CH2)fnNHCoR (wherein R and m have the above-mentioned meanings) can be produced by the method of the first-order general reaction scheme.

It goes without saying that in the above reaction diagram, the p-toluenesulfony h group (Tom) as a protecting group can be replaced with any other suitable protecting group.

Therefore, according to the second invention, a compound of the linear formula [wherein n is zero or an integer from 1 to 6] is converted into a compound of the following formula % and a compound of the following formula R'OH C in the formula R' -(CHRsCH2), OR'
Thea0, R3゜R4 and p have the above meanings]
Step (a) of producing a compound of the following formula [wherein R6 has the above meaning] by reacting with a compound of and a step (b) of reacting with an acid chloride of the following formula C, in which r has the meaning given above, to produce a compound of the following formula [wherein R has the meaning given above], or A compound of the following formula a OR [wherein R7 is a group -0 (Cl(R5CH2), OR'
where R3, R4 and p have the above meanings] in the presence of cupric oxide and potassium iodide to form a compound of the following formula [wherein R7 has the above meanings] or step (C) of producing the following formula RCOC/ [wherein R has the abovementioned meaning] by reacting with an acid chloride and triethylamine of the following formula [wherein R and m have the abovementioned meaning] ] How many times in step (d) to produce the compound
It is characterized by consisting of one of the following: Provided is a method for producing a thiophene compound represented by the general formula [wherein R and R have the above-mentioned meanings] - The above general formula (1)
The thiophene compound or thiophene derivative of the present invention can be polymerized to give the corresponding polythiophene derivative. The polymerization includes, for example, i! ! A gas chemical polymerization method or a chemical polymerization method can be used, and the polythiophene derivative is obtained as a conductive polymer by the polymerization.

The conductive polymers thus obtained can be used in thin film technology as EMI/RF shielding materials and in electrochromic disyrlays.
) device, further as an antistatic material, as a sensor for ions and..., as an electrode material for a storage battery, in a switch device α, as a protective coating for ma&'flEi, as an electrode for selective electrodeposition of metal ions, and as an electrode for selective electrodeposition of metal ions. It can be used as a self-heating regulator.

For example, the conductive polymer can be blended with conventional polymers to prepare a conductive plastic material for use as an EMI/RF (electromagnetic interference) shielding material. Alternatively, the conductive polymer can be formed in situ on a conductive or non-conductive surface to form a corrosion-resistant conductive surface layer. Soluble such conductive polymers can be applied to a surface by dissolving them in a solvent to form a conductive overcoat layer, or -
Co-electropolymerization (co-electropolymerization) together with one conventional fL polymer precursor on the surface of
The conductive polymer can also be formed as a solid mass of conductive material.

The conductive polymer precursor obtained from the thiophene compound of the general formula (1) of the present invention is prepared by co-vaporizing the polymer with an epoxy resin (e.g., bisphenol A/bisphenol F/phenylglycidyl ether) using VCN gas chemistry. , photochemically or photoelectrochemically copolymerizing, an electrically conductive adhesive material is obtained.

When the conductive polymer is used in a gas sensor and LC, the change in conductivity of the polymer that occurs when it comes into contact with a gas such as Co, No, NH, No2°C2H4, etc. Use gas f! When used in an electrochromic display device, electrochromic (e
Select and use a conductive polymer with electrochromic properties.The conductive polymer can also be detopped.
Alternatively, it can also be doped with cations and anions to be doped.

This r-pinging property makes it suitable for use in making red mass storage battery electrodes.

Furthermore, the monomeric thiophene compound of the present invention of the general formula (r) can be homopolymerized by itself or copolymerized with one or more copolymerizable monomers. Depending on the conditions, the reaction can be polymerized under conditions that allow the formation of a fibrous polymer or copolymer. That is, according to the present invention, there is provided a copolymer of a thiophene compound (derivative) of the general formula (1') and other monomers copolymerizable therewith - such other monomers that can be copolymerized. An example of a body.

Methyl methano 11-rate, nylon, styrene.

Vinyl carbazole or acrylonitrile LJ, Al or seven others. Conductive fibers produced in this way are used in the production of printed circuit boards.

The electrochemical polymerization of the monomer compound of the present invention of the general formula (1) can be carried out using, for example, platinum or isidium-titanium oxide (lrc
), or tungsten, titanium.

It can be carried out in a single chamber using a niobium, lead or graphite anode.

Therefore, according to another aspect of the present invention, the general formula (1
) is electrically positive (positive) at least as high as the oxidation potential of the thiophene compound.
It consists of subjecting an electrochemical oxidation reaction in a non-aqueous solvent to an electric pressure of .

A method for producing a polythiophene derivative is provided.

According to still another aspect of the present invention, a repeating unit of the first-order general formula [wherein R and R have the same meanings as defined in claim 1] and a counter ion of the formula Z (
However, 2 is a chloride ion, a bromide ion, an IRR1 ion, and a heavy 2P2 (bisulfate) ion.

Nitrate ion, tetrafluoroborate ion, alkylsulfonate ion, alkylsulfonate ion.

Arlene carboxylate ion, alkylcarzanate ion, alkylcarzanate ion, polystyrene hphonate ion, polyacrylate ion.

Cellulose/sulfonate ion, cellulose/sulfate ion, anthracene sulfonate ion.

