serial chromatopyrography- mass spectrometry of … · applications of serial pyrolysis-gas...

MLM TR 86-4 FAD 4-0

' SERIAL CHROMATOPYROGRAPHY-

- MASS SPECTROMETRY OF NATURAL

RUBBER VULCANIZATES

ALFRED J. DEOME and CHRISTOPHER J. KULIGPOLYMER RESEARCH DIVISION

JACOB PATIU.S. ARMY TANK-AUTOMOTIVE COMMAND

March 1986

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US ARMYLABORATORY COMMANDMATERIALS TECHNOLOGY U.S. ARMY MATERIALS TECHNOLOGY LABORATORY--LABORATORY Watertown, Massachusetts 02172-0001

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4. TITLE (and Subtitle) 5 TYPE OF REPORT & PERIOD COVERED

SERIAL CHROMA.TOPYROGRAPHY-MASS SPECTROMETRYOF NATURAL RUBBER VULCANIZATES Final Report

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Alfred J. Deome, Christopher J. Kulig, andJacob Patt*

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U.S. Army Materials Technology Laboratory D/A Project: IL162601AH91Watertown, Massachusetts 02172-0001ATTN: SLCMT-OP

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U.S. Army Tank-Automotive Command March 1986

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Gas chromatography PyrolysisMass spectrometry Natural rubber

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ABSTRACT

Applications of serial pyrolysis-gas chromatography-mass spectrometry,developed at the U.S. Army Materials Technology Laboratory, are used todetermine the qualitative organic formulation and polymer composition of twoproprietary experimental natural rubber formulations.

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INTRODUCTION

Previous work in the area of pyrolysis-gas chromatography-mass spectrometryI-5

has shown that this technique is a powerful analytical tool well suited forstudying the complex composition of intractable materials, such as vulcanized elas-tomers. An interesting and particularly valuable application of the many pyrolysistechniques available is serial chromatopyrography-mass spectrometry (Ser-Py-GC-MS).This technique appears to be very applicable to separating residual vulcanizateformulation components from polymer composition without the need for complicatedsample manipulation procedures. Instrumental techniques employing a combination ofserial pyrolysis techniques, high resolution capillary gas chromatography, and massspectrometry have been developed at the U.S. Army Materials Technology Laboratory,Watertown, MA, in collaboration with the U.S. Tank-Automotive Command (TACOM),Warren, MI, during the last several years. The technique is used as a means ofaccurately accessing and reconstructing formulations of vulcanized elastomers wherefew, if any, straightforward analytical procedures are available for this type ofwork.

This report documents the application of Ser-Py-GC-MS in determining thecomposition of two experimental natural rubber formulations. The vulcanized ten-sile sheets, both of proprietary composition, are referenced in this report asSample LG-1 (465 VI and II) and Sample LG-2 (465 X-5).

EXPERIMENTAL

Thermal gravimetric analysis (TGA) was performed on each sample using a DuPont1090 thermal analyzer to determine temperature profiles at which the organic formu-lation is thermally desorbed from the polymer and inorganic component matrix of thevulcanizates. Pyrolysis experiments were performed on each sample using a ChemicalData Systems, Inc., Model 122 pyrolysis unit interfaced to a Hewlett-Packard Model5996 gas chromatograph-mass spectrometer system under computer control (Hewlett-Packard 1000 Data System). The samples were each subjected to an initial pyrolysistemperature of 350*C followed serially by a second pyrolysis at 600 0 C. The pyrol-yzate from each experiment was chromatographed on a 12-meter fused silica capillarycolumn of crosslinked methyl silicone (SE 30). The gas chromatograph was pro-grammed from 50 0 C for 4 minutes to 280%C for 15 minutes at 10 0C/minute. Massspectra of the chromatographic effluent were collected and stored; a mass range of33 to 450 amu was repeatedly scanned at approximately 1.5-second intervals for theselected mass range. Reconstructed mass pyrograms and mass spectra were generatedsubsequent to each analysis from the stored data. Identifications were facilitatedby the use of computer library search routines of the Wiley-NBS data base ofreference mass spectra.

