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UNCLASSIFIED
AD NUMBER:
LIMITATION CHANGES
TO:
FROM:
AUTHORITY
THIS PAGE IS UNCLASSIFIED
AD0466539
Approved for public release; distribution is unlimited.
Distribution authorized to U.S. Gov't. agencies and their contractors; Administrative/Operational Use; 23 Apr 1965. Other requests shall be referred to the Army Natick Labs, Natick, MA 01760
Eugene C. Stump, Ward H. Oliver, and Calvin D. Padgett
23 April 1965
Peninaular ChemReeearch, Inc. Poet Office Box 14318 Gaineeville, Florida
i
I !
QUARTERLY REPORT NO. 7
CONTRACT NO. DA 19-129-AMC-152(N)(019H6)
WITH
U. S. ARMY NATICK LABORATORIES
Report Period: 1 January 1965 - 31 March 1965
SYNTHESIS AND POLYMERIZATION OF
FLUORINATED SULFUR MODIFIED
NITROSO RUBBER
By
Eugene C. Stump, Ward H. Oliver, and Calvin D. Padgett
23 April 1965
Peninsular ChemResearch, Inc. Post Office Box 14318 Gainesville, Florida
t
FOREWORD
This report was prepared by Peninsular ChemResearch, Inc. /SX'
under Contract No. DA 19-129-(AMC)-P&?-(N) (OI 9116) for the U. S. Army
Natick Laboratories with Mr. C. B. Griffis as Project Officer. This is the
seventh Quarterly Report under this contract and covers the period 1 January
1965 through 31 March 1965.
Personnel engaged in this research are Dr. Eugene Stump,
Project Supervisor (27.5%), Dr. W. H. Oliver, Senior Research Chemist (90%)
Calvin Padgett, Research Chemist(97. 6%).Analytical work was performed under
the supervision of Van May. Drs. Paul Tarrant and George Butler are acting
consultants.
It is estimated that 90% of the work is completed and that 89. 9%
of the estimated costs have been incurred to date. To the contractor's best
knowledge the funds remaining unexpended are sufficient to complete the work
called for in the contract.
- i
*
ABSTRACT
Perfluorobutadiene has been reacted with oxygen in sunlight to
give a mixture of products possibly containing perfluorobutadiene monoxide.
Reaction of tetrafluoroethylene with nitrosyl bromide gave CF^BrCF^NO and
a lower boiling nitroso compound, as yet unidentified. Perfluorosuccinic
anhydride did not react with nitrosyl chloride at room temperature. Pyrolysis
of CH^OOCCF^CF^COONO gave a blue product believed to be CH^OOCCF^CF^NO.
A larger reactor for the pyrolysis of CF^COONO was constructed. About
120 g. of CF^NO is produced in 8 hours. The addition of nitrosyl chloride to
CF^NO/CF2=CFCF=CF2 copolymer gives a blue polymer containing nitroso
groups and having a Tg of -85°. CF^OF was added to CF^NO/CF^CF^/
CF2=CFCH=CH2 terpolymer. A gum copolymer having a Tg of -48* has been
prepared from CF NO/CF SCF=CF Copolymers of CF =CFBr with CF NO j ó £ Cd j
and terpolymers with CF NO/CF =CF have been prepared. CF =CFBr j Cd C* Cd
apparently has a higher reactivity ratio than CF^CF^ in this polymerization.
An attempt to incorporate p-trifluorovinylbenzoic acid as a termonomer was not
successful.