A polymer is provided, which comprises: - fluorinated, π-aryanion).

The electrolyte store used in the electrochemical oxidation reaction is selected to provide the counter ion Z.

Preferred examples of the non-aqueous solvent used in this electrochemical oxidation reaction include acetonitrile, dichloromethane, chloroform, dichloroethane, nitromethane, nitrobenzene, teropyrene carbonate, N-methylpyrrolidone, sulfolane, dimethylformamide, and dimethylsulfonate. (in the middle).

These solvents can be used individually or as a mixed solvent of two or more.

The monomeric thiophene compound of the present invention represented by general formula (1) can be polymerized simply by chemical methods. Therefore, according to another aspect of the present invention, a monomeric thiophene compound of the following general formula [wherein R and R have the same meanings as above] is subjected to a standard oxidation process higher than the oxidation potential of the thiophene compound. There is provided a method for producing the polythiophene derivative, which comprises oxidizing the polythiophene derivative with an oxidizing agent having a reduction (redox) voltage. This oxidation can be carried out as a single-phase or multi-phase reaction in the presence or absence of a catalyst. Suitable examples of nyvmm oxidants include Ag, Cu, Ce, Mo,
Ru, Mn.

KCrO,l(O or (NH4)2S208),
The oxidation degree reaction may be carried out in the presence of a catalyst if desired.

The catalyst is often an ion of a transition metal,
Suitable examples thereof are Mo, Ru and Mn.

If a single phase reaction is required, the solvent may be toluene, dichloromethane, dimethylformamide, chlorobenzene, chloroform or nitrobenzene.

Alternatively, a mixed solvent of two or more of these is preferred; or, if a multiphase reaction is required, a solvent system in which the aqueous phase and organic solvent phase are immiscible can be used. In order to carry out the chemical polymerization reaction in this way, the reaction temperature is preferably in the range of 20 to 1109C, and the produced polymer can be obtained as a thin film at the interface of an immiscible solvent system, or For example, it can be obtained as a powder by precipitation with hexane.

The thiophene monomer compound of the present invention l) general formula (1) is:
Other monomers 1 For example, virol or thiophene, or any other monomers which are copolymerizable with each other, such as styrene and N-vinycarbazole, can also be copolymerized.

-Ma72. The polymer of the thiophene monomer compound of the general formula (1) obtained by the invention can be obtained by combining it with other types of polymers,
For example, polyvinyl chloride, f! ll ethylene.

, J? Lipropylene, 7y? 11 Styrene, nylon,
Acrylonitrile/butadiene/styrene co-M combination.

It can be blended with poly-11 ethylene terephthalate or polyethylene oxide to form a blend.Such polymer blends contain 5 to 70% (weight t) of the polymer of the thiophene compound of general formula (1). ) and another type of polymer 95~
30% (by weight). These polymer formulations have good electrical conductivity and good antistatic properties.

The polymer of the monomer thiophene compound of the general formula (I) of the present invention is prepared by a chemical oxidative polymerization method or an electrochemical polymerization method on a porous film of a polymer such as polyvinyl chloride. Deposited directly.

Alternatively, or at the same time, it can be infiltrated into the porous film. The surface of the composite thus formed is permanently conductive and has good antistatic properties (δ of the surface: 1O-5S), and such a surface can be coated with dyes and pigments. and its color can be modified without compromising its antistatic properties. By using this method, antistatic flooring or mats can be produced from the composite material.Furthermore, the polymer of the thiophene monomer compound according to the present invention can be used to prepare non-conductive materials such as talc and mica. It can be coated with a chemical substance, and oxidative or electrochemical polymerization methods can be used for this coating. The powder material coated in this manner is useful as a filler for conductive polymer composites of form α.

Example 1 Preparation of 3-(methoxyethoxymethyl)thiophene (1) Dissolve 3-(bromomethyl) in carbon tetrachloride (25d)
a solution of thiophene (6.2 g, 0.035 mol),
Sodium dissolved in methoxyethanol (90d)
was added to a solution of methoxymethoxide (s,q 9.0.0 (7 mol)) and the mixture was heated to reflux for 2 hours. After cooling to room temperature, the solvent mixture was removed under reduced pressure and the resulting oil was dissolved in dichloromethane (100 rnl), extracted with distilled water (2x+oo-) and dried over potassium carbonate. After removal of the solvent, the crude oil was distilled under reduced pressure to give 3-(methoxyethoxymethyl). Thiophene (
3,09゜50%) k gain 7t e 8 points 100~l O
IoC/l OmtnHg・Actual measurement 1st shift: c, ss, 0; H, 6-3; S,
+7.64C8H1202S calculation value: C,55
4; H, 7,0; S, 1g-6'SEI m/e
Strength (%): 172 (5, M+), 97 (
12°C4H,S,CH2); δIT(CDC/,
) Near, 05-7-24 (3H, r*), a, 5
3 (2H, s), 3.54 (4H, m) and 3.3
4 (3H, s); δC (CDL: +5) ”59
．． 6. 67.0.69.7.72.5゜173.4.
126.5. 127.9. 140.0 ppm Example 2 Sodium methoxyethoxyethanol (too-) dissolved in methoxyethoxyethanol (too-)
A solution of 3-(bromomethyl)thiophene (12,49,0
,07 mol) and the mixture was heated to reflux for 12 hours. Working as described in Example 1, a crude oil was obtained which was distilled under reduced pressure to give 3-(methoxyethoxyethoxymethyl)thiophene (7,o, La
61I) was obtained. Boiling point 136-13811C/lO
nlnlHg.