1. DEOME, ALFRED J., KANE, PETER J., and PATT, JACOB. The Determination of Temperature-Dependent Degradation Mechanismsin Track Pad Elastomers by Pyrolysis-Gas Chromatography-Mass Spectroscopy. U.S. Army Materials Technology Laboratory, AMMRCTR 82-53, October 1982.

2. DEOME, ALFRED J., and HAGNAUER, GARY L. Pyrolysis-Gas Chromatography-Mass Spectroscopy of AE 502 Rubber Fuel HosesU.S. Army Materials Technology Laboratory, AMMRC TR 81-12, March 1981.

3. WUEPPER, JOHN L. Pyrolysis Gas Chromatographic-Mass Spectrometric Identification of Intractable Materials. Anal. Chem., v. 51,no. 7, 1979, p. 997.

4. IGLAUER, N., and BENLEY, F. F. Pyrolysis GLC for the Rapid Identification of Organic Polymers. J. Chromatog. Sci., v. 12,1974, p. 23.

5. CHIH-AN HU, J. Pyrolysis-Gas Chromatography Analysis of Rubbers and Other High Polymers. Anal. Chem., v. 49, no. 4, 1977,p. 537.

RESULTS AND DISCUSSION

The thermal gravimetric analyses of the respective samples under investigationare shown in Figures 1 and 2. Both rubber sytsems appear to be very similar ther-mally in that the organic additive portions of both vulcanizates are liberated attemperatures of less than 350 0 C. The temperature region where the formulation isdesorbed from the polymer is critical in order to separate the additives from thepolymer during the serial pyrolysis experiments. Table 1 shows the various tem-perature and weight lossrelationships associated with the two samples underinvestigation.

Table 1. THERMAL GRAVIMETRIC ANALYSIS DATA

Sample Organic Additives Polymer Filler Residues

LG-1 361.OC (0.929 mg) 422.6C 618.6C 633.9C

LG-2 366.6C (1.00 6 mg) 428.5C 645.8C 660.9C

In order to desorb the organic formulation from the respective samples, apyrolysis temperature of 350'C was selected. Samples weighing approximately 5 mgwere used in the pyrolysis experiments. A quartz tube probe was heated at 20 0 C/msand held at the maximum temperature for 20 seconds. The gas chromatograph programand data aquisition were then started. The 350 0 C mass chromatopyrograms of LG-1and LG-2 are shown in Figures 3 and 4. These components represent the major por-tion of the formulation added to the rubber polymer during the mixing process. Itwould seem that the fatty acid materials of hexadecanoic and octadecanoic acids arederived from the polymer system rather than from the formulation. The antioxidantin both LG-l and LG-2 is N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine; themass spectrum of this component is shown in Figure 3 a. Polymer identificationswere achieved through pyrolysis of each sample at 600 C subsequent to each 350 0 Canalysis. The reconstructed mass chromatopyrograms are shown in Figures 5 and 6.Essentially, these pyrograms indicate the presence of 2-methyl-i,3-butadiene(isoprene) as shown in Figure 5a.

In addition to the serial pyrolysis experiments performed, each sample wasalso extracted with acetone for 16 hours (ASTM D297). The extract was evaporatedand concentrated to approximately 5 ml. Two microliters of each extract wereinjected using the gas chromatographic-mass spectrometric parameters previous de-scribed. The mass chromatograms are shown in Figures 7 and 8, respectively. Thecorrelation of low temperature pyrolysis with the extract chromatography is excel-lent. The extract showed additional compounds indicative of the sulfur acceleratorused in the formulation. The representative mass spectra corresponding to theindividual components used for identification purposes are shown in Figures 7a, 7b,and 8a-8c.

