Document 2qDQqvqpZwO2JQNnrgKEx5o7N
Monsanto Industrial Chemicals Co.
St. Louis, Missouri
Date: May 19. 1977
X D Uo-tJl
APPLIED SCIENCES REPORT
Report Type: Report Number: Job Number(s): Reported By:
Special Study
S-77-SS-3
A 3-000-760 2 1 - 8400009
T. W. Hunter M. W. Dietrich
CJ CJ fir p ti&A
- f<r
i
6^
Distribution:
M. W. Dietrich
W. c. Harrmann P. r. Heimsch T. w. Hunter
R. E. Keller L. R. Stark
T2B T3A W4A T28 TIB W4A
C0NK1DF.NTIAL INFORMATION. This report must not be sent outside the company without approval. The recipient is accountable for its safekeeping and proper disposal.
HONS 201786
S-77-SS-3
DETERMINATION OF DECOMPOSITION PRODUCTS Or THERMINOL VP-1
INTROOUCT ION'
Thern'inol VP-1 was bomb exposed for 1000 hrs. at 750C by the Functional Products business group and submitted for GC/MS analysis to determine the identity and concentration levels of the decomposition products. Also submitted was unexposed Thenmnol VP-1.
SUMMARY
Analysis of the decomposed Thorminol VP-1 indicated the presence of over forty compounds. Most of these compounds were high boilers whose general structures ap peared to be different combinations of_beo7ene chains and benzene chains with ether linkages. The concentrations of the minor components" ranged from 8500 ppm to less than 10 ppm. Undecomposed Therminol VP-1 (diphenyl ether and biphenyl) accounted for about 92% of the sample.
The unexposed Therminol VP-1 had almost no high boilers in detectable amounts and less than ten minor components. Generally the concentrations of the minor components were less than 150 ppm.
EXPERIMENTAL
All samples were analyzed via a Hewlett Packard 5980 GC/MS. Samples which were not analyzed as neat materials were diluted to about 1000 ppm in methylene chloride.
Mass`spectra 1jv^jpj^e^atJon_ - The identity of the components of the mixtures analyzed were determined "mainly from the mass spectrum associated with a chiomatographic peak. The most reliable identifications were those in which there was agreement of both the retention times and mass spectra of the sample peak and a known standard. In cases where known standards were unavailable identity was assigned on agreement between the sample spectrum and a published spectrum. If identification of a chromatographic peak could not be determined using the pre vious routes, an identification was assigned by the author which was consistent with molecular weight and fragmentation patterns. In all cases tentative ident ifications were reviewed to see if they were consistent with the sample origin and other identified sample components.
Sample quanti tatjon_ - Ideally quantitation of all peaks in an unknown should be done Ygnins't known'"standards. However m this case less than ten compounds wore available os external standards. Therefore quantitation of all peaks was done
MONS 201787
S-77-SS-3
Page Two
DETERMINATION OF DECOMPOSITION PRODUCTS OF THERMINOL VP-1
against an average response factor of the known standards. The two major components in both mixtures (biphenyl and diphenyl ether) were quantitized against their re spective standards, Use of an average response factor leads to estimations of concentration levels and not exact concentrations.
Instrumental conditions - Mixtures were separated chromatograph!cally under the following G*C conditions'"
Column: 2M X 2mm 5X silicone UC-W98Z on 80/100 mesh Chromosorb Q
Temperature; Oven - Q-300C & 8/min. Injection port - 25QC
Carrier Gas: Helium @ 30 ml/min.
The mass spectrometer was operated in the total ion mode of operation with the spectrometer being scanned from 35 to 500 amu in electron ionization and from 50 to 500 amu in chemical ionization.
The decomposed Therminol VP-1 sample was investigated by both electron and chemical ionization. Chemical ionization was used to confirm molecular weights and the presence of co-eluting components. Unexposed Therminol VP-1 was investigated only with electron ionization. Quantitation was done on chromatograms obtained with electron ionization.
RESULTS AND DISCUSSION
Figure? 1 and 2 are the total ion chromatograms of exposed and unexposed Therminol VP-1, respectively. Tables 1 and 2 are the compilation of the peak identifi cations and concentrations. From the identifications made it appears that Therminol VP-1 decomposes to compounds having either three or four benzene rings, with varying number (0 to 3) of ether groups. Also apparently present are com pounds which have two benzene rings which are connected together by a double bridgehead consisting of either or both carbon and oxygen. In cases where identi fied compounds could have structural isomerization no attempt was made to assign exact structures. (One exception being the terphenyls which were identified with the aid of known standards.)
Compounds which were in the exposed Therminol VP-1 and which had concentrations of less than 50 ppm were probably not detected above baseline noise especially in the high boiler region. Also many of the peaks in the high boiler region consisted of co-eluting compounds which made identification somewhat tenuous and probably masked the presence of some compounds.
HONS 201788
TABLE 1
COMPOUNDS IN RECOMPOSED THERMINOL VP-1. ASSIGNMENTS OF POSSIBLE STRUCTURES WAS CON SI STINT WITH MASS SPECTRA.
