Intrinsically microporous ladder-type Tröger's base polymers

A method of synthesizing an intrinsically microporous ladder-type Tröger's base polymer comprising:

• (a) forming a ladder-type diamine monomer by catalytic arene-norbornene annulation (CANAL) polymerization of a halogenated arylamine and norbornadiene or a derivative thereof, wherein the molar ratio of the halogenated arylamine to norbornadiene or the derivative thereof is 2:1, or
• (a1) forming a first intermediate ladder-type compound by CANAL polymerization of a halogenated arene and norbornadiene or a derivative thereof, wherein the ratio of the halogenated arene to norbornadiene or the derivative thereof is 2:1;
• and
• (a2) nitrating the first intermediate ladder-type compound to form an intermediate ladder-type dinitro compound;
• and
• (a3) reducing the two nitro groups of the intermediate ladder-type dinitro compound to form a ladder-type diamine monomer;
• and
• (b) reacting at least two of the ladder-type diamine monomers to form the intrinsically microporous ladder-type Tröger's base polymer comprising a repeat unit represented by formula (I):
• wherein each Ar is independently selected from an unsubstituted or substituted aryl group;
• X is a carbon or heteroatom bridging moiety selected from —[O]—, —[S]—, —[B(O)Ra]—, —[NRa]—, —[P(O)Ra]—, —[(PO)(O)Ra]—, —[CO]—, —[—CRaRb]—, —[C(O)Ra(O)Rb]—, or —[Si(O)Ra(O)Rb]—, and Ra and Rb are independently selected from the group consisting of hydrogen, alkyl groups, aryl groups, and heterocyclic groups;
• R1 and R2 are independently selected from the group consisting of hydrogen, linear unsubstituted and substituted alkyl groups, branched unsubstituted and substituted alkyl groups, unsubstituted and substituted alkoxy groups, unsubstituted and substituted aryl groups, heterocyclic groups, halogen groups, —CHO, groups having an —O— moiety, groups having an —O(CO)— moiety, groups having an —O(CO)O— moiety, groups having an —O(CO)N< moiety, groups having a —S— moiety, groups having a —B< moiety, —NO2, groups having a —N< moiety, groups having a —P< moiety, groups having a —(PO)< moiety, groups having a —(CO)— moiety, groups having a —(CO)O— moiety, groups having a —(CO)N< moiety and groups having a —Si═ moiety;
• and n is an integer greater than 1.

A method of separating a chemical species in a fluid composition comprising:

• (a) contacting a membrane comprising an intrinsically microporous ladder-type Tröger's base polymer with a fluid composition comprising at least two chemical species;
• and
• (b) separating a first chemical species from the fluid composition;
• wherein the intrinsically microporous ladder-type Tröger's base polymer comprises a repeat unit represented by formula (I):
• wherein each Ar is independently selected from an unsubstituted or substituted aryl group;
• X is a carbon or heteroatom bridging moiety selected from —[O]—, —[S]—, —[B(O)Ra]—, —[NRa]—, —[P(O)Ra]—, —[(PO)(O)Ra]—, —[CO]—, —[—CRaRb]—, —[C(O)Ra(O)Rb]—, or —[Si(O)Ra(O)Rb]—, and Ra and Rb are independently selected from the group consisting of hydrogen, alkyl groups, aryl groups, and heterocyclic groups;
• R1 and R2 are independently selected from the group consisting of hydrogen, linear unsubstituted and substituted alkyl groups, branched unsubstituted and substituted alkyl groups, unsubstituted and substituted alkoxy groups, unsubstituted and substituted aryl groups, heterocyclic groups, halogen groups, —CHO, groups having an —O— moiety, groups having an —O(CO)— moiety, groups having an —O(CO)O— moiety, groups having an —O(CO)N< moiety, groups having a —S— moiety, groups having a —B< moiety, —NO2, groups having a —N< moiety, groups having a —P< moiety, groups having a —(PO)< moiety, groups having a —(CO)— moiety, groups having a —(CO)O— moiety, groups having a —(CO)N< moiety and groups having a —Si═ moiety;
• and n is an integer greater than 1.