Circularly Recyclable Polymers Featuring Topochemically Elongated Carbon-Carbon Bonds

A method of topochemically producing a polymer, comprising:

• providing a crystalline polymer formed from at least two monomers independently selected from the group consisting of Formula I, Formula II, and Formula III,
• wherein Formula I is
• wherein each R is independently a C1 to C20 linear chain alkyl or a C1 to C20 branched chain alkyl, wherein any —H maybe substituted with —F,
• wherein Formula II is
• wherein A, B, C and D are independently selected from —C(═O)—R, —C(═O)—OR,
• —C(═S)—R,
• —C(═O)—NRR,
• —C(═O)OM, —S(═O)OM, —S(═O)(═O)OM,
• —NO2, —OR, —OC(═O)R,
• —H, —F, —Cl, and —CH3,
• wherein each R is independently H, —NO2, a C1 to C20 branched chain alkyl or a C1 to C20 straight chain alkyl, wherein the branched chain alkyl or the straight chain alkyl is optionally substituted with —O—, —NRR or —S—, and any hydrogen can be substituted with —F,
• wherein X is a halogen or hydrogen, at least one X is a halogen, M is an organic or inorganic cation, and n=0 to 20 and
• wherein Formula III is
• wherein each E, F, G, and H is independently —C(C═O)OR or —CN, wherein each R is independently a C1 to C20 branched chain alkyl or a C1 to C20 straight chain alkyl, wherein the branched chain alkyl or the straight chain alkyl is optionally substituted with —O—, —NRR or —S—, and any hydrogen can be substituted with —F,
• wherein the monomers are chemically bound to each other by at least one carbon-carbon single bond to form the crystalline polymer;
• mixing the crystalline polymer with a solvent to form a mixture;
• sonicating the mixture to form a suspension;
• and
• vacuum filtering and heat pressing the suspension.

A method of thermoplastic production of a polymer, comprising:

• providing a crystalline polymer formed from at least two monomers independently selected from the group consisting of Formula I, Formula II, and Formula III,
• wherein Formula I is
• wherein each R is independently C1 to C20 linear chain alkyl or a C1 to C20 branched chain alkyl, wherein any —H may be substituted with —F,
• wherein Formula II is
• wherein A, B, C and D are independently selected from —C(═O)—R, —C(═O)—OR,
• —C(═S)—R,
• —C(═O)—NRR,
• —C(═O)OM, —S(═O)OM, —S(═O)(═O)OM,
• —NO2, —OR, —OC(═O)R,
• —H, —F, —Cl, and —CH3,
• wherein each R is independently H, —NO2, a C1 to C20 branched chain alkyl or a C1 to C20 straight chain alkyl, wherein the branched chain alkyl or the straight chain alkyl is optionally substituted with —O—, —NRR or —S—, and any hydrogen can be substituted with —F,
• wherein X is a halogen or hydrogen, at least one X is a halogen, M is an organic or inorganic cation, and n=0 to 20, and
• wherein Formula III is
• wherein each E, F, G, and H is independently —C(C═O)OR or —CN, wherein each R is independently a C1 to C20 branched chain alkyl or a C1 to C20 straight chain alkyl, wherein the branched chain alkyl or the straight chain alkyl is optionally substituted with —O—, —NRR or —S—, and any hydrogen can be substituted with —F,
• wherein the monomers are chemically bound to each other by at least one carbon-carbon single bond to form the crystalline polymer;
• mixing the crystalline polymer with a first solvent to form a mixture;
• subjecting the mixture to heat to form a viscous polymer solution;
• mixing the viscous polymer solution with a second solvent to form a residue;
• and
• drying the residue.

A method of depolymerization, comprising:

• providing a crystalline polymer formed from at least two monomers independently selected from the group consisting of Formula I, Formula II, and Formula III,
• wherein Formula I is
• wherein each R is independently a C1 to C20 linear chain alkyl or a C1 to C20 branched chain alkyl, wherein any —H maybe substituted with —F,
• wherein Formula II is
• wherein A, B, C and D are independently selected from —C(═O)—R, —C(═O)—OR,
• —C(═S)—R,
• —C(═O)—NRR,
• —C(═O)OM, —S(═O)OM, —S(═O)(═O)OM,
• —NO2, —OR, —OC(═O)R,
• —H, —F, —Cl, and —CH3,
• wherein each R is independently H, —NO2, a C1 to C20 branched chain alkyl or a C1 to C20 straight chain alkyl, wherein the branched chain alkyl or the straight chain alkyl is optionally substituted with —O—, —NRR or —S—, and any hydrogen can be substituted with —F,
• wherein X is a halogen or hydrogen, at least one X is a halogen, M is an organic or inorganic cation, and n=0 to 20, and
• wherein Formula III is
• wherein each E, F, G, and H is independently —C(C═O)OR or —CN, wherein each R is independently a C1 to C20 branched chain alkyl or a C1 to C20 straight chain alkyl, optionally substituted with —O—, —NRR or —S—, and any hydrogen can be substituted with —F,
• wherein the monomers are chemically bound to each other by at least one carbon-carbon single bond to form the crystalline polymer,
• wherein the carbon-carbon single bond has a bond length between about 1.57 Å and about 1.70 Å,
• mixing the crystalline polymer with a solvent to form a mixture,
• heating the mixture to a temperature between about 125° C. to about 375° C., and
• recovering the monomers.