Method of making sulfur-containing polymers from hexahydrotriazine and dithiol precursors

A method of preparing a polymer material, comprising:

• mixing an N-substituted hexahydrotriazine with a dithiol to form a first mixture;
• and
• heating the first mixture to form a product mixture comprising a polythioaminal polymer, the polythioaminal polymer represented by
• wherein:
• each R1 is independently a hydrocarbon species, an aromatic species, a polyol species, or a polyether species,
• each R2 is independently a hydrogen, a fluorine, an alkyl substituent, a cycloalkyl substituent, or an aromatic substituent, wherein each R2 has a molecular weight no more than 120 Daltons,
• X is selected from the group consisting of a hydrogen, an alkane thiol, an aromatic thiol, a peptide, a thio-acid, a nucleotide, and combinations thereof,
• Z is selected from the group consisting of a hydrogen, an alkane thiol, an aromatic thiol, a peptide, a thio-acid, a nucleotide, and combinations thereof,
• at least one of X and Z is not hydrogen, and
• n is an integer greater than or equal to 1.

A method of preparing a polymer material, comprising:

• mixing an N-substituted hexahydrotriazine with a dithiol to form a first mixture, wherein a substituent bonded to one or more nitrogen atoms of the N-substituted hexahydrotriazine forms a hydride that is volatile at temperatures less than 200° C.;
• and
• heating the first mixture to form a product mixture comprising a polythioaminal polymer, the polythioaminal polymer represented by
• and a segment represented by
• wherein:
• R1 is independently a hydrocarbon species, an aromatic species, a polyol species, or a polyether species,
• each R2 is independently a hydrogen, a fluorine, an alkyl substituent, a cycloalkyl substituent, or an aromatic substituent, wherein each R2 has a molecular weight no more than 120 Daltons,
• X is a linking group selected from the group consisting of hexyl, dihydroxybutyl, and polyethylene glycol,
• K is selected from the group consisting of hydrogen, an alkane thiol, an aromatic thiol, a peptide, a protein, a thio-acid, a nucleotide, and combinations thereof, and
• the wavy bond represents a bond to another atom in the chemical structure.