TECHNUC.

REPORT
6-2-CM

W;

NITROSO RUBBER HANDBOOK

by
Malcolm C. Henry and Charles B. Griffis,

L'

AJI.CD

/January

1966

Clothing and Organic

Materials Division
Ci-OM-15

The findings in this report are not to be construed as an

official Department of the Army position unless so designated

by other authorized documents.
Citation of trade names in this report does not constitute
an official indorsement or approval of the use of such items.

DDC AVAILABILITY NOTIC11

Distribution of this document is un1imited.

Destroy his report when no longer needed, Do not return

it to the originator.

AD

Distribution of this
document is unlimited

STECHNICAL

REPORT
66-2 CM

NITROSO RUBBER HANDBOOK

by
U

Malcolm C. Henry
Materials Research Branch
and

Charles B. Griffis
Rubber, Plastics and Leather Engineering Branch

Project reference:

C&OH-15

1C024401AK'29

January 1966

Clothing and Organir.Materials Division

U. S. ARMY NATICK LABORATORIES

Natick, Mas~achusett 01760

FOREWORD

*that

Military operations conducted on a global scale require a

variety of equipment that must operate under all climatic conditions. This imposes severe requirements on construction materials,
particularly rubber whose properties are severely affected by
temperature extremes. To assure that rubber materials are available
meet requirements, a continuing Army research program is maintained. Out of this research, new rubbers are developed. Work both
in-house and under Army contract has contributed to the availability
of these new types of rubbers, the result of many and varied efforts
of a number of persons. This report deals with such a new product,
"nitroso" rubber, which is not a single polymer but rather a family
of many rubbery polymers.
The story of nitroso rubber development is spread over a number
of contractor repoi'ts, published and unpublished papers, scientific
meeting presentations and laboratory notebooks. This handbook
summarizes in one convenient volume all of the work performed on this
subject. It is designed for the use of materials engineers looking
for specific applications and for research scientis'-s interested in
synthesizing new materials.

S. J. KENNEDY
Director
Clothing and Organic Materials Division

G. R. THOMAS
Associ.te Director
Clothing and Organic Materials Division
APPROVED:
DALE H. SIELING, Ph.D.
Scientific Director
W. W. VAUGHAN
Brigadier General, USA

Commanding

ii

TABLE OF CONTENTS
Page No.
List of Tables

vi

List of Figures

viii

Abstract

ix

I Introduction

II Terminology and Nomenclatu.re

III
IV

Historical Development

Nitroso Rubber Chemistry

A. Monomer Syntheses

1.
2.
3.
4.
5.
6.
7.

6
6
7
7
7
8
8

Tetrafluoroethylene, C2F4
Trifluoronitrosomethane, CF3 NO
p-Bromotetrafluoronitrosobenzene, p-BrC 6 F4 NO
Methylperfluoronitrosopropionate
P-Nitrosoperfluoropropionic Acid, HOOCCF 2 CF2 NO
"r-Nitrosoperfluorobutyric Acid, HOOC(CF 2 )3 NO
Miscellaneous

B. Polymerizations

1. Kinetics and Postulated Mechanisms

2. Copolymerizations
3. Terpolymerizations

8
10
11

C. Pilot Plant Scale-Up

11

D. Basic Polymer Property Studies

25

1.
2.
3.
4.
5.
6.
7.

Solvent Properties
Infrared Spectroscopy
Nuclear Magnetic Resonance Spectroscopy
X-ray Diffraction
Glass Transition Temperature (reboudd method)
Thermogravimetric Analyses
Linear Thermal Expansion Coefficients (apparent)

26
26
26
28
28
28
32

iii

TABLE OF CONTENTS (continued)

Page No.
V

VI

VII
VIII
IX

Properties of Nitroso Rubber

32

A. Copolymers

33

B. Properties of Nitroso Rubber Terpolymer

(carboxyl-nitroso rubber)

36

C. Properties of Special Interest

37

Compounding Studies

42

A. Materials and Test Methods

42

B.