2

CONCLUSIONS

Serial chromatopyrography-mass spectrometry experiments and gas chroma-tography-mass spectrometry of 16-hour acetone extracts have revealed a reasonablyconclusive qualitative analysis of the formulation additives in Samples LG-1 andLG-2. The polymer is identified as cis-polyisoprene (natural rubber). Theformulation additives are:

a. N-cyclohexyl-2-benzothiazole-2-sulfenamide (accelerator),

b. Hydrocarbon blend of wax or oil (processing/protective), and

c. N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (antioxidant).

Both samples are identical in qualitative formulation as evidenced from theresults presented in this report. No attempt was made to evaluate these samplesquantitatively. The polymer composition, shown to be of polymerized 2-methyl-1,3-butadiene (m/z 68) also shows various natural products and essential oils.There is no indication of polymer blending.

ACKNOWLEDGMENT

Appreciation is extended to Ms. Jane Brousseau for the thermal gravimetricanalyses performed on these samples, and to Dr. Robert E. Sacher for his helpfulinterpretation of the data,

3

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COMPONENT IDENTIFICATION

1. Hexadecanoic Acid2. Octadecanoic Acid (Stearic Acid)4. N- (1,3-Dimethylbutyl) -N '-phenyl-p-phenylenediamine (Antioxidant)

5 -12. Hydrocarbons

Figure 3. The reconstructed mass pyrogram of Sample LG-1 pyrolyzed at 3500 C.

7

File >LGI 300 C PY-GC-MS NATURAL RUBBER Scan 598Bpk Ab 4687 SUB ADD DVC 21.84 min.

211

4888

200 'J'' 43" 7 "" . 7 167, 183 "4,., 0

6S~~~~89 101 2 1r4.240 80 120 160 200 240

File >BIGDB Phenol, Z-tZ-benzoxazoll- Scan 6e934Bpk Ab 9999 0.00 min.

211

888

183 F40800 63 91 127 129 154 213 48

4 61 88 18 168

40 ... .. .......... 160. 205 240

File >BIGDB 2-Phenazinol, 6-amino- Scan 5e933Bpk Rb 9999 8.88 min.

211

400-/ 184 2124881L19 166 -- -40______

On, .. . ... I. . ... ,.I. . . . .,. . . .

48 so 120 1"0 280 240

File >LG2 308 C PY-GC-MS NATURAL RUBBER Scan 664Bpk Rb 4670 SUB ADD DVC 23.86 min.

211

2868- 43 77 , .66t 128 154 13 G .L

48.....................3 167213 {268 K1 .-. 7.,. . 11.. . .h " 40

4..98 i "".......1�8........20 240 Be18 9 40

File >BIGDB b,(-I1METHYL-bH-E4,b-BJtl,4JTHIRZINL-4,6tjH,7HIjI Scan 68917Bpk Rb 9999 0.89 min.

211

888 168-J42 9/ 12

4i's. ... .. .l.e 190. ---' 2 0 . . 2.. 4 8 '

F: ICDD Pentadecane, 2,6,18,14-totramethyl- Scan 60157Bpk Rb 9999 9.98 min.

268

800 183 81124000 1 84 /164 21 2 3 4

/ 154

a-. , " . I "" 1 , ,2 I ! 1 ", .. I . 0

4t 891 " , " 2 " 0 .2 .9 . . "'240 8

Figure 3a. The mass spectrum of the antioxidant [N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine], m/z 268,

derived during the 3501C pyrolysis experiments on LG-1 (top) and LG-2 (bottom).

8

File >LG2 .33.0-458.0 amu. 308 C PY-GC-MS NATURALADC TIC

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1. Hexadecanoic Acid2. Octadecanoic Acid (Stearic Acid)3. N-(1,3-Dimethylbutyl)-N'-phenyl-p-phenylenediamine (Antioxidant)

4- 8. Hydrocarbons

Figure 4. The reconstructed mass pyrogram of Sample LG-2 pyrolyzed at 350 0 C.

