N-acryloyl pyrrolidone was synthesized by the reaction of pyrrolidone with acryloyl chloride. First, the polymerization of N-acryloyl pyrrolidone and copolymerization of N-acryloyl pyrrolidone with styrene were carried out at 60℃, using 2.2'-azobisisobutyronitrile as an initiator. Kinetic studies showed that the rate of polymerization could be expressed by :
$$R_p=\mbox{K(AIBN)}^{\frac{1}{2}}\mbox{(NAP)}$$
The reactivity of N-acryloyl pyrrolidone was found to be larger than that of N-methacryloyl pyrrolidone. The overall activation energy was calculated to be 24.3 kcal $mol^{-1}$.
The following monomer reactivity ratio and Q,e value were obtained : NAP(Ml)-St(M2) ; r1=1.5, r2=0.35, Q1=0.42, and el=1.6. Second, ring-opening polymerization of pyrrolidone using N-acryloyl pyrrolidone as an activator was carried out. Third, graft copolymers were synthesized by reacting pyrrolidone, in the presence of catalytic amount of its potassium salt, with poly(acryloyl pyrrolidone-styrene).
The pair of cobaltous chloride with N,N-dimethylaniline(DMA) has been investigated as an initiator for the polymerization of acrylamide in aqueous media 30, 40, and 50℃ in a nitrogen atmosphere. The rate of polymerization was found to be proportional to the $\mbox{(monomer)}^{1.0}$ over the range of $0.5-2.0\times10^{-2}M$. The reaction order related to the cobaltous chloride concentration was 0.53, which indicated a bimolecular mechanism for the termination reaction in the range of $0.2-2.0\times10^{-4}M$. The rate of polymerization and the maximum conversion falled as the temperature rised above 40℃. The apparent activation energy was 9.38 kcal/mol in the temperature range of 30-50℃. Methanol decreased the rate of polymerization and polymerization was completely stopped when benzoquinone was added during an induction period. The reaction mechanism was proposed on the basis of the experimental data.
두 가지의 관능기를 가지고 있는 기능성 단량체인 N-Acryloyl Pyrrolidone(NAP)는 pyrrolidone과 acryloyl chloride의 반응으로 합성하여 이 단량체의 중합에 관한 연구를 진행하였다.
첫째, 개시제인 AIBN 을 사용하여 NAP 를 종합시켜 높은 분자량의 고분자를 얻었다.
둘째, 스티렌과 공중합을 시도한 후 고분자의 조성비로 부터 반응성비를 구한 결과 NAP 는 1.5, 스티렌은 0.35의 값을 얻었다.
세째, NAP 를 pyrrolidone의 개시제로 사용한 결과 pyrrolidone중합의 좋은 개시제의 작용을 한다는 사실을 밝혔다.
네째, 스티렌과 NAP 의 공중합체를 pyrrolidone 중합의 개시 제로 사용한 결과 좋은 개시제의 작용을 한다는 사실을 밝혔고 이것은 곧 새로운 Graft 중합체를 얻을 수 있는 방법임을 알았다.