Actual value: C, 56, O; I (, 7, O; S, +
5. l 4C7l) H16032) Calculated values: c, s
s, s; l(,7,4; S, +4.8%EI
m/e strength (%): 2+6 CI2 M+), 9
7 (too.

C, H3S, CH, ); δH (CDcz, ):
6.96-'L17 (311, m), 4. a5(2
skin m), 3.50 (all, m).

3.40 (41 (, m) and 3.26 (3Ii + s
), δC(CDCj5)”5g, 3.66.1.69-
2.70-2°70.4.7+, 7,121.7°+25-2. 126-7, 139.6 ppm.

Example 3! Tokishetokishetokishet Beef Jetanol (25.
09. Potassium gold i(O, 1 mol) was prepared by art-known methods from tetraethylene glycol, sodium hydroxide, glutyl chloride (IQ:l:I) and then dissolved in tetrahydrofuran for 1.5 hours at room temperature. 3,9,9,
0.1 mol).

3-(bromomethyl)thiophene (17,79°0.1
mol) was added dropwise and the mixture was stirred under reflux for 24 hours. After cooling and filtration, the tetrahydrofuran was removed in vacuo and the residue was dissolved in methylene chloride, washed with water and dried over potassium carbonate.

The solvent was removed and the crude oil was distilled to give 3-butoxyethoxyethoxyethoxyethoxyethoxymethine)thiophene (
25.7 g, 57% was obtained. boiling point! 62~163°C/
O, I 5 nmHg.

Actual measurements: C', 5g, 6; H, g, 7; S, 9.
54C1,H3oO5S) Calculated value: C,5L9; H
, I3.7; S, 9.3%EIm/c intensity ('l)
: 346 (9,M+), 97 (+00゜c
4H,S, C1(2), 57(75, caH9); δ
Fl(CDC15): 1-26 (In, rn)7
．． 20 (IH, m), 7.06 (IH.

+n), 4.56 (2H, +1), 3.65(+
6H,m), 3.45 (2H,tLl-53(2H
, m), 1.34 (28゜m) and 0.91 (3
H, L); δC (CDC/3): 13.6. +8.9°3
+, a, bs first, 69.0.694°70.0.70
．． 3. 122.5. 125.5°H6,7,139
, 1 ppme Example 4 Preparation of potassium phthalimide (s, 7 g, o, 3 moles) and 18-crown-6-ether (50 v).

3 dissolved in N,N-dimethylformamide (7ou)
-(bromomethyl)thiophene C5,59° (0.03 mol)). This mixture was heated to sO for 3 hours.
Stir at 90'C and then cool. The F solution was crushed and added to Yuice (approximately +ooy), stirred for 5 hours, and the resulting solid was collected.

When dried and recrystallized from absolute ethanol, 3-(N-
7-talimidomethyl)thiophene < 5.2 g.

72%). Melting point 128-130°C6 Actual value:
C, 64, 4; H, A, O; N, 5.5; S, 13.
Calculated value of 3 CI 5H9NO2: C,64,2; H
, 3, 7; N, 5. g; S, 13.2% EIm/e intensity (4): 243 (too, M)
, 97 (+4°CH8, CH2); IR (nujol): 169Qcm;
δH (CDe/ ): 7.65-1-FE5
(4H, m), 7.15-7.35 (3H, m),
a, ga (2H, a); δC (CDC/,): 36
．． 2.123.3°124.2.126.2.128.
1゜132.1.134.0.136.6゜167.8
1) I) m Hydrazine hydrate C1,4-, 0,03 mmol) and 3-(N-phthalimidomethyl)thiophene (&, 4,9° 0,026 mmol) in absolute ethanol (200 m) The mixture was refluxed for 12 hours.

My salt a2(5-)k with water was added and reflux was continued for an additional 30 minutes. The solution was then stored at O'C for 16 hours and Part F was evaporated in vacuo leaving a white solid. This solid was dissolved in distilled water (50v) and the dissolved g! After Ltp filtration, the P solution was evaporated in vacuo to give a yellow product. Recrystallization from anhydrous ethanol gave 3-(aminemethyl)thiophene[acid [(3,519o4)].

Melting point + bs″cC decomposition) Actual value: C, Ao, 4: H, 5, O; N, 9.
6;8.21.2 Calculated value of C5H8NSCI: C,40,l;H
, 5, 3; N, 9.4; 3.21.4 4 S)! (1)20): '1.04~7.2A C3
11m), 5.33 (@Hiro.

s), 1 replacement during D2Q), 3.80 (2
)1°3); δC(D20): 40.7. +
2L7. 130.3°+3s, g ppm.

Triethylamine (o, a 6 g, a, a mmol) was suspended in anhydrous dichloromethane (20 mg) maintained under nitrogen at -5''C to give 7'h3-(aminomethyl).
Add KM to a stirred suspension of thiophene hydrochloride (0.6i 4 mmol) and after 15 minutes add acenal chloride (0.31 g, 4 mmol).
mmol) into the solution, and then the solution was heated to 15°C.
The mixture was stirred at C for 3 hours. After this stirring period the reaction mixture was diluted with dilute HC/(soat, 0.5 M) and dilute NaO.
Washed sequentially with H (50 m, 0.5 M).

