Document 4agnq1gzkpD6Dk8njkNvg2Z6j
K690917
B. F. Goodrich Chemical Company
A DIVISION Or THC S. F. QOOOPO* COMPANY
DEVELOPMENT CENTER
7 o'//
Degradation tad CadHwcloa Produce* Prop Poly(vlnyl Chloride)
VI Fyrolyele of Chlorinated PVC
by M.M. O'Hara
Date Completed: Kay 23, 1969
Date Issued: June 16, 1969
Distribution:
Akron Canaral Chenice1 Plant P.T. Vhicaire - R.S. Reynolda
Henry C.B. Cooper - J.P. Piers
Akron Laaal Dent. B.K. Scan
Lona Beech tf.D. Robb - A.V. Clements
Avon Laka Can. Chap. Plane *R.H. Rylanda - R.tf. HcKay-
J.M. Vhlcoay
Brccksyillo Raaaarch Cantar J.A. Awry H.L. Daania R.J. FoveaCC
C.F. Gibb# D.t. Harvey P.K. Zakrlefcl Raaaarch Library
Cf.imt.Sltg C.L. Wood* - 0.6. Scbrock
Cleveland V.F. Bixby W.E. Brodlne +t.U. Barrington
M.W. Larson - C.O. Segner (7) P.H. Levrenca +C.K. Hedger
R.O. Scott J.L. Naiaon B.M.G. Zvibfcar - J. Valentine
Louisville L.C. Crunkleton - S.S. Michele
Klaaara Jails T.R. Llaek - J.A. Klupar
Development Center
L.F. Arnold
J.A. Nlkora
L.A. Bennett
C.B. Parks
R.R. BLoor
J.W. Ryan
L.A. Chaodler
M.H. Shervood
B.A. Colline
J.A. TePas
L.B. Crider
C.L. Wheeiock
L.H. Conklin
R.J. Volf
B. C. DeCaplte
R.A. Yount
B.A. DlLlddo
Technical Council
J.L. Dorach
C.T.F. (3)
P. Dmyterko
C.B. Fleming
D.P. taechtfes
*C.H. Kothelner
BFG045\3
R.M. Kraagar
C.B. Lufter
R.J. Hsyer
2 T04":tB.t. Mikola Ivy
TOOTS^O
MAJOR OBJECTIVES
The major objective# of chi* research problem ar:
1. eo correlate the pyrolysis product* from typical polymer* with flammability, toxicity, corroaion and polymer structure, and
2. to develop the necessary technology for degrading polymers In Che presence of air and for measuring the various degradation products.
LIMITED OBJECTIVES
The limited objectives of the current study were:
1. to determine the degradation product* from two differently processed chlorinated PVC samples (aqueous chloriostioa vs. solvent swollen chloriostioa),
2. to determine the presence of say structural differences In the two ssaples ss evidenced by high sod/or low temperature pyrolysis and/or ocher analytical techniques, and
3. to predict, from the degradation products in an Inert atmosphere, any possible toxic degradation product* that would ba evolved la an oxygsn rich ataoapbare.
SlMiARY AMD CONCLUSIONS
l. Low ta^erature pyrolysis (300*0, In vacma) of T-574 CHl-Temp, Solvent swell chlorination) and of T-573 (Bi-Temp, aqueous chlorination) revealad difference* due only to the medita of chlorination in which the two samples were prepared. The following su^Mrises these findings:
T-574
t
Da gradation (300*0 Products
BCi (major)
Sense ne
Chlorobeoseoe
Dlehlorobenseoe
CCl4 CUC13
} C residual
solvent
T-S7S
HC1 (major)
Benzene Chlorobensene Dtchlorobencene
20681002
U BFG04514
2. High temper** Cure pyrolysia (600*0 revealed che following degradation profiles:
Product HCl
Volatile Hydrocarbon Fraction Carbonaceous Ash
T-5 74 <-- Wc.7. --> T-575
60.5
68.6
13.1 26.4
5.7 23.7
The volatile hydrocarbon fractions had che following compos It Ions:
Product CHClj Beocene CCI4 Toluene C2CI4 Chlorobenzene
Dichlorobencene Dichlorobenzene
Uonerlc
T-574 i----- C.C . Area X --> T-575
2.3 nil
46.6 (major) (minor)
25.8 nil
5.1 trace
5.2 nil
27.1
37.0
9.4 26.1
4.3 u.i
The higher level of HC1 la the pryolytate of T-575 Indicate*
that a higher degree of chlorination had taken place la the
preparation of this reala.
This hypothesis Is substantiated
by the chlorine analysis (T-574 67.73*%, T-575 69.49%) sod
by N.M.R. analysis (see below) of the two polymers.
3. Nuclear magnetic resonance spectrscopy (J. Westfehl) indicated the following distribution of <CBCl CHCl-CHCl and C82 * CHC1 linkages (minor contributions from vinylIdane linkages were not considered) In the two polywra:
-- CH?-CBC1 -
Hoi. % -* - CHCl-CHCl-CHCl-
T-574 T-575
53 4
' 47 96
4. The two chlorinated reslna were subeiltted to R. Krueger at the Research Center for stability evaluations. The results of that study showed that when both resins were heated at 220*C, T-574 exhibited e 5.5 minute Induction period, (before dehydroctelorloatlon began) while T-575 had a corresponding 9.5 eln. induction period. The longer Induction period of T-575 can be accounted lor by the higher degree of chlorination (wore --CHCI-CHCl-CHC1 -- linkages)
_____ Ip this resin,______________________________________________
*due, In part, to residual solvent
0681003
BFG04515
in
3. Based on knowledge of Che degradation product* In an Inert atmosphere, the following combustion produces would most probably result from the burning of T-574 and T-575 in air;
Resin
Probable Combustion Products
T-575
HCl, C02 snd CO
T-5 74
HCl, CO21 CO, unknown levels of phosgene
The phosgene in the combustion gases of T-574 would result from the pyrolysis of residual solvent and not from reain degradation. The amount of phosgene would be proportional to the residual solvent and chit may be as high as 1.2 - 1.3X.
0681004
lv BFG04516