Graft copolymers with polybutyramide (nylon-4) grafts onto a polyacrylonitrile backbone were prepared by reacting 2-pyrrolidone in the existence of potassium pyrrolidonate with a backbone chain fitted with randomly distributed acryllactam functions, which act as "promoters". To achieve this goal, N-(acryloyl)-2-pyrrolidone was chosen as comonomer of a backbone. The synthesis of N-(acryloyl)-2-pyrrolidone has been carried out by the reaction of pyrrolidone with acryloyl chloride and also new purification method for improving the yield was developed. The copolymerization of N-(acryloy 1)-2-pyrrolidone and acrylonitrile was performed in N, N-'dimethylformamide and the monomer reactivity ratio was obtained by using IR working curve and M. Fineman and S.D. Ross equation. It is found that copolymer of N-(acryloy 1)-2-pyrrolidone and acrylonitrile is good polymeric initiator for anionic polymerization of pyrrolidone with potassium hydroxide as a catalyst.
The effects of concentration of catalyst, polymeric initiator, temperature, and various additives on graft copolymerization were investigated. The highest equilibrium conversion and viscosity were obtained when the concentration of catalyst and initiator were 5.0 and 1.0 mole% at 50℃. The highest inherent viscosity of grafted nylon-4 was measured to be 2.1 dl/gr and the highest percent graft was 4985%. The rate constant ($k_p$) of graft anionic polymerization at 40 and 50℃ were determined by least square method.
새로운 acrylimide로서 N-(acryloyl)-2-pyrrolidone를 합성하여, NAP와 AN의 copolymer를 이용하여 graft nylon-4를 합성하였다.
NAP는 N-(methacryloyl)-2-pyrrolidone과 달리 매우 reactive했으며, 열적으로도 중합이 진행되었다. AN과 NAP의 공중합시에 각 monomer의 reactivity ratio를 구하였다. 그 결과 생성되는 copolymer는 pyrrolidone의 음이온 graft중합에 적절한 acryloyl lactam function을 가지고 있음을 알았다. 이 copolymer를 개시제로 하여, graft된 nylon-4를 합성하였으며, 이때 최고점도는 2.1이었고, 최고 percent graft는 4985 %였다.
그리고 additive salt와 temperature effect가 관찰되었고, $k_p$가 구해졌으며, 그 값은 40℃와 50℃에서 각기 2817과 2927 mole/lㆍmin이었다.
끝으로 이 실험에서의 몇가지 문제점 및 앞으로의 연구방향이 지적되었다.