9

File >LGIA 33.0-450.0 amu. 608 C PY-GC-MS NATURALADC TIC

~~2884 y8 6ý81108

78880 1,0000

60007008&•

3

40008

38800

20000

10080 2

4 a 12 16 20 24 28 312 36 48


1. 2-Methyl-i,3-Butadiene (Isoprene)

2. Bornylene3. Limonene4. Natural Products


10

File >LGIR 608 C PY-GC-MS NATURAL RUBBER Scan 88Bpk Rb 14268 SUB ADD DYC 3.17 min.

6739 53

183812 41 48 51 6163 6 6 9

49 6/ 641 68

File >BIGDB I o3-Butadiene, Z-methyl- Scan 1068Bpk Rb 9999 8.68 min.

67

39 53 6

48

400-81 43 41 51 55 63 656643714 64 661 6 69

6 4 6

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File >BIGDB B,2-Pontadiene Scan 1864Bpk Rb 9999 0.08 min.

39 63 68

800 41 8N1 42 -

48000 37 /43 48 1 663 6566 411 /49' 54b 61 69

48 44 48 52 66 60 64 68

1. 13-Butadiene, 2-methyl- 68 C5H82. 1,2-Pentadiene 68 C5H83. 1,3-Pentadiene, (E)- 68 C5HO4. 13-Pentadienej (Z)- 68 C5H85. 1,3-Pentadiene, (Z)- 68 C5H8

Figure 5a. The mass spectrum of isoprene (2-methyl-i,3-butadiene), m/z 68, resulting from the6000 C pyrolysis of Sample LG-1.

11

File >LG2A 33.0-450.0 amu. 600 C PY-GC-MS NATURALADC TIC

9000

6

6000

40008

30006

26000 19

1360 23 3 17

T2-T r4 610 1'2 1'4 1'6 18 2'0 22 2 4


1. 2-Methyl-i,3-Butadiene (Isoprene)2. 3-Methyl-1,3,5-Hexatriene3. 1,4-Dimethylbenzene

4. 4-Vinyl-i,4-Dime~tl.ylcyclohexene5. 2,7-dimethyl-3-octen-5-yne

6. Limonene7. Farnesene


12

File >LGIE 33.8-450.8 ADC TIC 16 HOUR ACETOHE EXTRACT

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1. 4-Hydroxy-4-methyl pentanone3. Decane

4. N-Isopropylidene-cyclohexylamine (Accelerator Decomposition)

5. Hydrocarbon

6. Benzothiazole (Accelerator Decomposition)7. Hexadecanoic Acid

9. Octadecanoic Acid (Stearic Acid)

11. N-(1,3-Dimethylbutyl)-N'-phenyl-p-phenylenediamine (Antioxidant)

Figure 7. The reconstructed mass chromatogram of the 16-hour acetone extract of Sample LG-1.

13

File >LGIE 16 HOUR ACETONE EXTRACT 15.28 Scan 134Bpk Ab 2913 SUB ADD DVC 6.63 min.

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48 12sole

File >BIGDB N-I$OPRUPYLIDE-CYCLOHERYLRMINE Scin 2659Bpk Rb 9999 0.00 min.

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File >BIGDB N-ISOPROPYLIDENE-CYCLOHEXYLAMINE Sca'n 17189Bpk Rb 9999 8.98 min.58*1 /

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1. N-ISOPOPYLIDENE-CYCLOKEXYLPiINE 139 COWN2. N-ISOPROPYLIDENE-CYCLOHEXYLAMINE 139 C9HUN3. Azetidine, 1-cyclohexyl- 139 C9HUN4. Cyclohexane, cyclopropyl- 124 C9H165. Spiro[3.4Ioctan-5-one 124 C8N120

Figure 7a. The mass spectrum of N-isopropylidene-cyclohexylamine, m/z 139, found in Sample LG-1

(16-hour acetone extraction).

14

File >LGIE 16 HOUR ACETONE EXTRACT (3.20 Scan 187Bpk Rb 1447 SUB ADD DVC 7.54 &in.

