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1 2 1 MS 300 TRT MS JDI g MS Py MS GC Py-GC Py GC 50 Py MS MS Py GC PY-GC 2 JDI-800 MS JDI-800 QP 2000 QP 1000 QP 2000 Fig 1 QP 1000 CI PEG MS EI CI MS PEG 3 10 g Fig MS

2 3 JDI-800 JMS AX 505 MS JMS AX 505 AX 505WA AX 505HA JDI-800 EI CI 10KV Fig 2 AX 505 EI C60 C70 MS m z 720 z 840 C60 z 360 C60 2 z 697 z 673 z 649 Fig 3 -MMA MS MS 1ng Fig 3 Py GC

3 ORIGINAL RESEACH REPORT Development of a Curie-Point pyrolyzer for mass spectrometry and application to Synthetic polymer analysis Naoki Oguri Akira Onishi and Sigeki Uchino Japan Analytical Industry Co., Ltd. 208 Musashi, Mizuho, Nishitama, Tokyo , Japan ABSTRACT A Curie-Point direct injection probe that can be used as an injector for mass Spectrometry is described The probe consists of an injection probe and a radio frequency power supply 48 W 10 MHz. The pyrolysis part of the injection Probe is made from ceramic and metals without using organic material around The Curie-Point heating area for decreasing a signal noise. The induction period for reaching constant temperature and the heating period of the probe are 0.2 sec and sec respectively The detail of the construction and its evaluation of the proposed injection probe are described Pyrolysis mass Spectrometry by using this device is applied for the discrimination between a blended polymer the corresponding a grafted polymer of polypropylene Polystyrene and polypropylene Styrene grafted polymer Keywords Curie Point direct injection probe mass spectrometry Pyrolysis Copolymer blend polymer graft polymer MS 10 MHz 48 W MS Py MS Py-MS Chromatography R 10R ISSN

4 GC Py GC Py-GC 50 Py-MS MS Py-GC Py-GC 5 MS 300 TRT Py MS 6 10 m z 200 m z 200 JDI JDI-800 Fig.1 JDI mm 280mm MS Fig.1 Schematic view of the Curie-point direct injection probe.

5 0.3mm 15 2mm 9mm 2 g 0.1 vol wt 1 l MHz 48W mm JDI-800 TRT , JDI-800 QP 2000A MS EI 70 ev St MMA PSMMA St 70 MMA 30 ABS Py GC St 60 PP PP PS Pressure Chemical Mn 110,000 BR cis 1,4 BR ER0l SBR Py GC St 43 % w w PS BR B PSBR St 43 % BR 57 % PP PS B PPPS G PPS 9 St 1 1 Fig Py MS 0 MS 1.15 TIC Curve 1 m z 44(CO2 Curve 4 m z 32 O2 Curve3 m z 28 N2 Curve 2 SIM Selected Ion Monitering

6 TIC % Py MS 10 2 Py MS EI 70eV 16 70eV

7 Fig g PSMMA Py MS MMA m z 69{CH2=C(CH3) -C + O} MMA { M } + m z 100 m z 78{ [M] + } m z 91 [M] + m z 104 PSMMA 2 z g PSMMA m z Py GC Fig.4. St MMA n % Py MS Py GC 4.3 Py MS 12 Fig 3 3 Fig 4 30 Py GC 99 Py MS MS Py GC 100 Fig 4 SM SS SSS Fig 3 EI

8 3 Py MS Py GC Py MS MS 7 Fig.5 JDI 800 ABS Py MS ABS AN Bu St Py MS m/z 53, m/z = 54, m/z = 104. St Bu Fig 7 SBR m z 129{ [ CH2=C(Ph)-CH=CH2-1] + AN St m z 156 [C=C CN -C-CPh 1] + } St l AN 2 m z 210 [C=C(CN)-C-C(CN)-C-C-Ph] + 3 AN Bu St AN Bu EI m/z tert 4 BHT BHT ABS 315 lmg ABS MS 10 ABS MS Fig.6 Fig 6 MS BHT [M] + (m/z 220) [M-CH3] + (m/z=205) [M 75] + m/z 145 BHT St m z Py MS

9 BHT d i Oguri 7 Py GC Py MS 13 Py MS MS Fig 7 B SBR Py MS PS BR B PSBR Py MS A A St m z 104 m z 77 m z 91 m z 207 m z 312 Py GC EI B A St m z 104 m z 77 m z 321 m z 207 m z 312 SBR B z 129 z z 262 A 4 5 A BR

10 5 PP PS B PPPS Py MS Fig 8A 4 PS St m z 104 m z 77 m z 91 m z 207 m z 312 PP 2 1 M 1 + m z M 1 + m z 12S M CH3 1 m z 153

11 Fig 8B G PPS A B 4 A m z 312 B St B PPPS PP Py GC PP PP PP m z 125 I125

12 St ISt Ist/I125 Ist/I PP m z 125 St

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