Some New Copolymers by Ionic Polymerization

Abstract

In the first part the cationic polymerization of a homologous series of cyclic with ring sizes of 11, 14, and 17 atoms is described. During the polymerization of triethylene glycol formal (TGF) an equilibrium is reached and besides high polymers cyclic oligomers are formed. The oligomers and the polymers are built up of a regular sequence of one oxymethylene unit and three oxyethylene units -f-(OCH2) (OC2 H4 h+x· They are therefore be labelled a "sequenced copolymer." The equilibrium concentrations of the cyclic oligomers with a polymerization degree from 2 to 15 follow the equation. The 14-and 17membered monomers POC and HOC forms cyclic oligomers and high polymers of the general formula +COCH2) 1 (OC2H4)y+x with y=4 and y=5,respectively. The melting points of these sequenced copolymers withy= 1-5 are determined. Furthermore, the cationic polymerization of 1,3-dioxacycloundecane (OMF) and 1,3,6,11-tetraoxacyclotridecane (DDF) was studied. 1 H and 13 C NMR spectra show that again regular copolymers are formed: In the first case an alternating I: I copolymer +COCH2) (OC8H16)+, in the latter case a terpolymer with the regular sequence +COCH2) (OC2 H4 ) (OC4 H8) (OC2 H4 )+x· The second part deals with the polymerization of 2isopropenylnaphthalene. With maleic anhydride at room temp a charge-transfer complex is formed; at higher temp a reaction occurs. Only at low temp with UV initiation or redox initiation a copolymer is formed. With cationic catalysts a mixture of dimer, trimer, and tetramer but no polymer is obtained. The anionic polymerization yields polymers with molecular weight from 10,000 to 300,000 and melting points of 280°C and glass-transition temp of 220°C. By "living polymer" techniques block copolymers are available.

Thermal Polymerization of 1,2-Dithiane

“…Namely, it is clear that a concentration of the monomer is an important factor for the thermal polymerization of DT. 11,12 To determine a kinetic order of the polymerization with respect to the monomer concentration, the polymerization of DT was carried out at different DT concentrations. The relationships between overall rate of polymerization (R p ) and log [DT] gives a linear line as shown in Figure 2.…”

“…[11][12][13] However, it is not clear the ceiling temperature and equilibrium monomer concentration of the polymerization of DT.…”

“…[2][3][4][5][6][7][8] In ringopening polymerizations of cyclic compounds, a equilibrium monomer and polymer should be considered. [11][12][13] In the polymerizations of cyclic disulfides, a torsional strain of -C-S-S-C-bond angle seems to play a role to determine a activity for the polymerization. 9,10,14 Recently, much attention has been paid to synthesis of interlocked polymers such as polyrotaxanes and polycatenanes consisting of cyclic components.…”