Organic/at-separated and dried over magnesium sulfate.

Removal of the solvent in vacuo produced a crude product which was recrystallized from hexane to yield N-(3-thienylmethyl)acetolimide (0.52.1 g 5%).

Melting point 46-47°C Measured value: C, 53,5; H, 6-2; N, g,
7;S.

20.4 4 Calculated value of C,H7NO8: C054,2; H,5
4: N, 9-0: S.

20.7% IR (Nujol): 3250.1650cm
; E1m/e strength value): 155 (37,
M).

+12 (55, C4HSS, CH2NH), 97C
29,C4H,S,CI(2183(+2°C,H,S
); δH (CDC/3) 7.00-7.29 (3H
, m), 6-26 (Il, wide, S).

4.41 (2H, d), 1. '? 3 (3H
,s): δC(cDez,): 23.1.38-7
゜122.2. 126-3. 127.3. 139
．． 8゜170.0 ppm・Example 5 (5) Production Using the same reaction conditions as Example 4 and 11, 3-(aminomethyl)thiophene salted u (4 mmol) triethylamine (a, S mmol) was reacted with octanoyl chloride (40 mmol) to obtain N-(3-thienylmethyA-)octanamide (0,85189 units). Melting point 71~
72°C0 Actual value: C, 65, O; H+g, a; N, 5.7
;S.

13.2% C45H2, NOS calculation value: C,65,3;
11. S-8; N, 5.9; S.

13.4% El, m/e strength (4”): 239 (+9. M
), 97 (63°C4H3S, CH2); δH(
CDc/,)7.03-7-33 (3H,m), 5
-60 (IH-wide, 3), 144 (2'H.

d), 2.19 (2H,L), 1.61 (2B,
m), 1.2g (1!, rn).

0.87 (3H, t); δC (CDC/5): +
a, 2+ 22.7.25.8.29.1゜2q, 3.
3+, L 36.9.38! .

122.3. 126.5. 127.1°+4o,o
, 173.1 pT) m.

Preparation of Example 6 Under the same reaction conditions as Example 4, 3-(amino/ , l
f, %) foffene hydrochloride (4 mmol) totriethylamine (a, a mmol) and dodecanoyl chloride A
(4 mmol) to obtain N-(3-thienylmethyl)dodecane esteramide (+, +, 9.924) Melting point g3-84°C6 Actual position: C, 6g, 9; H, IO, 2; N, 4.
g; S, Io, 8% C,, H2, NO8o Calculated value: C, 69, l; H,
94; N,, 4.7; S, IO, 9-connection E engineering m/e strong gf%): 295 (IL M)
, 97 (46°CHS, C1(); δH(CD
Cj) 7.01-7.30 (3H, m), 5-
a.

(IH, wide, s), a-46 (2H.

d), 2.20 (21(, t), +, g.

(2H, m), 1.25 (16H, to).

0.87 (3B, t); Example 7 Sodium (2,C) 5J, 87ml (11 mol) was added to methoxyethanol Cl (25m/) under an argon atmosphere. ,. n) When IIium is dissolved, the oxidation calculation I C
U') (1,25u, 16 mmol) and potassium iodide (0,05,!v, 0.3 mmol) were added together followed by 3-bromothiophene (5,y', 31
millimo/L-) and the mixture was further incubated for 2 days at 1
It was stirred at 000C. The crude monochrome chromatograph was chromatographed on a silica column eluted with diethyl ether to produce 3-(methoxy)thiophene (
3.3g, 68g) was obtained.

Actual value: C, 52,8; H, 6, O; S, 20
．． 1 俤C7H,. Calculated value of O8: C, 53, I;
H, 6, 3; S, 20.3 EI m/e intensity i: +sg (25, M), too
(26°C, H40S), 59 (+00.C,H
, O).

As (50, C2H60); δ11 (CDC/S)6
．． 23-7.16 (3H, m), 4.07 (2) 1.
t), 3.70 (2H, t).

3, C2 (3B, a); δC (CDCi, ): 5g
, 9.69.2, 70.8. '? 7.2°119.4.
124.5 ppmG Example 8 Preparation of (8) Using the same reaction conditions as Example 7, sodium (2.0 g) in jetoxyethanol (+25. ) and potassium iodide (0,05
9') and 3-bromothiophene (5, Ofl,
0.031 mmol). Chromatography of the crude material on a silica column eluted with dienal ether yielded 3-(methΦ)thiophene (2,1y, 34%) as a colorless oil. Found: C,53 ,O; I(,6,8; S・1
Calculated value of 5.7%C6H1405S: C, 53, A
; H, 6,9; S, +5.9 %II m/e
Strength 1%): 202 (3,M), +00
((?.

C4H408), 59(53, C3H70).

45 (+2. C2H50); δH (cpei,)6
．． 22-7.15 (3H, m), 4.05 (2) 1
．． m), 3-76 (2H, m).