-li¬
li
TABLE OF CONTENTS
I. INTRODUCTION.
II. DISCUSSION .
A. Monomer Synthesis . ..• *
B. Synthesis of CF^NO.
C. Reaction of CF„OF and C1NO with Unsaturated Polymers.
D. Polymerization.
III. EXPERIMENTAL.
A. Monomer Synthesis.
1. Pyrolysis of Perfluoro(2-methyl-3, 6-dihydro-l, 2, 2H-oxazine
2. Reaction of Perfluorobutadiene with Oxygen.
3. Reaction of Tetrafluoroethylene with Nitrosyl Bromide.
4. Reaction of Perfluorosuccinic Anhydride with Nitrosyl Chloride.
5. Pyrolysis of CH^OOCCF^CF^COONO.
6. Synthesis of 4-Methyl- a. , ß, ß-trifluorostyrene
B. Synthesis of CF^NO.
C. Reaction of CF OF and C1NO with Unsaturated Polymers.
1. Reaction of CF OF with cf3no/cf2=cf2/cf2=cfch=ch2
Terpolymer.
2. Reaction of C1NO with CF NO/CF =CFCF=CF Copolymer.
3 2 ¿ D. Polymerization.
1. General Procedures for Polymerizations Described in the Tables.
iii -
1
2
2
4
4
6
14
14
14
14
15
15
15
15
16
16
16
16
17
17
#
IV. MONOMER PROCUREMENT.. 18
V. SAMPLES SUBMITTED. 19
VI. MONOMER LIST 20
TABLES
Table 1 Copolymerization with CF^NO. 9
Table 2 Terpolymerization . .. 10
Table 3 Miscellaneous Polymerizations. 13
FIGURES
Figure 1 Infrared Spectrum of Unidentified Nitroso Compound . 23
Figure 2 Infrared Spectrum of Volatile Products from Perfluorobutadiene-Oxygen Reaction. 23
Figure 3 Infrared Spectrum of CF^NO/CF^CFCF^F^
Copolymer after Reaction with C1NO. 23
Figure 4 Infrared Spectrum of CF^NO/CF^CF^/
CF2=CFCH=CH2 Terpolymer after Reaction
with CF3OF. 24
Figure 5 Infrared Spectrum of CF^NO/CF^SCF^F^
Copolymer. 24
Figure 6 Infrared Spectrum of CF3NO/CF2=CFBr
Copolymer. 24
- IV -
#
CORRECTIONS TO QUARTERLY REPORT NO. 6
Page 25, Figure 5 should read "Infrared Spectrum of
cf3no/cf2=cf2/cf2=cfcf=cf2/cf2=cfch=ch2. "
(t
I. INTRODUCTION
The research described in this report is part of a continuing
program sponsored by the U. S. Army Natick Laboratories and concerned with
the development of so-called "nitroso rubber", a 1:1 copolymer of trifluor
nitrosomethane and tetrafluoroethylene. A list of references describing
prior research was given in the First Quarterly Report.
The primary objective of this contract was to enhance the
desirable properties, in particular the low-temperature flexibility, of nitroso
rubber by the incorporation of sulfur atoms in a modified polymer structure.
Secondary objectives included the synthesis of desirable monomers, including
monomers not containing sulfur, and their polymerization in the nitroso rubber
system. This research has been described in previous reports.
Recently, the objectives of the contract were modified and
increased in scope. During this quarter major emphasis was placed upon
the incorporation of termonomers in the nitroso polymer system. The
objective of this work is to provide a cross-linking site along the polymer
chain which would not require the use of the ususal diamine cure.
1 -
#
IL DISCUSSION
A. Monomer Synthesis
Concurrent with our polymerization effort we are carrying out
research on the synthesis of several ccmpounds of potential interest as
termonomers.
Since nitroso-substituted perfluoroacids have been shown to
terpolymerize in the nitroso system to give a polymer which may be cured
through the carboxy group, * the synthesis of an ester derivative,
CH OOCCF CF NO, has been initiated. This synthesis involves the conversion 3 ù Cà
of perfluorosuccinic anhydride to its half-acid ester by reaction with methanol,
followed by formation of the silver salt and its conversion to the nitrite with
nitrosyl chloride.
CF C = O I > + CH OH
CF C = O > CH3OOCCF2CF2COOH
i AgzO
CH3OOCCF2CF2COONO < C1NQ- CH3OOCCF2CF2COOAg
The final step consists of pyrolysis of the acid nitrite to the desired product.
