Polymerisable thiophene monomers, their production and polymers prepared therefrom

Claim 2

A compound having the general formula wherein R 1 is -(CH 2 ) m NHCOR, -O(CH 2 ) m NHCOR, -(CH 2 ) m CONHR 5 -0(CH 2 ) m CONHR 5 , -(CH2)nO(CHR3CH2)pOR4, aryloxyalkyl, amino, aminoalkyl or substituted aminoalkyl which is substituted on the nitrogen atom by at least one alkyl, aryl or substituted aryl group; R is an alkyl group containing from 1 to 18 carbon atoms; R 2 is the same as R 1 , or 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 containing from 1 to 6 carbon atoms; R 5 is an alkyl group containing from 1 to 18 carbon atoms, an aryl group optionally substituted by an alkyl group or an alkylaryl group; m is an integer of from 1 to 6; n is 0 or an integer of from 1 to 6; p is an integer of from 1 to 6.

Claim 3

A compound as claimed in claim 1 wherein the group R 1 is -(CH 2 ) n O(CH 2 CH 2 )pOR 4 where n is 0 or 1 and p and R 4 are as defined in claim 1; -CH 2 NHCOR' where R' is an alkyl group containing from 1 to 12 carbon atoms; or -O(CH 2 CH 2 )NHCOR" where R" is an alkyl group containing from 6 to 18 carbon atoms.

Claim 4

A compound as claimed in claim 1 or claim 2 which is 3-(methoxyethoxymethyl)thiophene, 3-(methoxyethoxyethoxymethyl)thiophene or 3-(butoxyethoxyethoxyethoxyethoxymethyl)thiophene.

Claim 5

A compound as claimed in claim 1 which is N-(3-thienylmethyl)acetamide, N-(3-thienylmethyl)-octanamide or N-(3-thienylmethyl)dodecanamide.

Claim 6

A compound as claimed in claim 1 which is 3-(methoxyethoxy)thiophene or 3-(methoxyethoxyethoxy)thiophene.

Claim 7

A compound as claimed in claim 1 which is N-(3-0-thienylethoxy)octanamide or N-(3-0-thienylethoxy)dodecanamide.

Claim 8

A process for the preparation of a compound as claimed in claim 1 which comprises one of the following a) reacting a compound of the formula where n is as defined in claim 1, with Na + OR 6 - and R 6 0H where R 6 is -(CHR 3 CH 2 )pOR 4 and R 3 , R 4 and p are as defined in claim 1 to give the compound b) reacting a compound of the formula where m is as defined in claim 1 with triethylamine and an acid chloride of the formula RCOCI where R is as defined in claim 1 to give the compound of the formula c) reacting a compound of the formula with Na + OR 7 - where R 7 is the group -O(CHR 3 CH 2 ) p OR 4 in the presence of cupric oxide and potassium iodide to give the compound of the formula ; or d) reacting a compound of the formula where m is as defined in claim 1 with an acid chloride of the formula RCOCI and triethylamine where R is as defined in claim 1 to give the compound of the formula

Claim 9

A polymer which comprises repeating units of the general formula where R' and R 2 are as defined in claim 1, and counterions of the formula Z, where Z is chloride, bromide, sulphate, bisulphate, nitrate, tetrafluoroborate, alkylsulphonate, arylsulphonate, arenecarboxylate, alkylcar- boxylate, arenedicarboxylate, polystyrenesulphonate, polyacrylate, cellulose sulphonate, cellulose sulphate, anthracene sulphonate, H 2 PO 3̅ , H 2 PO 4̅ , PF 6̅ SbF 6̅ , AsF or a perfluorinated polyanion.

Claim 10

A process for the preparation of a polymer as claimed in claim 8 which comprises subjecting a thiophene monomer as claimed in claim 1 in a non-aqueous solvent to electrochemical oxidation at an electrode potential which is at least as electropositive as the oxidation potential of the thiophene monomer.

Claim 11

A process as claimed in claim 9 wherein the electrolyte is chosen to as to provide the counterions Z as defined in claim 8.

Claim 12

A process as claimed in claim 9 wherein the solvent is acetonitrile, dichloromethane, chloroform, dichloroethane, nitromethane, nitrobenzene, propylene carbonate, N-methylpyrrolidone, sulpholane, dimethylformamide or dimethylsulphoxide.

Claim 13

A process for the preparation of a polymer as claimed in claim 8 which comprises oxidising a thiophene monomer as claimed in claim 1 with an oxidant having a higher standard redox potential than the oxidation potential of the monomer.

Claim 14

A process as claimed in claim 12 wherein the oxidant is Ag", Cu" , Cew, Mo v , Ru III , Mn III , K 2 Cr 2 O 7 , H 2 0 2 or (NH 4 ) 2 S 2 O 8 and the reaction is optionally carried out in the presence of a catalyst.

Claim 15

A copolymer of a thiophene derivative as claimed in any one of claims 1 to 6 with another monomer which is polymerisable therewith.

Claim 16

A copolymer as claimed in claim 14 wherein the other monomer is thiophene, pyrrole, styrene or N-vinylcarbazole.

Claim 17

The use of a polymer as claimed in claim 8 as an EMI/RF shielding material, in an electrochromic display system, as an antistatic material, or an ion or pH sensor, as a battery electrode material, in a switching device, as a protective coating for an electrode, as an electrode for the selective deposition of ions or as a self-heating regulator.