3.65 (2H, m), 2.53 (2H.

m), 3.34 (3H, @); δC (CDCi, ): 5L6.69.2°6'LA,
70.3.7+, 6.97.2° 9.2. 124.
4 ppm.

Example 9 Sodium (2, Ofi ) in ethylene glycol (+2sy) using the same reaction conditions as Preparation Example 7.

Oxidized steel (n) (1,259) and iodizing power I] Ram (
Q, 05g) to 3-bromothiophene C5,09°0.
031 mmol). Elution was first carried out with dichloromethane and then dichloromethane/methanol (95:5).
) elute with a mixture of! - Tm-W gold chromatography on a silica column yielded 3-(hydroxyethoxy)thiophene (1,9p, 43%) as a white solid. Melting point 38-39°C.

Actual measurements: C, C9,2; H, 5,3; S,
Calculated value of 21.94C6H6o2S: C,50,
Oi ) 1.5.6; S, 22.34EI m/e
strong ip): 14 & (100,M), too
(47°C, H40S), As (+7.C2
H50); δH(CDCt,)6.10-7.11 (
3H.

rn), 4.16 (2H, m), 3.8a (2I(
, m); δC(CDCi,): bo4°7+, 4
．． 97.7. 119.4. +244°157.
4 ppm.

Solid p-thenesulfonine chloride (0,88
fl, 4.6 Mi II Mox) t-1 anhydrous k”)
Added portionwise to a cold (-5°C) solution of 3-(hydroxyethoxy)thiophene (o, 6 g, 4.2 mmol) dissolved in y (50d). The mixture was stirred for 10 minutes and then incubated for 4 g hours at -20°C.

This mixture was then stirred with crushed ice for a total of 5 hours.

The solid was recrystallized twice from high-g medium saline to give 3-(toluenesulfoethyl)thiophene (+, O, lg 3%) as a white crystalline product.

Melting point 76-77°C.

Actual value: c, 52-1; li, a, 5; N, 21
．． 8. Calculated value of C1, H44S204: C,5',
3; H, 4, 7; N, 21.5 壬EI rn/
e strong f <@: 79B (0,5M), +9
9 (57° Tosyl-OL:H2C) (2); a
H(CDC/,)'1.3-1. '7 (AH, m),
7.0 (IH.

m), 6.5 (IIl, m), 6.0 (I)
I.

m), 4.2 (2H, t), 4.0 (2H.

t), 2.4 (3)(,8),δC(CDC!,)
: 21.7. 6? ,5. 610. 9g, 1゜119.3.125.0.12g, 0゜1'9.9 p
pm@ Production of ene 3-(Toluenesulfonylethoxy)thiophene (0,
4,9,+,a mmol) and hypotarium phthanimide (
0.3 g, 1.6 mmol), dimethylformamin
18-crown-6-ether (5
Stir together at 65 °C for 12 hours. The mixture was cooled to room temperature and stirred in crushed water for two hours.

The resulting solid was filtered and recrystallized from absolute ethanol to yield a white crystalline product (0,261724').
Melting point 146-147°C0 Actual value: C, 62,3; H, a, I; N, A,
9; S, 10g C) Calculated value of INO8: C, 61,5; H,
4, O; N, 5. l; S, 111-7 4EI/e intensity ei19: 273 (4,1M
), +74 (+00°phthal-NCH2CH2);
aH (crx:t, )7.6-7.9 (aH,
m), 7-0 (lH, mL 6.6 (heat H, m), 6.2 (IH, m), 4.1 (2
8,t).

4.0 (2H, t); δc (cDcl'): 37.2
．． 66J, 97.9. 119.5°123.3
．． 12a, 7. 132.0゜134.0 ppm
Preparation of a Hydrazine hydrate (0.7m, 0.015 mmol) was dissolved in hot absolute ethanol (200-).
N-(phthalimidoethyl)thiophene (2,69,
'? , 5 and 11 mol) and the mixture was stirred at reflux for 12 hours under nitrogen. a Hydrochloric acid (5-)
was added regularly to the reaction system and reflux was maintained for an additional 30 minutes. After cooling and filtration, the P solution was evaporated to dryness, leaving a white crystalline solid that was extracted with water. After filtration and water removal, 3-(aminoethoxy)thiophene (+,
5g, gs4).

Actual measurement @: C, 39, g; H, 5, 8: N, g,
l Calculated value of %C6H1°N08C/: C,40,
I; H, 5,6; N, 7.84δH (CDCl2)
7.1 (IH, m), 6-7 (IH, m), 6
-2 ('H, m), 3.9 C2H, t), 3.
0 (2H, t); δc (cDe!2) '4
0.8.71-5.96.7. l1g, 7. 12
4.1 ppm.

Troethylamine (+, 3ag+ '?, 2 mmol) t - anhydrous dichloromethane CbO, t cooled to 5 °C
3-(aminoethoxy)thiophene salt (+, 59.8.4 mmol) was added over 10 minutes with stirring at 1 turbidity. Then dichloromethane (20- ), lubricate with octanoyl nonachloride (1,37,9,8,4 mmol) and stir at -5°C for 4 hours.Then, this mixture is mixed with hydrochloric acid (2X50+++/.).

o, lM) and sodium hydroxide (2 × 5
05g+o-'M) and dried over magnesium sulfate. After filtration and evaporation of the bath, a white solid was obtained, which was recrystallized from hot hexane to give N-(
3-0-thienyl ethyl)octanamide (1,4g
, Section 62). Melting point: 75-76°C6 For practical use: C, 61,9; H, 8,6;
N, 4.9 Calculated values of 4C, 4H, NSO2: C
, 62, 4; H, 8, 5: N, 5.2 connected cI m/
e strength (%): 270 (0,5,M),
+70 (+oo, C4H,5OCH2CH2NHC
O):IR (nujol): 3300°1635cyn; δH(CDCj')7.1
9 (II (, m), 6.75 (IH, m).

