Polymers of intrinsic microporosity (pims) containing locked spirobisindane structures and methods of synthesis of pims polymers

A method of preparing a polymer of intrinsic microporosity homo-polymer or a co-polymer, wherein the method includes the step of

• (a) reacting a biscatechol of Formula (V);
• wherein
• each R1 can be the same or different, each R2 can be the same or different and wherein R1 and/or R2 are selected from any one or more of H;
• straight or branched, saturated or unsaturated lower C1-C6 alkyl groups, wherein the lower alkyl groups can include aromatic or non-aromatic ring structures R3OR4, R3O(C═O)R4, R3C(═O)OR4, or R3OH, wherein each of R3 and R4 are the same or different and are selected from straight or branched, saturated or unsaturated lower C1-C6 alkyl groups;
• and
• wherein,
• (i) X is —CH2—Y—CH2—, and wherein Y is O;
• CH2;
• C(═O);
• C(OR7)(OR8);
• NH;
• NR9;
• S;
• S(═O);
• SO2;
• C(═S);
• PH;
• PR10;
• BH;
• BR11 or BOR11;
• and wherein R7 and R8 are selected from any one or more of H or C1-C6 alkyl groups;
• and wherein R9, R10 and R11 are selected from any one or more of H or straight or branched, saturated or unsaturated lower C1-C6 alkyl groups, wherein the lower alkyl groups can include aromatic or non-aromatic ring structures;
• or
• (ii) X is —CH2-CH2—, —CH═CH—, —(═O)O—, —C(═O)NH— or —CHR12-CHR12—, wherein R12 are selected from any one or more of H or straight or branched, saturated or unsaturated lower C1-C6 alkyl groups, wherein the lower alkyl groups can include aromatic or non-aromatic ring structures ;
• and
• wherein the silyl ether protecting groups are the same or different;
• or Formula (VII);
• wherein
• (i) X is —CH2—Y—CH2—, and wherein Y is O;
• CH2;
• C(═O);
• C(OR7)(OR8);
• NH;
• NR9;
• S;
• S(═O);
• SO2;
• C(═S);
• PH;
• PR10;
• BH;
• B R11 or BO R11;
• and wherein R7 and R8 are selected from any one or more of H or C1-C6 alkyl groups;
• and wherein R9, R10 and R11 are selected from any one or more of H or straight or branched, saturated or unsaturated lower C1-C6 alkyl groups, wherein the lower alkyl groups can include aromatic or non-aromatic ring structures;
• or
• (ii) X is —CH2-CH2—, —CH═CH—, —(═O)O—, —C(═O)NH— or —CHR12-CHR12—, wherein R12 are selected from any one or more of H or straight or branched, saturated or unsaturated lower C1-C6 alkyl groups, wherein the lower alkyl groups can include aromatic or non-aromatic ring structures;
• with a suitable tetrahalo aromatic linking monomer or
• (b) reacting together a first biscatechol monomer of Formula (V) or Formula (VII), a second biscatechol monomer that is different to the first biscatechol monomer, and a suitable tetrahalo aromatic linking monomer, or
• (c) reacting together a biscatechol monomer of Formula (V) or Formula (VII), a first suitable tetrahalo aromatic linking monomer, and a second suitable tetrahalo aromatic linking monomer that is different to the first suitable tetrahalo aromatic linking monomer,
• wherein the monomers are reacted in the presence of an organic base, an inorganic base and/or fluoride ions.

A polymer of intrinsic microporosity (PIM) homo- or co-polymer including at least one biscatechol monomer of Formula (VIII):

• wherein
• each R1 can be the same or different, each R2 can be the same or different and wherein R1 and/or R2 are selected from any one or more of H;
• straight or branched, saturated or unsaturated lower C1-C6 alkyl groups, wherein the lower alkyl groups can include aromatic or non-aromatic ring structures R3OR4, R3O(C═O)R4, R3C(═O)OR4, or R3OH, wherein each of R3 and R4 are the same or different and are selected from straight or branched, saturated or unsaturated lower C1-C6 alkyl groups;
• and
• R5 and R6 represent suitable linking monomers, wherein the linking monomers can be the same or different and are preferably selected from any one or more tetrahalo aromatic monomers;
• (i) X is —CH2—Y—CH2—, and wherein Y is O;
• CH2;
• C(═O);
• C(OR7)(OR8);
• NH;
• NR9;
• S;
• S(═O);
• SO2;
• C(═S);
• PH;
• PR10;
• BH;
• BR11 or BOR11;
• and wherein R7 and R8 are selected from any one or more of H or C1-C6 alkyl groups;
• and wherein R9, R10 and R11 are selected from any one or more of H or straight or branched, saturated or unsaturated lower C1-C6 alkyl groups, wherein the lower alkyl groups can include aromatic or non-aromatic ring structures;
• or
• (ii) X is —CH2-CH2—, —CH═CH—, —(═O)O—, —C(═O)NH— or —CHR12-CHR12—, wherein R12 are selected from any one or more of H or straight or branched, saturated or unsaturated lower C1-C6 alkyl groups, wherein the lower alkyl groups can include aromatic or non-aromatic ring structures.