This series of reactions was started by reaction of the silver salt (from PCR
stock) with nitrosyl chloride. The yellow, liquid acid nitrite was not isolated
but was heated under vacuum to give a blue vapor. This product has not yet
been isolated as a pure compound for identification but is thought to be the
(1) 3M Co. , Research Report on Contract DA-19-129-QM-a684, "Arctic Rubber", 23 December 1962.
- 2 -
é
desired nitroso ester. An attempt to isolate the nitrite by extraction with
ether resulted in its complete decomposition. Since a vigorous reaction also
occurs when sodium-dried ethyl ether is added to CF^COONOi it is apparent
that another solvent must be found if the nitrite is to be extracted from the
silver chloride by-product.
An attempt was also made to prepare the nitroso propanoic acid
by the sequence below. No reaction occurred,
GF G = O I ¿ + C1NO cf2c o
ONOOCCF2CF2COCl
A
ONCF2CF2COOH H2°
ONCF2CF2COCl
however, when perfluorosuccinic anhydride and nitrosyl chloride were mixed
at room temperature.
The reaction of tetrafluoroethylene with nitrosyl bromide in the
vapor phase with ultraviolet radiation has also been carried out to give
CF BrCF NO. About 69 g. of product boiling in the reported range were ù Câ
obtained but, of more interest, about 10 g. of a blue gas boiling at 0° was
obtained as a forerun. This compound is undoubtedly a lower molecular
weight nitroso compound. Its infrared spectrum (Fig. 1) is simple, exhibiting
No-O absorption at 6. 25 microns and C-F absorption at 8. 08 and 8. 75 microns.
This sample is being purified by GLC prior to NMR analysis and molecular
weight determination.
Since attempts to epoxidize perfluorobutadiene by the method
used to prepare perfluoropropylene epoxide were not successful, we are
3
«
investigating its reaction with oxygen in sunlight. After 5 days irradiation
a clear, colorless liquid had formed. The infrared spectrum (Fig. 2) of the
overgas exhibited a distinctive peak at 6.6 microns (similar to perfluoropropylene
epoxide) as well as a CF^CF peak at 5. 66 microns. The desired product,
CF =CFCF - CF , would be used as a c ross-linkable termonomer. ¿ 2
Since oxazetidines can be pyrolyzed to give interesting 2
intermediates such as I^N = CF^ and since a supply of perfluoro(2-methyl-
3, 6-dihydro-l, 2, 2H-oxazine) was available as a Diels-Alder by-product-5 of
our CF^NO/CF^CFCFiiCF^ copolymerization, we have pyrolyzed this oxazine
at 550°. Since the volatile mixture has not been separated the results of this
reaction will be described in the next report.
B. Synthesis of CF^NO
Increased scale polymerizations have necessitated scaling up 4 5
the pyrolysis reaction of CF^COONO ’ to supply sufficient monomer. The
apparatus currently in use is described in the Experimental section and
produces about 125 g. of pure CF^NO in an 8-hour day. This capacity is at
present adequate for our demands.
C. Reaction of CF^OF and CINQ with Unsaturated Polymers
The reaction of CF OF with CF NO/CF =CFCF=CF ■j 3 2 2
copolymer was described in the last Quarterly report. During this quarter
the copolymer was reacted in solution with nitrosyl chloride. The product
after precipitation was a light blue gum whose infrared spectrum (Fig. 3) is
very similar to that of the copolymer with the exception of a peak at 6. 2 microns,
(2) D. A. Barr and R.N. Haszeldine, J. Chem. Soc, , 1881 (1955) (3) Quarterly Report No. 6, this contract
(4) Thiokol Chemical Corp. , "Nitroso Rubber Research, Development and Production", Quarterly Report No. 5 on Contract DA-l9-129-AMC-69(x) for the period 1 March 1964 to 31 May 1964 and earlier reports.