6.27 (IH, m), 5.93 (1B.

Wide, 8), 4.0' (2H, t).

3.6a (2H, m), 2.19 (2H.

t), 1.63 (2H, t), 1.27 (1,
t), o, gg (3H, t); δC (CDCj)
: 13. L 22.3°25.4. 2LL
29.0. 31.4゜36.4.38.6.6g
・7・97.5・116.9. 124.7. 15
7.0゜173.2 1) pm Example 11 Preparation of amine 9αυ was described in Example io, and with the same emphasis as that of the friend, ethylamine (I O, Ost, 6. g mmol), 3-(aminoethoxy)thio 7 in methylene chloride (20 mg)
x t310 salt (0.89, a, 5 LL mol) and dodecanoyl chloride (1,
16-, 5,0LL mol) to react with N-(3-〇-
Thienylethoxy)dodecaneamidera was obtained.

Recrystallization is performed from Hegyu San.

Actual value: C, 66.6; H, 9.9; N, 3.9;
S, 9.7% C, 8H,, No2S Calculated value: C, 66,5;
H, 9, 5; N, A, 3; S,'? , 9 Melting point 97-98C; CI m/e strength ('*: 3
26 (7,M); aIm/e intensity C4: 226
(+00. CH3(CH2), 0C(0)N(H)
CH2CH2), 126 (5゜C4H5S, 0CH
=CH2), 9g (+1°CHO); δH(C
DCj') o, gg (3 skin t), 1.24
(16H, wide).

1.62 ('H, t, br), 2-19 (2
H, t), 3-64 (2H, rn), 4.02 (2H
,t), 5. qg C+a, wide).

6.27 (1B, m’), 6-14 (IH.

dd) and 7. I'? (IH, to); δC(CDC
j, ): 14.1.22.6°? 5.6.29.3
．． 31.8.36.7.3g, L 69.0. 91
．． FS, ++q, +.

124.9. Electrochemical polymerization of +73.3 and 184.3 ppm thiophene monomers in a single-compartment electrochemical cell using tetrabutylammonium hexafluorophosphate as the supporting electrolyte under a nitrogen atmosphere at a temperature of 10 °C. I'll go there.

The anode is platinum or indium-acid (ITO)
Is the DC conductivity of the Deatsutomo 6 polymer film measured while the film is adhered to the anode surface (using the 2-probe, mercury contact method)?

or - peeled off from the anode and free-st
anding) using polymer films (using the 4-probe method).

The polymerization conditions are shown in Table 1 (those not shown in the table are detailed above): The conductivities of some of these polymers are shown in Table 2.

The numbers assigned to compounds in Table m1 and Table 2 are used throughout this specification.

Chemical Polymerization of Example 13 A layer of Vc3-(methoxyethoxymethyl)thiophene (1,0 g) was formed on the surface of a solution of MOC/(0,59) in chloroform. After standing for 1 hour, the surface layer became dark, and when the 0 surface layer, in which a blood red solution was formed, was carefully siphoned out and n-san was added, a black powder was precipitated. This powder is 1 x 10 8
Volumetric conductivity of cn was totally blind (compression disc). When a film was re-formed from a solution of this powder in n-decyl acetate, the surface conductivity was 2.21×IO8.

The procedure was the same as in Example 13, except that the two-phase system was allowed to stand for 24 hours because the coloration indicating polymer formation was slow. Using the volumetric conductivity of the precipitated powder Fi5x + oslow 1 (compressed H plate).

25I117! In the water (l pull412"208 ('
09), Mn''(OAc) (0,19) and 3-(methoxyethoxymethyl) in toluene (25d) on a solution containing sulfonic acid (+og) t- A layer of solution containing thiophene (0,51) was formed.The solution was then stirred at 60°C to thoroughly mix the aqueous and non-aqueous phases and left for 24 hours.A black precipitate formed. This was filtered and washed with water, a small amount of acetone, and then n-hexane.The volumetric conductivity was +, +x+ost.

A solution of this black powder in acetone is then applied to a glass slide (with no apparent sign), and then the 4 layers have a surface conductivity of +, 4×, 0−10S and a volume conductivity of 1.4×IO8 cm. friend.

Example +6 A nitrobenzene solution (50 st) containing 1 og of 3-(methoxymethyl)thiophene, 0.29 cv FvInrn (OAe) and Ce stearate of IO& was subjected to mechanical stirring and The solution was heated for 4 hours at 100C with stirring and bubbling with nitrogen.The solution was then allowed to stand for 24 hours.
Next, dry at 40'C. When the obtained polymer was doped with iodine, a volume conductivity of 108cn was obtained.

