（4）複合分析法による最新の高分子化合物の分析（A）キューリーポイント Py−GC 法による PET フィルム上の超薄膜の定量分析要旨PET 上に塗布された起薄膜の PMMA フィルムの膜厚を Py-GC 法によって再現性良く測定することができた．1.350μの膜厚を測定することができる検量線が得られた．
Quantitative Analysis of the Ultra-thin Layer- ofPMMA on PET Film Surface by Curie-PointPyrolysis - Gas ChromatographySampleStandard samples: Ultra-thin layers with the thickness of 0, 100,240 and 360Å on PET films(thickness of 0.12 mm), respectively.
Unknown sample: Coded "a'' and "b".
ExperimentalSample size: 0.4 - 0.5 mg without pretreatment.
Pyrolysis: JAI JHP-3 Curie-point pyrolyzer with Pyrofoils of 315,423, 500 and 590.C for 5 see. Oven and transfer pipe temperature:210 and 200℃, respectively.
GC: HP 5890A GC system with Hitachi D-2520 Integrator. DB1701 fused silica capillary column(J & W Sci.). 30 m x 0.25 mm i. d.,30℃(10 min) to 300℃, lO℃/min, He 50 m1/min. split 50:1.
Results and Discussion1. As well known. the typical characteristic pyrolysate ofpolymethyl methacrylate(PMMA) on the pyrogram is methylmethacrylate(MMA. monomer), and pyrolysates of benzene(B),divinyl terephtalate(DET, monomer), etc. could represent thepresence of polyethylene tcrephtalate(PET) in sample [l].
Considering the relative Weights of PMMA in the samples areextremely small(1/10.000 to I/3,000 on thickness for standardsamples), all of the experimental.parameters, such as pyrolysistemperature, Sample size and GC separation conditions, have greatinfluence on the quantitative identification of PMMA fraction fromPET background. Therefore, it is necessary to vary and estimatethe experimental parameters carefully. When, the samples arepyrolyzed at lower temperatures(315 and 423oC). much of thepolymers are not pyrolyzed even if the time is increased [2,3].
Contrariwise, pyrolysis at higher temperatures(590℃, for example)formed much of the lower boiling point pyrolysates which couldoverlap the weak peak of PMMA.

Therefore, pyrolysistemperature of 500℃ is recommended in this work. Rather largesample size is necessary to identify small amount of PMMAfraction. But, the large amount of sample will influence thereproducibility, because the heat is transferred more slowly in alarge sample [4]. The smaller the sample size, the morehomogeneous is the temperature in the sample and the straighter isthe calibration graph. However, there is a reasonable sample sizerange in 0.4 - 0.5 mg that can be used for this study. Finally, theGC condition should be available for separation of MMA peak fromother peaks especially in relative small retention time range, sothat the minimum column temperature have to be set at a lowertemperature. The illustration pyrogram of a standard samplepyrolyzed at 500℃ is shown in Fig.1, in which a small andsignificant MMA peak could be found clearly.
2. As mentioned before, PET weight fractions are incomparablylarger than PMMA in the films, i.e. the relative contents of PET inthe samples can look upon as a constant. Therefore, the completeseparated chromatographic peaks and structural characteristicpyrolysates of PET, such as benzene(a), Styrene(S), DET etc. can bedefined as the internal standards for quantitative analysis. Theplots of peak area ratios of MMAIB, MMA/S and MMA/DET vs.
thickness of PMMA on PET films are shown in Fig.2. Excellent linerrelationships could be found in the ,.calibration curves, even for thetrace of PMMA. The data also reflected that the 'selection ofinternal standards, especially the intensity comparable peaks, isreasonable. Therefore, the calibration data can be used forquantitative analysis of the ultra-thin layer of PMMA on PET filmsurface on the level of 10-4 graduate.
3. The data for unknown samples of "a'' and ''b'' listed in Table 2.
That results showed that all of the calibration curves, i.e. theinternal standards, are available for quantitative microanalysis ofultra-thin layers of PMMA on PET films and giving correlativedata. The measured thickness of sample ''b'' also indicated thesensitivity limitation of this method may be extended to 1/20,000for PMMA-PET system.ConclusionMicroanalysis of polymer materials is getting interestedespecially in high technique field recently. Lack of the informationin this area made us to find new measurement for that purpose.
This work implied that Curie-point pyrolysis - gas chromatographyis perhaps a potential method for simple and rapid microanalysis ofpolymer materials without pretreatment.
ReferenceI[1] S.Tsuge, H.Ohtani, Pyrolysis Gas Chromalography - Fundamentaland Pyrogram Alias, Tech.Syst.. Tokyo, 1989, p.142. 310.
[2] I.Ericsson, I.Chromalog.Scl'., 16. l978, 340.
[3] I.Q.Walker. I.Chromalog.ScI'.. 15, l977. 267.
[4] I.Ericsson, J.Anal.Appl.PyroI., S. 1985, 73.（B）キューリーポイントヘッドスペース サンプラによるフロッピイディスクより発生する揮発性成分の分析フロツピイディスクを 7℃以下の低温下で使用するとフロッピイディスクが破損したり、磁気ヘッドを傷める事故が多くなる．それらの事故原因は、フロッピイディスクの表面上に浸析してくるオイル状物質の種頻とその量と言われている．最初のデータは、事故の最も少ないフロッピイディスクの分析例で、後のデータは事故の多いフロツビイディスクの分析例である．

