Anionic Ring-Opening Polymerization of N-(tolylsulfonyl)azetidines To Produce Linear Poly(trimethylenimine) and Closed-System Block Copolymers.

The anionic ring-opening copolymerization of N-( p-tolylsulfonyl)azetidine ( pTsAzet) and N-( o-tolylsulfonyl)azetidine ( oTsAzet) produces poly( pTsAzet- co- oTsAzet) as a statistical copolymer. The pTsAzet/ oTsAzet copolymerization is living and allows for the synthesis of poly(sulfonylazetidine) of target molecular weights with narrow dispersities. 1H NMR spectroscopy was used to monitor the kinetics of the polymerization and estimate the monomer reactivity ratios. It was found that the reactivity ratios for oTsAzet and pTsAzet at 180 °C are 1.66 and 0.60, respectively. The tosyl groups of p( pTsAzet- co- oTsAzet) were reductively removed to produce linear poly(trimethylenimine) (LPTMI). This represents the first route to LPTMI of controlled molecular weight and low dispersity. Finally, the slow kinetics of the sulfonylazetidine polymerization facilitated the synthesis of a block copolymer without requiring the sequential addition of monomer. Specifically, pTsAzet, oTsAzet, and ( N- p-toluenesulfonyl-2-methylaziridine) ( pTsMAz) were combined in solution. pTsMAz selectively polymerizes to form the first block at moderate temperature. After consumption of pTsMAz, the temperature was increased to copolymerize pTsAzet and oTsAzet and produce the block copolymer p( pTsMAz)- b-p( pTsAzet- co- oTsAzet).

Activated Monomer Polymerization of an N-Sulfonylazetidine.

Previously, N-(methanesulfonyl)azetidine (MsAzet) was found to polymerize anionically via ring-opening at temperatures >100 °C to form p(MsAzet) in the presence of an anionic initiator. In the current report, potassium(azetidin-1-ylsulfonyl) methanide (KMsAzet), formed from deprotonation of the methanesulfonyl group of MsAzet by KHMDS, is shown to undergo spontaneous AROP at room temperature to form p(N-K-MsAzet). The structure of p(N-K-MsAzet) differs from that of p(MsAzet), as the sulfonyl groups are incorporated into the polymer backbone of p(N-K-MsAzet). Reaction of p(N-K-MsAzet) with MeOH produces p(N-H-MsAzet), a semicrystalline polymer with a structure like that of polyamides, but with sulfonylamides in place of the carboxamides found in polyamides. Reaction of p(N-K-MsAzet) with benzyl bromide results in the formation of amorphous p(N-Bn-MsAzet). P(N-K-MsAzet) is hypothesized to form via an activated monomer anionic polymerization; this is supported by polymerization kinetic data and structural characterization of the resulting polymers.

Living Anionic Copolymerization of 1-(Alkylsulfonyl)aziridines to Form Poly(sulfonylaziridine) and Linear Poly(ethylenimine).

The anionic ring-opening copolymerization of 1-(methylsulfonyl)aziridine (MsAz) and 1-(sec-butylsulfonyl)aziridine (sBsAz) produces a soluble random copolymer P(MsAz-r-sBsAz), which can subsequently be converted to linear poly(ethylenimine) (lPEI). The copolymerization of MsAz and sBsAz is living and allows for the synthesis of copolymers with low molecular weight distributions. Sequential anionic polymerization of MsAz and sBsAz with 2-methyl-1-(methylsulfonyl)aziridine (MsMAz) creates P(MsAz-r-sBsAz)-b-P(MeMsAz). Removal of the sulfonyl groups from P(MsAz-r-sBsAz)-b-P(MsMAz) gives lPEI-b-poly(propylenimine). For the first time, lPEI can be synthesized by a controlled anionic polymerization.