화학공학소재연구정보센터
홈 로그인 로그아웃 연락처 사이트맵
Polymer(Korea), Vol.41, No.4, 648-655, July, 2017
DOI10.7317/pk.2017.41.4.648  Export Citation
아민 리간드의 화학구조가 2,6-디메틸페놀의 산화중합에 미치는 영향
Effects of Chemical Structure of Amine Ligands on the Copper-catalyzed Oxidative Polymerization of 2,6-dimethylphenol
신민제, 김용태1, 김중인1, 김지흥, 남성우, 김영준†
  • 성균관대학교 화학공학과
  • 1제일모직 연구소
Min Jae Shin, Yong Tae Kim1, Joong-In Kim1, Ji Heung Kim, Sung Woo Nam, and Young Jun Kim†
  • School of Chemical Engineering, Sungkyunkwan University, Suwon 16419, Korea
  • 1Chemical R&D Center, Samsung Cheil Industries Inc, Uiwang 437-711, Korea
E-mail:
초록
리간드의 화학구조가 poly(1,4-phenylene ether)(PPE) 중합반응에 미치는 영향을 알아보기 위해서 copper(II)chloride와 copper(I) chloride를 중합촉매로 사용하고 여러 종류의 용매 및 리간드를 사용하여 중합반응을 수행하였다. 이 때 사용된 중합용매는 anisole 또는 toluene 단독 용매 혹은 anisole/methanol 또는 toluene/methanol 혼합 용매였고 리간드로는 지방족 아민 화합물, pyridine 류, pyrimidine 류, pyrazine 류, pyridazine aniline 등의 방향족 아민 화합물을 사용하였으며 이들 용매 및 리간드가 중합반응에 미치는 영향을 조사하였다. 중합 후 얻어진 고분자시료의 수율을 구했고 UV spectroscopy를 이용하여 중합반응 부산물인 5,5'-tetramethyl-4,4'-diphenoquinone(DPQ)의 생성량을 측정하였으며 gel permeation chromatography(GPC)를 이용하여 PPE의 분자량을 측정하였다. 실험결과 리간드의 화학구조에 의한 입체적 장애가 있을 경우 PPE 중합체의 분자량의 저하 및 낮은 중합수율이 관측되었고 사용된 리간드의 염기성 범위에서는 염기도가 증가할수록 중합체의 수율은 높아졌다.
To investigate the effect of chemical structure of amine ligands on poly(1,4-phenylene ether) (PPE) polymerization, it was performed with copper (I) chloride and copper (II) chloride as catalysts. The polymerization solvents were anisole or toluene alone or mixed solvents of anisole/methanol or toluene/ethanol. Various aliphatic amine compounds and aromatic amine compounds such as pyridine, pyrimidine, pyrazine, pyridazine or aniline were used. The yield of polymer samples obtained after polymerization was determined. The amount of 5,5'-tetramethyl-4,4'-diphenoquinone (DPQ) produced as by-product was measured using UV spectroscopy. The molecular weight of PPE was measured using gel permeation chromatography (GPC). Experimental results showed that the increase in steric hindrance of the ligand decreased the molecular weight of the PPE polymer and lowered the polymer yield. Also, as the basicity of the ligands increased, higher polymer yield was obtained.
Keywords:poly(1,4-phenylene ether);oxidative coupling;ligand;copper catalyst
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