加硫したゴムの分析 - customs.go.jp

1 46 69 * * * Analysis of Vulcanised Rubbers Kenji TAKEMOTO*, Hiroyuki WATANABE* and Fumio NAKAMURA* *Central Customs Laboratory, Ministry of Finance 6-3-5, Kashiwanoha, Kashiwa, Chiba 277-0882 Japan We made various vulcanised rubbers and examined the method to detect the structure of vulcanisation with sulphur. By using solid state 13C nuclear magnetic resonance spectrometry (13C-NMR) and pyrolysis gas chromatography (Py-GC), we detected the structure of vulcanisation with sulphur in natural rubber (NR). And by using raman spectrometry and Py-GC, we detected the structure of vulcanisation with sulphur in styrene-butadiene rubber (SBR). And by using Py-GC, we detected the structure of vulcanisation with sulphur in acrylonitrile butadiene rubber (NBR), ethylene-propylene-diene rubber (EPDM) and polybutadiene rubber (BR).

2 Especially, by using atomic emission detector (AED) as the detector of Py-GC, we detected the structure of vulcanisation with sulphur high sensitivity. NR 13C- 13C-NMR Py-GC SBR Py-GC NBR EPDM BR Py-GC Py-GC AED 40 ( ) 39 13C- 13C-NMR Py-GC ( ) (NR) (SBR (NBR) (IIR (EPDM) (BR (SEBS) * 277-0882 6-3-5 70 NMR CMX-300( ( )))))

3 13C 5 PST pulse saturation /MAS magic angle spinning IR spectrometer Magna760/FT-Raman Module 1200 cm-1 Py-GC 6890A Agilent PY-2020 FRONTIER LAB JAPAN 550 C HP-5 30m m 300 C 320 C He 50:1 GC 50 C 2 10 C/ 320 C 10 FID AED EI NMR NMR 13C-NMR - 300 g 550 C FID AED 13 - NR 13C-NMR 45 60ppm 1) 2) NR BR 13C-NMR NR 45 52ppm 3)

4 BR SBR NBR IIR EPDM SEBS 13C-NMR NR BR 13C-NMR Fig. 1 The 13C PST/MAS NMR spectra of (A) NR and (B) vulcanized NR. Fig. 2 The 13C PST/MAS NMR spectra of (A) BR and (B) vulcanized BR. Fig. 3 The 13C PST/MAS NMR spectra of various vulcanized rubbers, (A) SBR, (B) NBR, (C) IIR, (D) EPDM and (E) SEBS. Sx CH2 CH Sx HCSx 46 71 SBR 438 cm-1 475 cm-1 509cm-1 438 cm-1 475 cm-1 509cm-1 4) SBR NR NBR IIR EPDM Fig.

5 4 Raman spectra of (A) SBR and (B) vulcanized SBR. Fig. 5 Raman spectra of various vulcanized rubbers, (A) NR, (B) NBR, (C) IIR and (D) EPDM. - NR SBR NBR EPDM IIR SEBS AED NR 3 4 5) SBR NBR EPDM NR 11 NR SBR NBR EPDM AED IIR SEBS IIR SEBS SEBS IIR Fig. 6 Comparison of pyrograms of various vulcanized rubbers, (A) NR, (B) SBR, (C) NBR, (D) EPDM, (E) IIR and (F) SEBS. 13C-NMR Py-GC SBR Py-GC NBR EPDM BR Py-GC Py-GC AED IIR SEBS 72 1 , :Rubber Chemistry and Technology, 60, 252 (1987).

6 2 , :Rubber Chemistry and Technology, 60, 278 (1987). 3 , :Die Makromolekulare Chemie, 189, 1239 (1988). 4 , , :Rubber Chemistry and Technology, 45, 173 (1971). 5 , , :Journal of analytical and applied pyrolysis, 10, 31 (1986).