Polymerization of 2,4‐dimethyl‐6‐vinyl‐s‐triazine

Abstract

2,4‐Dimethyl‐6‐vinyl‐s‐triazine (A) is readily polymerized by free radical initiators to a high molecular weight product. Copolymerization studies with reference monomers (M1), styrene and methyl methacrylate, gave reactivity ratios with styrene: r1 = 0.12, r2 = 0.92; with methyl methacrylate: r1 = 0.37, r2 = 1.75. The following Q−e values were calculated: with styrene Q2 = 12, e2 = +0.92; with methyl methacrylate Q2 = 2.6, e2 = +1.09. These values indicate that the dimethyl triazinyl moiety is a radical stabilizing and electronegative substituent. Poly(2,4‐dimethyl‐6‐vinyl‐s‐triazine) (PDMVT) is soluble in water and in all the common organic solvents with the exception of aliphatic hydrocarbons. Poly(isopropenyl‐s‐triazine) (PIT) is soluble only in dimethylformamide and chloroform. The latter also softened at a much higher temperature than PDMVT. These differences were considered a result of hydrogen bonding between chains in PIT.

Revised insights into templating radical polymerization within nanoreactors

“…reactivity of the vinyl groups; styrenic (VBA), methacrylic type (DMET) and vinyltriazine type (VDAT), the latter with very high reactivity. 29 As expected, VDAT is extremely reactive and leads to very intense secondary SEC peaks, which are sometimes significantly larger than the template peak* [ Fig. 4(C)].…”

“…Inter‐association equilibrium constants ( K a ) have been measured by 1 H NMR titration experiments in CDCl 3 at room temperature, resulting in 530 M −1 (adenine‐thymine) and 890 M −1 (diaminotriazine‐thymine) . One would expect a more pronounced templating effect with the diaminotriazine moiety because of stronger complexation with PVBT; (2) The difference in reactivity of the vinyl groups; styrenic (VBA), methacrylic type (DMET) and vinyltriazine type (VDAT), the latter with very high reactivity …”

Preparation and Polymerization of Vinyl Heterocyclic Compounds

“…homopolymerization with free radical initiators. It is soluble only in DMF and chloroform, and softens a t a much higher temperature than 76 (R,R' = CH,), owing to hydrogen bonding between polymer chains [395]. The diamino derivative (77, R,R' = NH,) was also synthesized [398].…”