Conjugated Polymers

• US 20110111350A1
• Filed: 03/26/2009
• Published: 05/12/2011
• Est. Priority Date: 03/26/2008
• Status: Abandoned Application

• Current Assignee: Cranfield University
• Original Assignee: Cranfield University
• Inventors: Whitcombe, Michael James, Chianella, Iva, Lakshmi, Dhana, Piletsky, Sergey Anatoliyovich
• Application Number:
  US12/934,811
• Publication Number:
  US 20110111350A1
• Time in Patent Office: Days
• US Class Current: 430/325
• CPC Class Codes: C07C 219/08 having at least one of the hydroxy groups esterified by a carboxylic acid having the esterifying carboxyl group bound to an acyclic carbon atom of an acyclic unsaturated carbon skeleton
• CPC Class Codes: C07C 233/38 having the carbon atom of the carboxamide group bound to a carbon atom of an acyclic unsaturated carbon skeleton
• CPC Class Codes: C08F 20/34 Esters containing nitrogen , e.g. N,N-dimethylaminoethyl (meth)acrylate
• CPC Class Codes: C08F 20/54 Amides , e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
• CPC Class Codes: C08F 222/102 of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
• CPC Class Codes: C08G 2261/14 Side-groups
• CPC Class Codes: C08G 2261/1432 containing amide groups
• CPC Class Codes: C08G 2261/3221 containing one or more nitrogen atoms as the only heteroatom, e.g. pyrrole, pyridine or triazole
• CPC Class Codes: C08G 2261/3223 containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
• CPC Class Codes: C08G 2261/74 Further polymerisation of the obtained polymers, e.g. living polymerisation to obtain block-copolymers
• CPC Class Codes: C08G 61/124 with a five-membered ring containing one nitrogen atom in the ring
• CPC Class Codes: C08G 61/126 with a five-membered ring containing one sulfur atom in the ring
• CPC Class Codes: C08G 73/0266 Polyanilines or derivatives thereof
• CPC Class Codes: C08G 73/0611 with only one nitrogen atom in the ring, e.g. polypyrroles polysuccinimides C08G73/1092
• CPC Class Codes: C08J 2300/12 Polymers characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
• CPC Class Codes: C08J 2379/02 Polyamines
• CPC Class Codes: C08J 3/246 Intercrosslinking of at least two polymers

Abstract

A monomer M-S has a first polymerisable moiety (M) capable of forming a conjugated polymer, and a second polymerisable moiety (S) with a double bond susceptible to addition polymerisation. Polymerisation of the M-moieties is caused, generally by electropolymerisation or chemical oxidation. Polymerisation of the S-moieties is also caused, generally by a radical mechanism, before, after or simultaneously with the M-polymerisation. Suitable monomers include N-(methacrylamidoethyl)-aniline, N-(acrylamidoethyl)-aniline, N-(methacryloyloxyethyl)-aniline and N-(acryloyloxyethyl)-aniline.

Claims

1. A method of preparing a polymer comprising:

(a) providing a monomer of the form M-S where M is a moiety capable of polymerisation to form a conjugated polymer chain, and S is a moiety including a double bond whereby it is capable of addition polymerisation;

(b) causing polymerisation of the M-moieties, optionally together with a comonomer, to form a conjugated polymer chain;

(c) causing polymerisation of the S-moieties, optionally together with a comonomer;

wherein steps (b) and (c) are carried out in either order or simultaneously.

2. A method according to claim 1, wherein the M-moiety is an optionally substituted aniline, pyrrole or thiophene residue.

3. A method according to claim 2, wherein the M-moiety is an optionally substituted aniline group, and the S-moiety is connected to the aniline nitrogen atom.

4. A method according to claim 2, wherein the M-moiety is an aniline group which is unsubstituted at the 4-position.

5. A method according to claim 1, wherein the conjugated polymer chain is a polyaniline, polypyrrole or polythiophene chain.

6. A method according to claim 5, wherein the M-moiety is an optionally substituted aniline, pyrrole or thiophene residue.

7. A method according to claim 5, wherein the conjugated polymer chain is a polyaniline.

8. A method according to claim 1, wherein the S-moiety comprises an acrylate ester group, a methacrylate ester group, an acrylamido group or a methacrylamido group.

9. A method according to claim 1, wherein the monomer is selected from N-(methacrylamidoethyl)-aniline, N-(acrylamidoethyl)-aniline, N-(methacryloyloxyethyl)-aniline and N-(acryloyloxyethyl)-aniline.

10. A method according to claim 1, wherein step (b) is carried out using chemical oxidation or electropolymerisation.

11. A method according to claim 1, wherein step (c) is carried out using free radical polymerisation.

12. A method according to claim 1, wherein step (b) is carried out before step (c), to produce a composition comprising a first polymer containing a conjugated polymer chain and including polymerisable S-moieties.

13. A method according to claim 12, wherein a composition containing said first polymer is used to coat a surface, whereafter step (c) is carried out to produce a polymer coating on the surface.

14. A method according to claim 12, wherein said first polymer and a photochemically or thermally activated iniferter are reacted together with irradiation or heating to cause attachment of the iniferter to double bonds of the S-moieties to produce a second polymer;

and the second polymer is immersed in a solution containing additional monomer(s) which are grafted to the second polymer.

15. A method according to claim 14, wherein said grafting is carried out in the presence of a template substance which is subsequently removed to leave cavities, whereby the end product is a molecularly imprinted polymer.

16. A method according to claim 1, wherein step (c) is carried out before step (b).

17. A method according to claim 16 in which a film or layer comprising the monomer M-S is formed on a surface and said polymerisation step (c) is carried out to form a polymer coating on the surface.

18. A method according to claim 17 in which said film or layer is partially covered by a mask, exposed portions are irradiated to effect polymerisation, and thereafter the non-exposed and non-irradiated portions are selectively removed.

19. A method according to claim 16 in which the polymer resulting from step (c) is applied to an article to form a surface coating.

20. A method according to claim 16 in which the polymer resulting from step (c) is formed into fibres.

21. A method according to claim 16, including a subsequent polymerisation step (b) effected by treating the step (c) polymer with a solution capable of initiating step (b) polymerisation.

23. A polymer derivable from monomers comprising monomers of the form M-S where M is a moiety capable of polymerisation to form a conjugated polymer chain, and S is a moiety including a double bond whereby it is capable of addition polymerisation;

said polymer having conjugated polymer chains as derived from polymerisation of said M moieties, optionally together with a comonomer;

said conjugated polymer chains being cross-linked by linkages as derived from polymerisation of said S moieties, optionally together with a comonomer, as produced by the method of claim 1.

24. A monomer of the form M-S suitable for use in the method of claim 1 selected from N-(methacrylamidoethyl)-aniline, N-(acrylamidoethyl)-aniline, N-(methacryloyloxyethyl)-aniline and N-(acryloyloxyethyl)-aniline.

26. A method according to claim 8 wherein the spacer is connected to the M moiety by a spacer group 2-6 atoms n length.

27. A method according to claim 20 including a further step of using said fibers to produce articles comprising said fibres.

22. A polymer derivable from monomers comprising monomers of the form M-S where M is a moiety capable of polymerisation to form a conjugated polymer chain, and S is a moiety including a double bond whereby it is capable of addition polymerisation;

said polymer having conjugated polymer chains as derived from polymerisation of said M moieties, optionally together with a comonomer;

said conjugated polymer chains being cross-linked by linkages as derived from polymerisation of said S moieties, optionally together with a comonomer.

25. The polymer of claim 22, wherein the monomer of the form is M-S is N-(methacrylamidoethyl)-aniline.