(5) G. H. Crawford, Jr., U. S. Patent 3, 162, 692 (22 Dec. 1964). (6) See Fig. 9, Quarterly Report No. 5, this contract.
4-
i
probably due to N-O absorption. Since less than an equivalent amount of
nitrosyl chloride was used, the polymer still exhibits CF2=CF- and -CF=CF-
absorption at 5. 61 and 5. 8 microns, respectively. The presence of pendent
nitroso groups in the polymer might allow cross-linking with a fluorodiene by
oxazetidine formation.
CF.CF -
2I F-C-NO CF =CF
I FCF
Cl
+ (CF ) ' 2 X
Cl FCF
I F - C - NO
! - CF2CF —
cf2-cf
CF.CF -
2| FC —N— O
I I I FCF CF -CF
Cl I F CF CF-CF
I ! 2 I F C - N - O
I CF2CF-
Another particularly interesting feature of the polymer is its
reduced glass transition temperature7. Tg of the copolymer is -43" while
that of the nitrosyl chloride adduct is -85°. The reason for this unusually
low Tg is not immediately apparent.
The addition of CF^F to the CF3NO/CF2=CF2/CF2=CFCH=CH2
terpolymer has also been carried out. A s in the addition to CF3NO/CF2=CFCF=CF2
copolymer, little (if any) residual unsaturation remained as indicated by the
infrared spectrum (Fig. 4) of the polymer.
The fact that additions of this type to double bond in the polymer
can be accomplished is encouraging and suggests that a cross-linking reaction
would occur with the proper difunctional agent.
(7) Determinations by U.S. Army Natick Laboratories
- 5 -
t
An attempt to cross-link a small sample of CF3NO/CF2-CFCF=CF2
copolymer by heaung a solution in refluxing FC-43 was not successful. The
reaction desired was a cyclization of the pendent trifluorovinyl groups to give
cross-link.
CF - CF
D. Polymerization g
An early attempt to copolymerize CF2NO with CF3SCF=CF2
produced a small amount of high-boiling liquid which appeared to be a mixture
of oxazetidine and low molecular weight polymer. This polymerization has
been repeated using larger quantities of the reac.ants in a smaller reactor and,
consequentially, higher pressure. Again, a viscous liquid was obtained but
upon removal of volatile material under vacuum a colorless gum copolymer
remained. The infrared spectrum (Fig. 5) shows a distinctive CF3S peak
at 13. 1. NMR analysis corroborates the copolymer structure. The glass
transition temperature of this sample9 was found to be -48°. Since the Tg
of nitroso rubber is -51°, it would appear that the incorporation of CF^ as
pendent groups in nitroso polymer will not enhance its low temperature
properties.
A copolymer of CF^O and CF^CFBr has been prepared in
order to investigate to possibility of curing by abstraction of a bromine atom.
This polymerization occurs readily to give a tough gum. Intrinsic viscosity of
this copolymer could not be obtained since it was insoluble in FC-43. An
infrared spectrum of this polymer is shown in Fig. 6. Preliminary NMR
analysis indicates that the alternating copolymer structure is formed.
Elemental analysis also indicates a 1:1 copolymer [Ãnal. caled. : %N, 5. 4;
%Br, 30.8. Fd. :%N, 5. 3; %Br, 30. <f| . Conversions were high, in the
(8) Quarterly Report No. 2, this contract (9) DTA analysis by Sadtler Research Laboratories
- 6 -
order of 90%.
Terpolymers with varying amounts of CF^CFBr were also
prepared. Samples containing up to 21. 7 mole% CF =CFBr were soluble
in FC-43. Intrinsic viscosities of these samples were low (see Table 2 for
data). As expected, the glass transition temperature rises with increasing
amounts of CF_ = CFBr as shown: ^ Q
Mole % CF2=CFBr Tg
in polymer
9.4 -45°
21.7 -35°
31.0 -21°
50. 0 (copolymer) + 3“
It is also interesting to note that the ratio of CF^CFBr/CF^-CF^ incorporated
in the polymer was greater than that in the monomer charge and that the total
mole % CF2=CFBr
Sample No. ^
2
3
4
+ CF2=CF2 in the terpolymers exceeds 50%.
