The initiation of polymerization of unsaturated tertiary amines with carboxylic acids

• Published in: Die Makromolekulare Chemie 1981-05, Vol.182 (5), p.1595-1603
• Main Authors: Hrabák, František, Hynková, Vlasta
• Format: Article
• Language: English
• ISSN: 0025-116X; 0025-116X
• DOI: 10.1002/macp.1981.021820530

The polymerization rate (Rp) of N‐methyl‐N‐phenyl‐2‐aminoethyl methacrylate (MPAEMA) initiated with 2,2' ‐azodiisobutyronitrile (AIBN) at 50°C increased considerably after the addition of CCI3COOH, and distinctly after the addition of CH3COOH. Rp in a benzene solution of 2 mol. dm−3 MPAEMA and 5 · 10−2 mol. dm−3 CCl3COOH (without AIBN) was 13% · h−1. [η] DMF20 of the obtained polymer corresponded to 64 cm3 · g−1. The polymerization order of MPAEMA initiated with CCl3COOH is 0,93 with respect to monomer and 0,51 with respect to CCl3COOH. The overall activation energy of polymerization of MPAEMA calculated from the temperature dependence of Rp between 20 and 50°C is 43 ± 1,2 kJ · mol−1. In a benzene solution of 2 mol.dm−3 MPAEMA, 5 · 10−2 mol · dm−3CCl3COOH and 5 · 10−3 mol · dm−3 1,4‐benzoquinone at 50°C the polymerization does not proceed for 6 h. In a benzene solution of 2 mol · dm−3 4‐dimethylaminostyrene (4‐DMAS) and 2 mol · dm−3 CH3COOH (without AIBN), 40% of monomer polymerized within one hour. [η] DMF20 of the polymer was 4 cm3 · g−1. The overall activation energy of polymerization of 4‐DMAS in the presence of CH3COOH is ca · 54 kJ · mol−1. The addition of 5 · 10−3 1,4‐benzoquinone slows down the polymerization rate only slightly. The effect of acids on the elementary polymerization reactions is characterized.