3-(Methoquinethoxyethoxymethyl)thiophene (
+, 0. p) and Sin (oAc) (1,0 &)'
It was commonly understood to be 50-1 dichloromethane. When the solution was allowed to stand, a black precipitate formed. Form a suspension of black powder on a glass slide in a microscope environment and allow the solvent to evaporate at room temperature. 2.2+x l O8 port surface conductivity and 2.21x
A volume conductivity of lQ 3G was observed.

Example I8 10- & (3,0 g) and 3-(thiethoxymethyl)thiophene (9,0,9) -i) mixed with toluene and then (NH4)2''208 ('09
) and poly(sodium-4-styrene sulfonate) (11,0,120 wt. aqueous solution) f! - forming a layer of the above mixture on top of the containing aqueous solution; A black precipitate was immediately released. The precipitate was washed with water, acetone/hexane and then acetone and dried under vacuum at 70'C until constant. Product volumetric conductivity tilscM
Met.

Example 19 Polyvinyl chloride (unplasticized, powdered, Corvie S
A 154 (heavy JIIk metal) solution of 154 (bg/173) was applied to a platinum electrode (+cm x 3cm) and dried for 2 days at room temperature. The electrode was q, 2b mmol of 3-(dimethyl)thiophene in 1,000 sheds of methoxyethane, 1. ,? 9
6. Immerse in an undivided electrolytic cell containing g mmol of tetrabutynammonium hexafluorophosphate and hinitromethane (30, t/t). E + 7 mAm current density for 1 minute, then 2.3 mAcm current density lfite, total energization J4 (total charge) 25.8
Electrolysis was carried out to a temperature of 50°C to form a rose-colored elastic film, which was then washed in-hexane and air-dried.

Composite materials! f&, number of coulombs transmitted and 1! Based on flow efficiency, the weight ratio of thiophene polymer in polyvinyl chloride is 3.・Tsutsugi.

The film thus obtained is 1. IXI 0-5S mouth~
2X I O-' 3-hole surface 4' centrality and I x 105c
1n ~2Sc! It has a volumetric conductivity of n.

4-rivinyl alcohol (hydrolysis degree & 6.5
-89%) and then acetonitrile < Bu4N
PF6=o,o 5 M) of (3-methoxymethyl)thiophene in o,tMs solution
Electrolysis was performed at a current density of rnA CrH for a short period of time.

A brown film was obtained, which was a 1.94Xlo 3-way surface conductor. 1! rate and has a volumetric conductivity of 5.24XIOS-.

20-polyacrylic e11 (molecular weight 230.000)
3-(Jethoxymethyl in methoxyethane)thiophene(toy)6 under nitrogen atmosphere-3-25mAcyn-2
Then, electrolyze in soil for 8.3 hours. The slurry was then stirred at 55°C for 1/2 hour. The resin was cured by heating it in a circulating air oven at 80°C for 2 hours, then the resin was cured and applied as a paint or strip onto a microscope slide plus for 2 hours or +0°C.
Further harden for 1 hour at c.

Table 3 shows the electrical conductivity of the slightly colored semi-transparent film.

80°C 2 hours 2.6 x 10 1.
2 X IQ-5100℃ 1 hour 2.6 X
Io 1.2 x 10-5+00'c
6 hours 6.7 x 10 1.2
X 10-' The proportion of thiophene polymer in the resin was less than 5% by weight.

This high conductivity allows this resin to be used as an antistatic coating.Example 22 Thiophene monomer is copolymerized with other monomers in a similar manner to Example 12 and according to the conditions shown in Table 4. My friend.

The electrical conductivity of the polymer is shown in Table 5. All the electrical conductivities are as described in Example +2.
Measured by c&-probe method VC.

The copolymer [(methoxyethoxyethoxyethythmethyl)thiophene-vinybcarbazole]nBF4 produced by method (c) is a transparent green material. This copolymer is a transparent green antistatic material or EMI/+ RF shielding. Useful as a material. This polymer is soluble in n-butyl acetate and methyl ethyl ketone, and the reformed green film has only slightly reduced conductivity.

Procedural amendment (formality) August 27, 1986

Claims (1)