Mole Ratio Charged CF NO:CF =CF :CF =CFBr
J L* L* L*
6:5:1
6:4:2
6:3:3
Mole Ratio Found CF NO:CF =CF :CF =CFBr
•J ù Ct ù
6 : 5.6 : 1.2
6 : 4.1 : 2.8
6 : 2.7 : 3.4
Although the reaction of nitrosobenzene with tetrafluoroethylene 12
has been examined , no report of the reaction of CF2=CF2 with N-nitroso
compounds has been found. Since N, N'-dimethyl-N, N'-dinitrosoterephthalamide
is commercially available, an attempt was made to react this compound with
CF2=CF2. The nitroso compound was placed in acetone solution in a flask and
tetrafluoroethylene was admitted. After 5 days, however, there was no apparent
reaction.
(10) From Table 2. (11) By elemental analysis for N and Br (12) Quarterly Report No. 2, this contract
_ 7 _
An attempt was made to incorporate p-trifluorovinyl benzoic
acid as a termonomer by running both in solution and in suspension (using the
sodium salt). In neither case was a detectable amount of acid incorporated.
Similar results were obtained using 4-methyl- , ß, ß-trifluorostyrene,
perfluoroallyl trifluoroethyl ether and hexafluoroacetone as termonomers.
The polymerizations run during this quarter are summarized
1. Pyrolysis of Perfluoro(2-methyl-3, 6-dihydro-l, 2, 2H-oxazine)
The oxazine used was first distilled on a spinning band column
and the fraction boiling at 52-53* (13.2 g. ) was taken for the pyrolysis.
A 2-neck flask was fitted with an addition funnel containing the
oxazine and a 1" x 15" Vigreaux column vented to a trap cooled to -183*. The
system was evacuated to a pressure of 5 mm. the flask was heated to 80-100*
and the column was heated to 550*. The oxazine was added dropwise to the
heated flask. After all but 4 g. of material had been reacted the column became
overheated and it collapsed. The product was transferred to a pressure ampoule
and allowed to warm to room temperature. It then deposited a yellow solid. The
remaining product has not yet been examined.
2. Reaction of Perfluorobutadiene with Oxygen
A 1-1. Vycor flask was charged with CF2=CFCF=CF2 (2.4 g. ,
0.015 moles) and (0.48 g. , 0.015 moles) and placed in sunlight for 5 days.
At the end of this time the flask contained a water-white liquid. An infrared
spectrum of the overgas showed some unreacted diene and a peak at 6. 6
(thought to be -Cf^^CF^ as well as other peaks. A spectrum of the liquid
also showed absorption at 6. 5 - 6. .
The reaction was repeated on a larger scale. A 12-1. flask
was charged with (20. 7 g., 0. 128 moles) and 02 (8. 19 g., 0. 256 moles)
and irradiated with a u. v. lamp through a Vycor immersion well. After 24 hr.
an infrared spectrum of the vapor phase showed a peak at 6. byU and the reaction
was stopped. The products were removed to a trap in liquid air and stored.
They have not yet been separated and examined.
- 14 -
*
3. Reaction of Tetrafluoroethylene with Nitrosyl Bromide
A 72-1. flask was charged with CF^CF^ (127 g. , 1.27 mole)
and BrNO (140 g. , 1.27 mole) and irradiated with u. v. light for 24 hours. The
mixture which was originally brown had now turned blue-green and was
transferred to a flask for distillation. The mixture was distilled on a glass-
packed column to give approximately 10 g. of a blue product boiling at 0* and
69 g. of blue product boiling at 13-20°.