Claim 18

A process for the preparation of a compound having the general formula wherein R 1 is -(CH 2 ) m NHCOR, -O(CH 2 ) m NHCOR, -(CH 2 ) m CONHR 5 -O(CH 2 ) m CONHR 5 , -(CH 2 ) n O(CHR 3 CH 2 ) p OR 4 , aryloxyalkyl, amino, aminoalkyl or substituted aminoalkyl which is substituted on the nitrogen atom by at least one alkyl, aryl or substituted aryl group; R is an alkyl group containing from 1 to 18 carbon atoms; R 2 is the same as R 1 , or is a hydrogen atom, a halogen atom or an amino group. R3 is a hydrogen atom or a methyl group; R 4 is an alkyl group containing from 1 to 6 carbon atoms; R 5 is an alkyl group containing from 1 to 18 carbon atoms, an aryl group optionally substituted by an alkyl group or an alkyaryl group; m is an integer of from 1 to 6; n is 0 or an integer of from 1 to 6; p is: an integer of from 1 to 6; which process comprises one of the following a) reacting a compound of the formula where n is as defined above with Na + OR 6 - and R 6 0H where R 6 is -(CHR 3 CH 2 )pOR 4 and R 3 , R 4 and p are as defined above to give the compound b) reacting a compound of the formula where m is as defined above with triethylamine and an acid chloride of the formula RCOC1 where R is as defined above to give the compound of the formula c) reacting a compound of the formula with Na + OR 7- where R 7 is the group -0(CHR 3 CH 2 )pOR 4 in the presence of cupric oxide and potassium iodide to give the compound of the formula ; or d) reacting a compound of the formula where m is as defined above with an acid chloride of the formula RCOCI and triethylamine where R is as defined above to give the compound of the formula

Claim 19

A process for the preparation of a compound having the general formula wherein R 1 is -(CH 2 ) m NHCOR, -O(CH 2 ) m NHCOR, -(CH 2 ) m CONHR 5 -O(CH 2 ) m CONHR 5 , -(CH 2 ) n O(CHR 3 CH 2 ) p OR 4 , aryloxyalkyl, amino, aminoalkyl or substituted aminoalkyl which is substituted on the nitrogen atom by at least one alkyl, aryl or substituted aryl group; R is an alkyl group containing from 1 to 18 carbon atoms; R 2 is the same as R 1 , or is a hydrogen atom, a halogen atom or an amino group. R3 is a hydrogen atom or a methyl group; R 4 is an alkyl group containing from 1 to 6 carbon atoms; R 5 is an alkyl group containing from 1 to 18 carbon atoms, an aryl group optionally substituted by an alkyl group or an alkyaryl group; m is an integer of from 1 to 6; n is 0 or an integer of from 1 to 6; p is: an integer of from 1 to 6; which process comprises one of the following a) reacting a compound of the formula where n is as defined above with Na + OR 6 - and R 6 0H where R 6 is -(CHR 3 CH 2 )pOR 4 and R 3 , R 4 and p are as defined above to give the compound b) reacting a compound of the formula where m is as defined above with triethylamine and an acid chloride of the formula RCOC1 where R is as defined above to give the compound of the formula c) reacting a compound of the formula with Na + OR 7- where R 7 is the group -0(CHR 3 CH 2 )pOR 4 in the presence of cupric oxide and potassium iodide to give the compound of the formula ; or d) reacting a compound of the formula where m is as defined above with an acid chloride of the formula RCOCI and triethylamine where R is as defined above to give the compound of the formula

Claim 20

A process for the preparation of a polymer which has repeating units of the general formula where R 1 and R 2 are as defined in claim 1, and counterions of the formula Z, where Z is chloride, bromide, sulphate, bisulphate, nitrate, tetrafluoroborate, alkylsulphonate, arylsulphonate, arenecarboxylate, alkylcar- boxylate, arenedicarboxylate, polystyrenesulphonate, polyacrylate, cellulose sulphonate, cellulose sulphate, anthracene sulphonate, H 2 PO 3̅ , H 2 PO 4̅ , PF 6̅ , SbF 6̅ , AsF or a perfluorinated polyanion, which process comprises subjecting a thiophene monomer as claimed in claim 1 in a non-aqueous solvent to electrochemical oxidation at an electrode potential which is at least as electropositive as the oxidation potential of the thiophene monomer.

Claim 21

A process as claimed in claim 2 wherein the electrolyte is chosen to as to provide the counterions Z.

Claim 22

A process as claimed in claim 2 wherein the solvent is acetonitrile, dichloromethane, chloroform, dichloroethane, nitromethane, nitrobenzene, propylene carbonate, N-methyipyrrolidone, sulpholane, dimethylformamide or dimethylsulphoxide.

Claim 23

A process for the preparation of a polymer as defined in claim 2 which comprises oxidising a thiophene monomer as defined in claim 1 with an oxidant having a higher standard redox potential than the oxidation potential of the monomer.

Claim 24

A process as claimed in claim 5 wherein the oxidant is Ag", Cu", Ce IV , Mo v , Ru III , Mn III , K 2 Cr 2 O 7 , H 2 O 2 or (NH 4 ) 2 S 2 O 8 and the reaction is optionally carried out in the presence of a catalyst.

Claim 25

A copolymer of a thiophene derivative as claimed in any one of claims 1 to 6 with another monomer which is polymerisable therewith.