[Claims] 1. The following general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1) [In the formula, R^1 is the group -(CH_2)_mNHCOR, the group -O(CH_2)_mNH-COR, Group -(CH_2)
_mCONHR^5, group -O(CH_2)_mCONH
R^5, group -(CH_2)_nO(CHR^3CH_2
)_pOR^4, or an aryloxyalkyl group, an amino group, an aminoalkyl group or a substituted aminoalkyl group, and the nitrogen atom of these groups is an alkyl group,
It may have at least one of an aryl group or a substituted aryl group as a substituent, R is an alkyl group having 1 to 18 carbon atoms, and R^2 is the same as R^1 above, or R^2 is a hydrogen atom, a halogen atom, or an amino group, R^3 is a hydrogen atom or a methyl group, R^4 is an alkyl group having 1 to 6 carbon atoms, and R^5 is an alkyl group having 1 to 6 carbon atoms. 1
8, or an aryl group which may be substituted with an alkyl group or an alkylaryl group,
m is an integer from 1 to 6, n is zero or an integer from 1 to 6, p is 1
is an integer of ~6]. 2. The group R^1 is the group -(CH_2)_nO(CH_2CH
_2)_pOR^4 (where n is 0 or 1, p and R^4 have the same meanings as above), or a group -CH_
2NHCOR' (where R' is an alkyl group having 1 to 12 carbon atoms), or the group -O(CH_2CH_2)NH
COR'' (wherein R'' is an alkyl group having 6 to 18 carbon atoms). 3,3-(methoxyethoxymethyl)thiophene, 3-
The compound according to claim 1 or 2, which is (methoxyethoxymethyl)thiophene or 3-(butoxyethoxyethoxyethoxyethoxyethoxymethyl)thiophene. 4, N-(3-thienylmethyl)acetamide, N-(
3-thienylmethyl)-octanamide or N-(3-
The compound according to claim 1, which is thienylmethyl)dodecaneamide. The compound according to claim 1, which is 5,3-(methoxyethoxy)thiophene or 3-(methoxyethoxyethoxy)thiophene. 6, N-(3-O-thienylethoxy)octanamide or N-(3-O-thienylethoxy)dodecaneamide. 7. There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, n is zero or an integer from 1 to 6] The compound of the following formula Na^+OR^6 and the following formula R^6OH [Formula In the middle, R^6 is a group -(CHR^3CH_2)_pOR
^4, R^3, R^4 and p have the meanings given below] to form the following formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^6 has the meanings given above] Step (a) of producing a compound with the following formula ▲ There are mathematical formulas, chemical formulas, tables, etc. Step (b) of reacting with an acid chloride of [where R has the meaning given below] to produce a compound of the following formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [wherein R has the meaning given below] , or the compound of the following formula ▲ There are mathematical formulas, chemical formulas, tables, etc.▼
R^4, where R^3, R^4 and p have the meanings given below] in the presence of cupric oxide and potassium iodide to form the following formula ▲ mathematical formula, chemical formula, table, etc. ▼ Step (c) of producing the compound [wherein R^7 has the meaning above] or the following formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [wherein m is 1 to 6] An integer] is reacted with acid chloride and triethylamine of the following formula RCOCl [wherein R has the meaning below] to form the following formula ▲ Numerical formula, chemical formula, table, etc. ▼ [where R and m has the above meaning] General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1) [In the formula, R^ 1 is a group -(CH_2)_mNHCOR, a group -O(CH_2)_mNH-COR, a group -(CH_2)
_mCONHR^5, group -O(CH_2)_mCONH
R^5, group -(CH_2)_nO(CHR^3CH_2
)_pOR^4, or an aryloxyalkyl group, an amino group, an aminoalkyl group or a substituted aminoalkyl group, and the nitrogen atom of these groups is an alkyl group,
It may have at least one of an aryl group or a substituted aryl group as a substituent, R is an alkyl group having 1 to 18 carbon atoms, and R^2 is the same as R^1 above, or R^2 is a hydrogen atom, a halogen atom, or an amino group, R^3 is a hydrogen atom or a methyl group, R^4 is an alkyl group having 1 to 6 carbon atoms, and R^5 is an alkyl group having 1 to 6 carbon atoms. 1
8, or an aryl group which may be substituted with an alkyl group or an alkylaryl group,
m is an integer from 1 to 6, n is zero or an integer from 1 to 6, p is 1
is an integer of ~6]. 8. Repeating unit of the following general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^1 and R^2 have the same meaning as stated in claim 1] and the formula Z counter ions (where Z is chloride ion, bromide ion, sulfate ion, bisulfate ion, nitrate ion, tetrafluoroborate ion, alkylsulfonate ion, arylsulfonate ion, arelenecarboxylate ion, alkylcarboxylate ion) , allenedicarboxylate ion, polystyrene sulfonate ion, polyacrylate ion, cellulose sulfonate ion, cellulose sulfate ion, anthracene sulfonate ion, H_
2PO_3^-, H_2PO_4^-, PF_6^-,
SbF_6^-, AsF_6^- or a perfluorinated polyanion). 9. Monomer represented by the following general formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, R^1 and R^2 have the same meaning as stated in claim 1] Claim 8 comprising subjecting a thiophene compound to an electrochemical oxidation reaction in a non-aqueous solvent at an electrode voltage that is electrically positive at least as high as the oxidation potential of the thiophene compound. 2. Method for producing the polymer described in section. 10. The electrolyte solution used in the oxidation reaction is defined in claim 8.
10. A method according to claim 9, wherein the method is selected to provide a counter ion Z according to claim 9. 11. Non-aqueous solvents are acetonitrile, dichloromethane,
10. The method according to claim 9, wherein the solvent is chloroform, dichloroethane, nitromethane, nitrobenzene, propylene carbonate, N-methylpyrrolidone, sulfolane, dimethylformamide or dimethylsulfoxide. 12. Monomeric thiophene of the following general formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, R^1 and R^2 have the same meaning as stated in claim 1] 9. A process for producing a polymer according to claim 8, comprising oxidizing the compound with an oxidizing agent having a standard redox voltage higher than the oxidation potential of the thiophene compound. 13. Oxidizing agents are Ag^II, Cu^II, Ce^IV, Mo^
V, Ru^III, Mn^III, K_2Cr_2O_7, H
_2O_2 or (NH_4)_2S_2O_8,
13. The method of claim 12, wherein the oxidation reaction is carried out, if desired, in the presence of a catalyst.