MDI-페놀 부가물과 Diethylenetriamine으로 구성된 경화제 조성물에 의한 에폭시 수지의 경화 거동

김대중; 이대수; 이연식; Daejung Kim; Dai-Soo Lee; Youn-Sik Lee

Polymer(Korea), Vol.42, No.1, 1-7, January, 2018

DOI10.7317/pk.2018.42.1.1 Export Citation

MDI-페놀 부가물과 Diethylenetriamine으로 구성된 경화제 조성물에 의한 에폭시 수지의 경화 거동

Curing Behavior of an Epoxy Resin with Hardener Formulations Composed of MDI-phenol Adduct and Diethylenetriamine

김대중, 이대수 , 이연식 ^†

전북대학교 화학공학부

Daejung Kim, Dai-Soo Lee , and Youn-Sik Lee^†

Division of Chemical Engineering, Nanomaterials Processing Research Center, Chonbuk National University, 567 Baekje-Daero, Deokjin-gu, Jeonju, Jeonbuk 54898, Korea

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초록

에폭시 수지를 이용한 탄소섬유강화 플라스틱의 재활용을 위해 탄소섬유를 회수하기 위한 열분해에서 생성되는 유기물들 가운데 페놀류가 가장 큰 비중을 차지한다. 본 연구에서는, 이들을 재활용하는 방안에 대한 연구의 일환으로 페놀(P)과 4,4'-디페닐메탄디이소시아네이트(MDI)로부터 부가물 PMDI를 제조하고, 디에틸렌트리아민(DETA)과 PMDI로 구성된 경화제 조성물을 제조하여 비스페놀계 에폭시 수지의 경화거동을 연구하였다. PMDI의 함량이 0에서 20 wt%로 증가함에 따라, 경화 개시온도는 59 °C에서 72 °C로 증가하였고 경화반응 활성화에너지가 감소하였으며 경화속도는 증가하였다. 그러나 가교밀도의 감소로 인해 경화된 에폭시의 유리전이온도는 141 o°C에서 135 °C로 감소하였고, 고무상 탄성영역에서의 탄성률은 19.5 MPa에서 8.8 MPa로 감소하였다. 이러한 연구결과로부터 PMDI 부가물이 경화제 조성물 형태로서 에폭시 경화제로 사용될 수 있음을 알 수 있었다.

Phenols are one of major organic components generated on pyrolysis of carbon fiber reinforced plastics (CFRP) based on epoxy resins for recycling. In this study, phenol (P) was reacted with 4,4'-diphenylmethane diisocyanate (MDI) to give a PMDI adduct. Then curing behavior of a bisphenol A based epoxy resin with formulated hardeners composed of diethylenetriamine and PMDI was studied. As the PMDI content increased from 0 to 20 wt%, the curing onset temperature increased from 59 to 72 °C, and the curing rate also increased with decrease in the activation energy of the cure. However, the glass transition temperature of the resulting cured epoxy decreased from 141 to 135 °C, and the storage modulus in the rubbery plateau region decreased from 19.5 to 8.8 MPa, due to decrease in the crosslinking density. This study indicates that PMDI and possibly any other phenols-MDI adducts can be used as hardeners when formulated with other common hardeners.

Keywords:CFRP recycling;epoxy resin;phenol-MDI adduct;hardener;curing behavior

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[2] Oliveux G, Dandy LO, Leeke GA, Prog. Mater. Sci., 72, 61 (2015)

[3] Dauguet M, Procedia CIRP, 29, 734 (2015)

[4] Pickering SJ, Compos. Pt. A-Appl. Sci. Manuf., 37, 1206 (2006)

[5] Palmer J, Ghita OR, Savage L, Evans KE, Compos. Pt. A-Appl. Sci. Manuf., 40, 490 (2009)

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[9] Nahil MA, Williams PT, J. Anal. Appl. Pyrolysis, 91, 67 (2011)

[10] Lopez FA, Rodriguez O, Alguacil FJ, Garcia-Diaz I, Centeno TA, Garcia-Fierro J, J. Anal. Appl. Pyrolysis, 104, 675 (2013)

[11] Hua Y, Chun-xiang L, De-qi J, Xiang-Lin H, Chin. J. Polym. Sci., 32, 1550 (2014)

[12] Suyama K, Kubota M, Shirai M, Yoshida H, Polym. Degrad. Stabil., 92, 317 (2007)

[13] Yildirir E, Onwudili JA, Williams PT, J. Supercrit. Fluids, 92, 107 (2014)

[14] Pimenta S, Pinho ST, Waste Manage., 31, 378 (2011)

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[18] Ryan ME, Dutta A, Polymer, 20, 203 (1979)

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