APPLICATION OF CURIE POINT PYROLYSIS ANDHEADSPACE GC-MS IN FLOPPY DISK ANALYSISFloppy disk consists of PET film and double side magnetic coatinglayers, which are complex formulation of ferromagnetic powder(Fe304),polymeric adhesive and some kinds of small molecular additives. Onceproduced, it may be difficult to analyze since it usually is a multicomponent and insoluble polymer system. However, PyGC-MS shouldbe useful in the analysis of the insoluble polymer adhesive withoutseparation from ferromagnetic material, but the presence of semivolatile additives may interfere that process. In case such as this,combination' with headspace GC-MS could be available for floppy diskanalysis.
Sample and PretreatmentSample: Commercial 5 1/2 floppy disk.
Pretreatment: For PyGC-MS analysis, a small piece of disk is soaked inchloroform for a few min, then scrape off the magnetic coating materialfrom PET film in CHCl3 Carefully, remove CHCl3 by heating at 50℃.
Non-pretreatment for headspacc analysis.
Analysis ConditionsPyrolysis:JHP-3 Curie Point Pyrolyzer with a Pyrofoil of 590℃,pyrolysis time: 5 see, oven temp.: 200℃, interface temp.:200℃, sample weight: 1 mg including Fe304.

Headspace: JHS-100 Headspace Sampler, purging temp.: l50℃. time..
10 min, adsorption on Tenax, temp : -40℃, time: 10 min,desorpting temp.: 358℃ by a Pyrofoil, time:.10 see, :sample weight: 150 mg including PET and Fe304.
GC –MS:.

Shimadzu GCMS-QP 2000A, column: J & W Sci. DB-1fused silica capillary column (30 m × 0.25 mm i.d.)coated with bonded methyl silicone polymer, columntemp.: 40℃ to 250℃, l0℃/min, carrier gas: He, 50 mｌ/minsplit: 50:1, quadrupole MS, EI, 70 ev.ResultsFig.1-A illustrated the total ion current(TIC) pyrogram of the coatinglayer materials with the peak assignments.. The most characteristicdegradation products, tolylene diisocyanate(TDI) and benzene monocyanate(BMI), exclusively corresponded to TDI-polyurethane componentin the polymer materia1[1,2]. A cylic urethane(CU) peak yielded by thedecomposition through an ester exchange process of polyurethane alsoreflected that conclusion[3].

Some alicyclic pyrolyzates,cyclopentanone(CP) and tetrahydrofuran(THF), are formed from adipicacid and butanediol portions of the polyester segments,respectively[1,2].

Summarizing all of the pyrogram characters, thecoating polymeric material of the floppy disk is identified as TDIpolyester-polyurethane. Otherwise, a small and wide peak of benzonicacid(BA) is implied by the degradation of residual PET film. Somehigher aliphatic alcohols and acid peaks in Fig.1-A are though to arisefrom the additives of the material or/and that with partial degradation,which would be confirmed by using headspace GC-MS analysis.
The TIC chromatogram from headspase GC-MS of the floppy disk isshown in Fig.1-a with the peak assignments. The main peaks ofcyclohexanone(CH) and toluene(T) indicated the presence of the residualsolvents. There also are some higher aliphatic alcohols peaks in Fig.1-B,as the pyrogram. Therefore, they may be assumed as additive(s), forexample lubricant or antistatic agent in the material. But we prefer tosuggest that the original carbon numbers of the aliphatic chains areperhaps not definite, like the MS spectra showed. The reason could beattributed to the thermal cleaveges of the longer aliphatic chains,especially that with branching and unsaturated bond structures.
ConclusionThe combination of Cuire point pyrolysis and headspace GC-MSmeasurements is not only for the identification of the materialcomposition of the floppy disk in this work. but also shown it would be apowerful technique for the analysis of multi-component polymermaterials, especially of that including non-volatile, semi-volatile andvolatile component samples.References[1]S.Tsuge. H.Ohtani. Pyrolysis Gas Chromatography of Polymers - Fundamental andPyrogramAtlas, Tech.Syst., Tokyo, 1989, p358.