4. Reaction of Perfluorosuccinic Anhydride with Nitrosyl Chlorid^
In an attempt to prepare CIOCCF^CF^COONO, a 100-ml.
flask was charged with perfluorosuccinic anhydride (17. 2 g. , 0. 10 mole)
and C1NO (6. 5 g. , 0. 10 mole) and the contents stirred while the mixture warmed
to room temperature. The overgas was removed under vacuum and e. minaticn
of the liquid residue showed it to be only unreacted starting material.
5. Pyrolysis of CH^OOCCF-.CF^COQNO
A 20-ml. ampoule was charged with CH^OOCCF^CF^COOAg
(6. 5 g. , 0. 021 mole) and C1NO (6. 5 g. , 0. 1 mole) and shaken overnight at room
temperature. The ampoule was then opened to the vacuum system and the excess
C1NO removed. This left a solid wet with a light-yellow liquid. The ampoule
was now vented to a trap in liquid air and a vacuum was maintained while the
ampoule was heated with a heat gun. The yellow liquid began boiling and the
vapor phase turned blue. A blue product was trapped in the -183* receiver.
After heat had been applied for several minutes the material in the ampoule
detonated. The blue product has not yet been analyzed but may be the desired
ch3ooccf2cf2no.
The reaction was repeated on a larger scale with the intention
of washing the yellow liquid (proposed CH^OOCCF^F^OONO) free from the
solid (AgCl) with dry ether. However, the ethyl ether reacted vigorously with
the product resulting in complete decomposition.
6. Synthesis of 4-Methyl- a , ß, ß-trifluorostyrene
4-Bromotoluene (10 g. , 0.062 mole) was reacted with lithium
in ether to form the lithium reagent. The solution was placed in a 300-ml.
- 15 -
#
Fischer “Porter bottle and cooled in liquid nitrogen. The bottle was exhausted
and excess tetrafluoroethylene was condensed into the bottle. The bottle was
sealed and placed in a cold bath at -30° for 4 hours. The mixture was hydrolyzed
and the ether layer dried. Evaporation of solvent and vacuum distillation gave
4-methyl- a , ß, ß -trifluorostyrene (3 g. , 30%), B. p. 90-92B/70mm.
n(j = 1.478. Reported Bp=91. 5/70 mm, n^= 1.481.
B. Synthesis of CF^NO
Trifluoroacetylnitrite is added at a constant rate to a 5-1. flask
containing refluxing FC-43 (3000g. ). The FC-43 is refluxed through a
2" X 24" column topped by a water-cooled condenser. The products are passed
through the condenser to a wash column containing Raschig ring packing and
circulating 7% aqueous NaOH, then through a CaCl_ drying tube, Linde 4A Cá
Molecular Sieve, and finally into a trap immersed in liquid air.
In a typical run 352 g. of CF^NO was prepared from 945 g. of
a yield of 54%. About 120 g. of CF^NO is prepared per day using
this apparatus.
C• Reaction of CF^OF and CINQ with Unsaturated Polymers
1 • Reaction of CF^OF with CF^NO/CF^CF^/CF^CFCI^CIL.
Terpolymer
A 7 g. sample of CF3NO/CF2=CF2/CF2=CFCH=CH2 terpolymer
(3:2:1) was dissolved in Freon 113 and reacted with CF^F (2 g. ) as described
in Quarterly Report No. 6 (p. 18). Infrared (Fig. 4) and NMR analysis
indicated complete reaction of CF3OF with the double bonds.
2. Reaction of CINQ with CF^NO/CF^CFCFrrCF^ Copolymer
A 10 g. sample of copolymer was dissolved in 50 ml. of Freon 113.
About 0. 5 g. of C1NO was condensed into the tube, which was sealed and placed
in sunlight for 4 hours. The solution was green at this time. The polymer was
precipitated by addition of acetone. A blue polymer (9 g. ) was obtained upon
drying. The polymer had a Tg of -85° and decomposed upon heating. An
infrared spectrum of this sample is shown in Fig. 3.