REI ENT JON TT Ml (Mm)
MOLECULAR WEIGHT
PROBABLE CHEMICAL 1ORMULA
POSSIBLE ANSTDR/OURCTUNRAMEE,2
A 4.3
70 C6H6
--H benzene
CONCENTRA TTON'
1
B 6.6
92 C7H8
<i>--toluene
1
C 8.9 ]) 30.3
106 C8H10
120 w
^-CH^-CItj ethylbenzene
0
<f>--Cll,
,,.
3 acetophenone
2 2
26 ppm
E 31.6 E 15.6 0 19
94 C6Ii6
((>--OH phenol
128 C10H8 00 naphthalene
154 C12H1I
((>--<J) biphenyl
1 2 1
8290 ppm <10 ppm
1! 23. 5 J 22.3
24.0
170 C12H1< 168 C12H8' 170
, .<(j--0-<fr diphenyl ether 0 dibenzofuran
1
2
25.9
196
xanthone
204 dibenzofuluene2
26.3 27. S 27.7 29.5
230
C18H14
(f,_o-terphenyl
161 ppm
246 C18H14
U?&nyl
3280 ppm
244 Cl9"l6 <t>-p-0triphcnyl methane
289 ppm
230 CI8n]4 <|t-0-(ji m-terphenyl
26 6
Vu0
<J>-0-<Ji~4> dhihenyl phenyl
ether
J67 5 ppm
MONS 201789
TABLE II (cont'J)
TTAK y
RETENTION Tinr (Min)
30.0
MOLECULAR WEIGHT
PROBABLE CHEMICAL FORMULA
230
C18H14
POSSIBLE STRUCTURE AND/OR NA>lu
p-terphcnyl
ASSIGNMENT1 1
246
C18"U
diphenyl phenyl 2 ether
Q 30.9
202
C18M142
diphenoxyben- 3 zene
Possible other unidentified components
R 32.1
306
C24,!18
quaterphenyl 3
Possible other unidentified components
S 32. 9
322
C24H16
<|>--0--(f>--phenoxy terphenyl
4
T 33.7 U 34.3
338 306
C24H182 VlB
4>--0--41----o-- quaterphenyl
4 3
V 34.7
322
C24H18
338 306
C24Hl82 C24H18
4i-0-4>-4>-4> phenoxy terphenyl
--o~4*--^--0--4*
quaterphenyl
4 4 3
322
Vl8
$-0-$-$-$ phenoxy terphenyl
4
W 33.2
322
C24H18
0--<|>--<t>--
* " 338
CJ*"l82
0-<t--0--1ij>
4 4
X 35.7
322 w 338 C24H102
$-0-$-$-$ phenoxy terphenyl
$-0-$-$-0-$
4 4
CONCEMTRA')os3 2366 ppm 83 ppm 20 ppm 269 ppm 37 ppm 997 ppm
436 ppm
34S2 ppm 1436 ppm
V 37.3
306 C24ni8 322 C24niR
338 C24I!182
quaterphenyl
phenoxy terpheny l
3 4
826)1
4
HONS 201790
Tabic 1 (cont'd)
PI AX z
RETENTION TINE (MIN)
38.2
molecui.au WEIGH1
PROBARLE CHEMICAL
FORMULA
306 C24H18
322 C24lJl8
338 C24H182
POSSIBLE
STRUCTURE AND/OR NAME^
ASSIGNMENT1 CONCENTRATION3
quaterphenyl
2
<j>--0" <j>--
4
phenoxyt erphenyl
4>--0--0--<i
4
7313 ppm
AA 38.6
306 C24H18 322 C24H18 338 C2"l802
quaterphenyl
3
phenoxy terphenyl 4
2509 ppm
354
C24183
cj>--o----0--<p--o--<i
4
(1) 1 retention time and mass epeetrum consistent with standard compound.
2 mass spectrum consistent with published spectrum.
3 best judgment based on simularitles between this mass spectrum and others observed in the experiment.
4 best judgment based on interpretation of mass spectrum alone.
(2) structures assigned to oxygen containing compounds based on lack of ion fragments for other possible positions of oxygen.
(3) concentration for whole peak based on an average response factor.
HONS 201791
PEAK A
B C D E f G
H
TABLE 2
RETENTION TIME (MIN)
COMPOUNDS IN THERMINOL Vp-1
PROBABLE
POSSIBLES)
MOLECULAR CHEMICAL
STRUCTURE
WEIGHT
FORMULA
AND/OR NAME
ASSIGNMENT^1*
2.1
84 c2h2ci2 methylene chloride
2
4.3 6.8
78 C6H6 92 C7H8
benzene toluene
1 1
8.5
Column decomposition product
11.8
94 w
phenol
1
15.7
128 C10H8
Tlicrminol VP-1 biphenyl diphenyl ether
37% 64%
naphthalene
2
22.3
168 Ci2H8
2
dlbenzofuran
1
23.5
196 C14H13
4
(3)
CONCENTRATION 10 ppm 31 ppm tS* 10 ppm
111 ppm +** 19 ppm
53 ppm
35 ppm
methyl xanthane
(1) 1 retention time and mass spectrum consistent with standard compound. 2 mass spectrum consistent with published spectrum. 3 best judgment based on slmularities between this mass spectrum and others observed in the experiment. 4 best judgment based on interpretation of mass spectrum alone.
(2) structures assigned to oxygen containing compounds based on lack of Ion fragments for other possible positions of oxygen.3
(3) concent!at Ion for whole peak based on an average response factor.
HONS 201792
MONS 201793