[논문]Effect of Interface on the Properties of Polyamide 6/Carbon Nanotube Nanocomposites Prepared by In-situ Anionic Ring-opening Polymerization

Min, Jin Hong; Huh, Mongyoung; Yun, Seok Il

doi:10.7234/composres.2019.32.6.375

Effect of Interface on the Properties of Polyamide 6/Carbon Nanotube Nanocomposites Prepared by In-situ Anionic Ring-opening Polymerization 원문보기

Composites research = 복합재료, v.32 no.6, 2019년, pp.375 - 381

Min, Jin Hong (Department of Chemical Engineering and Materials Science, Sangmyung University) , Huh, Mongyoung (Affiliation Korea Institute of Carbon Convergence Technology) , Yun, Seok Il (Department of Chemical Engineering and Materials Science, Sangmyung University)

Abstract ▼ AI-Helper

Multiwalled carbon nanotubes (MWCNTs) are covalently functionalized with isocyanates by directly reacting commercial hydroxyl functionalized MWCNTs with excess 4,4'-methylenebis (phenyl isocyanate) (MDI) and hexamethylene diiosocyanate (HDI). HDI-modified MWCNTs results in a higher surface isocyanate density than MDI-modified MWCNTs. Anionic ring-opening polymerization of ε-caprolactam is conducted using a sodium caprolactam initiator in combination with a di-functional hexamethylene-1,6-dicarbamoylcaprolactam activator in the presence of isocyanate functionalized MWCNTs. This polymerization proceeds in a highly efficient manner at relatively low reaction temperature (150℃) and short reaction times (10 min). During the polymerization, the isocyanate functionalized MWCNTs act not only as reinforcing fillers but also as second activators. Nanocomposites with HDI modified MWCNTs exhibit higher reinforcement and faster isothermal crystallization than MDI modified MWCNTs. The results show that PA6 chains grow more effectively from HDI modified MWCNT surface than from MDI modified MWCNT surface, resulting in stronger interaction between PA6 and MWCNTs.

주제어

표/그림 (10)

그림 Fig. 1. Synthesis of isocyanate functionalized MWCNTs and sub-sequent PA6 chain growth from functionalized MWCNTs
그림 Fig. 2. FTIR spectra of the MWCNT-OH, MDI and HDI-modified MWCNT
그림 Fig. 3. TGA data for the MWCNT-OH, MDI and HDI-modified MWCNT
그림 Fig. 4. The effect of MWCNTs on the degree of conversion
그림 Fig. 5. Effect of MWCNT loading on the mechanical properties of PA6/MWCNT nanocomposites, (a) the tensile strength and (b) Young's modulus
그림 Fig. 6. DSC thermograms (cooling scan) of PA6 and PA6/MWCNT nanocomposites at various T_c at (a) 188 (b) 190 and (c) 192°C
그림 Fig. 7. Effect of surface modification on the relative degree of crystallinity, X(t) at different T_c
그림 Fig. 8. The variation of G value (=1/t_0.5) as a function of T_c for PA6 and PA6/MWCNT nanocomposites
그림 Fig. 9. The linear relation of ln[-ln(1 - X(t)] and ln t for PA6 and PA6/MWCNT nanocomposites at various T_c at (a) 188 (b) 190 and (c) 192°C
표 Table 1. Isothermal melt crystallization kinetic parameters for PA6 and MWCNT nanocomposites

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제안 방법

To date, no direct comparison between MDI and HDI for preparing isocyanate functionalized CNTs has been reported in the literature. In this study, compared to unmodified CNTs, the isocyanate functionalized CNTs, especially HDI modified CNTS, more effectively reinforced the nanocomposites and accelerate PA6 isothermal crystallization.

대상 데이터

MWNTs-OH (3.06 wt% OH) was purchased from US Research Nanomaterials, Inc (purity > 95%, diameter 10-20 nm, length 10-30 μm).
The ECL used was an anionic polymerization grade (APNylon® grade) supplied by Bruggemann Chemical (Heilbronn, Germany) as it has a low moisture content (<100 ppm). The MDI, HDI, dibutyltin dilaurate (DBDL) and anhydrous tetrahydrofuran (THF) were purchased from Sigma-Aldrich (US). A C20 as an activator and a C10 initiator were purchased from Brueggemann Chemical.

성능/효과

11 wt%, for the MDI and HDI modified MWCNT, respectively. Considering that the starting nanotubes have a hydroxyl group concentration of 3.06 wt%, the TGA results indicate that about 55.4% of the available hydroxyl groups reacted with HDI despite the poor solubility of MWCNTs in THF. However, for MDI modified MWNTs, only a 12.
The typical band at 2265 for isocyanate group was also observed [14,15]. The results indicate that the isocyanates were successfully incorporated into the surface of MWCNT-OH using the coupling agents, HDI and MDI. To gain a more quantitative picture of the extent of nanotube functionalization, TGA analysis was performed on the surface functionalized MWCNTs as depicted in Fig.
Nanocomposites with HDI modified MWCNTs showed higher reinforcement and faster isothermal crystallization than MDI modified MWCNTs. The results showed that PA6 chains grew more effectively from HDI modified MWCNTs than from MDI modified MWCNTs, resulting in stronger interaction between PA6 and MWCNT surface.

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