135

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File >BIGDB- enzothiazole Scan 31542Bpk Rb 9999 0.8.-min.

136

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49le 68 8818keFile >BIGDE Thleno'3,2-clpyridine Scan 31543Bpk Rb 9999 8.88 min.

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1. Dnzothiazole 135 CJSNS2. ThieTo[3,2-c]pyridir. 135 C7115NS3. 1,2-Benzisothiaole 135 C7J5NS4. Benzothiaole 135 C7H5NS5. Benzothiazole 135 C7JI5NS

Figure 7b. The mass spectrum of benzothiazole, m/z 135, found in Sample LG-1 (16-hour acetone extraction).

15

File >LG2E 16 HOUR ACETONE EXTRACT (3.26 Scan 17Bpk Rb 2236 SUP ADD DYC 1.34 min.

56

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File >BIGDB Cyclohxanamine Scan 1808Bpk Ab 9999 8.8e min.

56

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File >BIGDE Cyclohoxanamine Scan 2191Dpk Rb 9999 8.88 min.

66

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1. 4-Hydroxy-4-Methylpentanone

2. Cyclohexanamine (Accelerator Decomposition)

3. 3-Methyl Pyrrolidine4. N-Isoproplyidene cyclohexylamine (Accelerator Decomposition)

5. Hydrocarbon

6. N-(1,3-Dimethylbutyl)-N'-phenyl-p-phenylenediamine (Antioxidant)7. Hydrocarbon

8. Hydrocarbon

Figure 8. The reconstructed mass chromatogram of the 16-hour acetone extract of Sample LG-2.

16

File >LG2E 33.0-450.0 amu. 16 HOUR RCETONE EXTRACTRDC TIC

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12000

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Figure 8a. The mass spectrum of cyclohexaneamine, m/z 99, found in Sample LG-2 (16-hour acetone extraction).

17

File >LG2E 16 HOUR ACETONE EXTRACT (3.28 Scan 85Bpk Ab 1088 SUP ADD DYC 3.79 min.

58 ,

1200-41

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File >BIGDB NR-IOPRUrYLDLNLC-Y;LUHLXYLRMI9L Scan 2659Bpk Rb 9999 9.98 min.

58

866 41 e

-/ 68 83 96 12440e / 139 -4

-T I I

4e 68 B6 e, ikeFile >EDIGB H-ISOPROPYLIDEHE-CYCLOHEXYLAMIHE Scan 17199Epk Ab 9999 9.98 min.

G8

see@] 6 3 96 124

I . . . .I . . I . [ .. 1 I . . . .48 68 Be M~ k

Figure 8b. The mass spectrum of N-isopropylidene-cyclohexylamine found in Sample LG-2(16-hour acetone extraction).

ýFile >LG2E 16 HOUR ACETONE EXTRACT (3.20 Scan 486Bpk Rb 2727 SUE ADD DYC 18.24 min.

211

20'268

166 /43 77 128 67 183 4

4e 8 ,0 ..... 6i 2 e 246

File >BIGDB ZI3HJ-B*nzothl&zolethione, 6-@thoxy- Scan 56920Bpk Ab 9999 O.99 min.

183 211

7/

52 se 10

-,u• / i •• 19 138 2'1•l4

40 .....eo ..... "2e..... "*1*. . • ' " ;'4e86 120 160 208 246

File >BIrDB Phenol, 2-(2-benzoxazolyl)- Scan 560934Epk Rb 9999 9.9 mBin.

211

183

466( • 63 91 106 127 128 154 213 2-446 , . .. 1.",,0.2 ,, .6... -----,--... ..-..----.,

Figure 8c. The mass spectrum of the antioxidant [N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine] , m/z 268, found in Sample LG-2 (16-hour acetone extraction).

18

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serial chromatopyrography- mass spectrometry of … · applications of serial pyrolysis-gas...

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