[2]H.Ohtani. T.Kimura. K.Okamoto. S.Tsugc. Y.Nagatani. K.Miyata, J.Anal.Appl.Pyrpl., 12. 115 (1987).
[3]G.Montaudo. C.Puglisi. in N.Grassie ed. Development in Polymer Degradation vol.7.
Eisevier AppI.Sci.. London, I987. p.35.
[4]N.Oguri, A.Onishi, T.Hanai, J.High Resolullon Chromatog., 14', 79 (1991).（C）複合分析法による熱硬化性不飽和ポリエステルの分析試料 A（硬化剤）と試料 B（ポリマ）を分取 HPLC．Py−GC／MS．ヘッドスペースーGC／MS 及び DI Probe-MSを使って完全分析を行なった．

POLYMER ANALYSIS BY COMBINATION OF CURIEPOINT HEATING TECHHIQUES AND PRRPARATIVEHPLCEXPERIMENTA LSample;A set of uncured unsaturated -polyester resin separated to two parts(coded sample A and B) consists of prepolymer, reactive monomer,curing accelerator and additives.
Instruments and Expermental ConditionsPyrolysis:JHP-3 Curie-point Pyrolyzer with a Pyrofoil of 500 or 220℃for 5 sec. Oven and interface temperature: 200℃ and 250℃respectively. Sample size: 0.1 mg.

Headspace:JHS-100 Curie-Point Headspace Sampler, purging at 220℃for 1 min, adsorption on Tenax at –40℃, desorpting at 255℃by a foil for 10 sec, sample size: 0.3 mg.
DI Probe: JDl-800 Curie-point DI Probe is inserted in a mass systemup to the position where the sample cell (9 mm × 2 mm i.d.,quartz) at the tip of the probe can be connected to the ionsource.
GC-MS: Shimadzu GCMS QP 2000A with a J & W Sci. DB-1 fusedsilica capillary column, 35℃(5 min) to 300℃, 8℃/min,He: 50 m1/min, split of 50:1. Mass: El 70 ev, 250℃ HPLC:LC-908 Recycle Preparative HPLC with columns of Jaige1-lHand JaigeI-2H, CHCI3 3.8 ml/min. 40 Kg/cm2 , uv-254Hand RI detectors, injection: 3 ml, 50 mgRESULTS AND DISCUSSIONCurie-pint PyGC-MS, Py DI-MS, headspace GC-MS and preparativeHPLC were Combined for the compositional analysis of the polymer Theflowchart diagram of the analysis process is illustrated in Fig.1.The TIC pyrogram of sample A at 500℃ is showed in Fig.2, in whichsome pyrolysates, such as hexladiene(peak 2), hexeno1(peak 3) phthalicanhydride(peak 5), mono-cyclohexenyl phthalate(peak 7) and dihexenylphthalate(peak 11. monomer) reflected on the segments of aunsaturated polyester derived from phthalic acid and hexendio1 [1,2].
Other Pyrolysate peaks in Fig.2 may be caused by the presence of somearomatic compound(s) mixed with polyester. To confirm that. sample Awas separated and collected to two fractions, F-I and F-2 as shown inFig. 3, by recycle preparative HPLC [3], and then F-I and F-2 wereidentified by PyGC-MS again, respectively. The pyrogram F-1 showedall of the characters of poly(dihexenyl phthalate) giving the sameconclusion as before. The sufficient decomposition of F-2 at 220℃indicated it would be a thermally labile compound. Summarizing all ofthe pyrolysis features, F-2 could be assigned to benzoyl peroxide as acuring accelerator for the unsaturated polyester. as shown in Fig.4.
Finally a peak 12 in Fig.2 indicated a high aliphatic alcohol presented inthe material, implying that as a kind of surfactant.
Some acrylate monomer peaks, methyl acrylate(MA), methylmethacrylate(MMA) and iso-hexyl methacrylate(HMA) were identifiedon the pyrogram of sample B (Fig.5-a)[4]. Therefore sample a could bereasonably deduced as a copolymer of MA, MMA and HMA. Otherwise,a high aliphatic alcohol peak and a dioctyl phthalate (DOP) peak in Fig.4a regarded as some additives, perhaps as surfactant and plasticizer inthe material. respectively.
Fig.6 is the TIC pyrogram and corresponding mass spectrum of sampleB pyrolyzed at 500℃, which indicated the species observed is co(MAMMA-HMA)polymer from the monomer fragments with m/e values of86(MA), 100(MMA) and l70(HMA). Though the conclusion is the sameas that by PyGC, but it is suitable for fingerprint identification purpose.
In addition, a through-put of up to one sample was within few minutes,and then rapid analysis is getting possible [5,6]Headspace GC-MS was carried out at a purging temperature of 225℃,in which a monomer-free co(MA-HMA)polymer was analyzed first. Nosignificant pyrolysate formed at that temperature for the purifiedcopolymer. A headspace TIC chromatogram of sample B is shown inFig.4-b, in which. the monomer peaks of MMA and HMA presented withobverse intensities compared to sample size. The results pointed outthere are some reactive monomers dissolved in the copolymer as thecrosslinking agents of the unsaturated polyester [7].