Microporous polymers, methods for the preparation thereof, and uses thereof
A method for preparing a conjugated microporous polymer comprises the coupling of an alkynyl aryl monomer having a plurality of terminal alkyne groups with an iodo- or bromo-aryl monomer having a plurality of halogen atoms in the presence of a palladium (0) catalyst. The conjugated microporous polymer comprises nodes comprising at least one aryl unit and struts comprising at least one alkyne unit and at least one aryl unit, wherein a node is bonded from its aryl unit or units to at least two struts via alkyne units. Such polymers are useful in numerous areas such as separations, controlled release, gas storage and supports for catalysts.
1. A method for preparing a conjugated microporous polymer comprising the coupling of:
an alkynyl aryl monomer having a plurality of terminal alkyne groups; with
an iodo- or bromo-aryl monomer having a plurality of halogen atoms;
in the presence of a palladium (0) catalyst;
wherein either:
the alkynyl aryl monomer has three terminal alkyne groups and the iodo- or bromo-aryl monomer has two halogen atoms;
or:
the alkynyl aryl monomer has two terminal alkyne groups and the iodo-bromo-aryl monomer has three halogen atoms.
2. A method as claimed in claim 1 wherein the palladium (0) catalyst is a phosphine palladium (0) catalyst.
3. A method as claimed in claim 2 wherein the phosphine palladium (0) catalyst is tetrakis-(triphenylphosphine) palladium.
4. A method as claimed in claim 1 wherein the coupling is carried out in the presence of a co-catalyst.
5. A method as claimed in claim 4 wherein the co-catalyst is copper iodide.
6. A method as claimed in claim 1 wherein the coupling is carried out in the presence of a solvent.
7. A method as claimed in claim 6 wherein the solvent is toluene.
8. A method as claimed in claim 1 wherein the coupling is carried out in the presence of a base.
9. A method as claimed in claim 8 wherein the base is triethylamine.
10. A method as claimed in claim 1 wherein the aryl component in the alkynyl aryl monomer is unsubstituted benzene.
11. A method as claimed in claim 1 wherein the aryl component in the alkynyl aryl monomer is not unsubstituted benzene.
12. A method as claimed in claim 11 wherein the aryl component in the alkynyl aryl monomer is heteroaromatic.
13. A method as claimed in claim 1 wherein the aryl component in the iodo- or bromo-aryl monomer is unsubstituted benzene.
14. A method as claimed in claim 1 wherein the aryl component in the iodo- or bromo-aryl monomer is not unsubstituted benzene.
15. A method as claimed in claim 14 wherein the aryl component in the iodo- or bromo-aryl monomer is heteroaromatic.
16. A method as claimed in claim 1 wherein the aryl component in either or both of the alkynyl aryl monomer and/or the iodo- or bromo-aryl monomer carries one or more substituent.
17. A method as claimed in claim 16 wherein at least one of said substituents is selected from the group consisting of amino, alkyl, haloalkyl, an azide, fluorine, alkenyl, hydroxyl, thiol, ester, amide, urethane, carbonate, acetate, ether and thioether.