Epichlorohydrin의 양이온 개환 중합반응 조건이 α, ω-hydroxyl telechelic polyepichlorohydrin의 특성에 미치는 영향 연구

Abstract

본 연구에서는 oxirane계 단량체인 epichlorohydrin (ECH)을 BF₃/1,4-BD active condensate촉매 및 methylene chlororide (MC) 용매 하에서 양이온 개환 중합하여 PECH를 합성하였으며, BF₃/1,4-BD 혼합비 및 단량체 공급속도등의 반응조건이 α, ω-hydroxyl telechelic polyepichlorohydrin (PECH)의 분자량 및 분자량 분포에 미치는 영향을 고찰하였다. 분자량 및 분자량 분포는 gel permeation chlomatography (GPC)로 분석하였으며, 화학구조는 IR 및¹ H-NMR 으로 확인하였다. 반응온도는 10℃ 간격으로 -10℃ ~ 40℃ 범위에서 변화시켰으며, PECH의 분자량은 -10℃일 때는 가장 작았고, 0℃일 때 가장 크게 나타났다. 반응온도가10℃이상 일 때는 생성된 PECH의 분자량은 감소하였다. -10℃와 20℃에서 제조된 PECH 의 ¹H-NMR spectra에서는 미반응 단량체의 특성 peak가 관찰되었다. BF₃/1,4-BD비를 0.1, 0.2, 0.5, 및 1로 변화시켜 합성된 PECH의 분자량은 BF₃/1,4-BD 비가 높을수록 커지고 분자량 분포는 작아졌다. ¹H-NMR 분석 결과 BF₃/1,4-BD 비가0.1과 0.2일 때 미반응 단량체 ECH의 peak가 나타났다. 20℃와 -10℃ 반응온도에서 단량체 공급속도를 4ml/min, 2ml/min, 1.4ml/min, 및, 1ml/min로 변화시켜, PECH를 중합했다. 반응온도 20℃에서 합성된 PECH의 분자량 및 분자량 분포는 단량체 공급속도에 따라 거의 차이가 없었다. 그리고, 반응온도 -10℃ 일 때는 단량체 속도가 2ml/min 보다 1ml/min일 때 분자량은 커지고, 분자량 분포는 넓어진다. ¹H-NMR spectra도 공급 속도에 따라 차이가 없었다. 반응온도 0℃, BF₃/1,4-BD비 1, 그리고, 단량체 공급 속도 1ml/min인 조건으로 ECH를 양이온 개환중합하여 얻어진 PECH의 분자량과 분자량 분포는 각각 M_(n) 2270, M_(w) 2880, 및 PDI 1.33로 나타났다.; Epichlorohydrin (ECH) sorts of Oxirane-based monomer was synthesized for use in cationic ring opening polymerization under methylene chloride (MC) with a computer control and IMA. The influence of reaction temperature, catalysts, ratio of initiator mixture and monomer feeding rate on the properties of Molecular weight (M.W) and polydispersity of PECH was investigated. The structure of the product was determined by 1H-NMR, and molecular weight and polydispersity was determined by Gel permeation chlomatography. First, to investigate on the influence of reaction temperature was synthesized on the variation of -10℃ interval between -10℃ and 40℃. The result showed that molecular weight of PECH is higher at 0℃ and lower at -10℃. Also, that of PECH is gradually lower over 10℃. But, The result of 1H-NMR showed that the structure was same as a reaction temperature. So, reaction temperatue had an influence on the molecular weight and polydispersity. Second, to investigate on the influence of catalysts and ratio of initiator mixture was synthesized on the variation which mixture of BF3/1-4 BD active condensate ratio is 0.1, 0.2, 0.5, and 1. Molecular weight of PECH identified that the more mixture ratio of BF3/1-4 BD active condensate is high, the more molecular weight is large and polydispersity is small. And 1H-NMR analysis showed that ECH confirmed at the mixture ratio of initiator is 0.1 and 0.2. So, the mixture ratio of BF3/1-4 BD active condensate had an affect on the initiator reation of ECH. As a result, molecular weight and polydispersity of PECH was influenced. Finally, to investigate on the influence of feeding rate of monomer was synthesized on the variation which feeding rate is 1ml/min, 1.4ml/min, 2ml/min, and 4ml/min at 20℃ The molecular weight of PECH no varied by feeding rate, but polydispersity affected by that. And, 1H-NMR result of PECH is same. So, PECH was synthesized again on the variation which feeding rate is 1ml/min and 2ml/min. When feeding rate is 1ml/min, molecular weight of PECH is high. The result showed that the feeding rate of monomer had an affect on the polydispersity. We synthesized PECH (Mn=2270, Mw=2880 and PDI=1.33) from control that reaction temperature is 0℃, BF3/1-4 BD active condensate ratio is 1, and feeding rate of monomer is 1ml/min.