- 16 -
D. Polymerization
1. General Procedure for Polymerizations Described in the Tables^
Bulk polymerizations were run by condensing monomers into
ampoules or Fischer-Porter tubes. The tubes were evacuated, sealed at
liquid nitrogen temperature, and transferred to a cold bath for the time indicated.
The suspension polymerizations were run in a similar manner,
except the samples were shaken. The suspending medium was MgCC>3 in a
saturated LiBr-water solution.
In working up the products, the unreacted gases were vented
and the volatile materials recovered by vacuum distillation. The polymer was
then removed, washed and weighed after vacuum drying.
- 17 -
IV. MONOMER PROCUREMENT
During this quarter the following monomers were received from
outside sources:
25 g.
COOH
University of Florida
CF =CFCF OCH-CF L> L» U J
0. 7 g. University of Florida
Tetrafluoroethylene and perfluorobutadiene were obtained from
PCR stock. Trifluorobutadiene was prepared as described in previous reports.
- 18 -
V. SAMPLES SUBMITTED
During this quarter the following samples were submitted to the
U.5. Army Natick Laboratories for evaluation;
Designation
CQC 4. 3
CQC 8. 1
CQC 8. 2
CQC 8. 3
WD 46. 1
WD 51. 1
WD 54. 2
WD 56. 1
WD 57. 1
Charged Composition Amount (g.)
CF3NO(l)/CF2=CFBr(l) 5
CF3NO(6)/CF2=CF2(5)/CF2=CFBr(l) 5
CF3NO(3)/CF2=CF2(2)/CF2=CFBr(l) 5
CF3NO(2)/CF2=CF2(l)/CF2=CFBr(l) 5
CF3NO(3)/CF2=CF2(2)/CF2=CFCH=CH2( 1) 5. 5
CF3NO(3)/CF2=CF2(2)/CF2=CFCH=CH2( 1)+ 6.5
cf3of
CF3NO(l)/CF2=CFCF=CF2(l) + CINQ 2
CF3N0(6)/CF2CF2(5)/CF2=CFCF=CF2(1) 5
CF3NO(6)/CF2=CF2(5)/CF2=CFCH=CH2( 1) 5
- 19 -
#
VI. MONOMER LIST
The monomers listed below have been assigned the identification
numbers shown. These numbers will be used frequently throughout future
reports in place of cumbersome nomenclature or structures. A complete
list of monomer number assignments will be given in each report.
Number
400
401
402
403
404
405
406
407
408
409
Monomer
f2c=s
C6F5NO SF5CH=CH2
CF3SCF=CF2
(cf3)2c=s
CF3N=SF2
c6h5n°
[ICF3CF2CH2CH2Si(CH3)cQ 3
[CF3CF2CH2CH2Si(CH3)0] 4
cf3scf(no)cf2ci
F F F F
410
411
412
413
414
415
h2n
F F
F F
ON
F F
NH,
F F
F F
NO
F F
h2nnh
F F
O F F
NHNH,
NH„
HOOC
F F
COOH
F F
F F
416 SFgCF = CF2
#
417
418
419
420 (nc)2c = c(cn)2
4¿ 1
422 CF2BrC>¿nO
423 C: iOOCCF2CF2NO
- U -
i iirmr- 'iiwiniinmn rin irrrimrrir^f iijirwrflliwtiliïl1 iii 'lili i ' iii ^ ‘‘•IN1'H wlliBi'lillf",lll’Wfe ililiilHMIilliM
«
MrAVINUMftfk CM '
WOlNVMlti C
Figure 2. Infrared Spectrum of Volatile Products from Perfluorobutadiene -Oxygen Reaction
WAvtNUMMI CM
23
WAVINVMMI Cl«'
wâ*iiiNOn* M wcio*ii
Figure 4. Infrared Spectrum of CF^O/CF^CF^CF^CFCI^CI^
Terpolymer after Reaction with CF3OF
Figure 5. Infrared Spectrum of CF3NO/CF3SCF=CF2 Copolymer
Figure 6. Infrared Spectrum of CF3NO/CF2=CFBr Copolymer
24
#
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