42

Results and Discussion

C. Conclusions

53

Future and Potential Uses of Nitroso Rubber

53

Summary

53

Acknowledgments

54

X References

55

iv

LIST OF TABLES
Page No.
I Synthesis of Nitroso Monomers
II Copolymers with CF3NO
III
IV

13

Nitroso Copolymers Other Than CF3NO

16

Nitroso Terpolymers (CF3NO/F 2 C=CF 2 /A)

18

V NMR Spectroscopy of Nitroso Rubbers

VI

VII
VIII
IX

28

Apparent Linear Thermal Expansion Coefficients of

CF3 NO/CF 2 Nitroso Gums

32

Nitroso Rubber (raw polymer)

33

Nitroso Rubber (compounded)

34

Glass Transition Temperatures for Various Nitroso

and Fluorocarbon Polymers

35

X Carboxyl-Nitroso Rubber

36

XI

Carboxyl-Nitroso Rubber (compounded)

37

XIA

Nitroso Rubber Copolymer CF2NO/CF 2CF2

38

XIB

Resistance to ClF 3 Gas of Various Vulcanizates of

Carboxyl-Nitroso Elastomers

39

XIC

Resistance to ClF 3 Gas of Carboxyl-Nitroso Elastomers

Cured with Cr(CH 3 COO) 3 or with Cr(CF 3 COO) 3

40

XID

Fluid Resistance of Carboxyl-Nitroso Elastomers

Cured with Cr(CF 3 COO) 3

41

XII

Compounding Recipes and Test Results Amine Cures HiSIL 303 Filler

44

XIII

Compounding Recipes and Test Results Amine Cures Carbon Black Fillers

45

v4

LIST OF TABLES (continued)

Page No.
XIV

XV

Compounding Recipes and Test Results Amine Cures

Amine and Filler Variations

Compounding Recipes and Test Results Other Than

46

48

Amine Cures
XVI
XVII

XVIII

Mooney Viscosity of Various Batches of Nitroso Rubber

49

Cure Characteristics as Determined with Mooney

Viscometer (large rotor)

50

Differential Thermal Analysis Results

52

LIST OF FIGURES
No.

Title

Page No.

1. Equipment flow chart for CF3NO production

24

2. Equipment flow chart for C 2F4 production

24

3.

26

Material flow chart for nitroso rubber

4. Equipment flow chart for nitroso rubber production

26

5. Infrared spectrum (2-15u) of 56703-3 nitroso gum

27

6. Nuclear magnetic (F1 9 ) resonance spectrum of 56703-3

27

nitroso gum
7.

Rebound tester for 1000 cycles per second modulus

29

8.

1000 cycle per second modulus by rebound on sample XP5675

30

9.

Thermogravimetric analysis in air and helium of an amine-

31

cured nitroso copolymer

v
vii

____
____ ____
____

-~-...

___
___

____

__

ABSTRACT

"Nitroso" rubber is the generic name for a family of rubbery

high polymers having the common structural denominator of a repeating nitrogen-oxygen-carbon atomic sequence as follows:
~N-0-(C-)

Architecturally these nitroso polymers are the first of a whole

new class of materials. Nitroso polymers, as currently known, are
highly fluorinated or completely fluorinated and as such are members
of a specialty type of elastomer since only a limited number of
fluorinated elastomers are known. It is becoming increasingly evident,
however, that the combination of "nitroso" groups in the highly
fluorinated linear polymer chain is responsible for the introduction
of interesting and novel combinations of properties. Thus, nitroso
elastomers have good low temperature properties, solvent resistance,
stability to corrosive environments, and flame resistance.
Nitroso polymers have been developed to their present state by
the cooperative effort of Army scientists and contractors. Over the
past eight years, considerable insight has been gained as to the

nature and potential uses of nitroso rubbers. This handbook is an

attempt to assemble a summary of this accumulated knowledge. It is
hoped that the contents so compiled will aid in the future development of this new family of specialty elastomers.

Sq

NITROSO RUBBER IANDBOOK

I.

Introduction

The foundation upon which the U. S. Army's Research and Development Program is based rests upon the requirements of its tactical and
support forces- As a result of these requirements a continuing program
is carried out in an attempt to develop new and improved materialsz
Materials required by -the Army often must have properties or combinations of properties not required by others. Military operations
are rcutinely carried out in envircnments presenting severe stress upon
both personnel and equipment. Arctic Cperations at -651F and lower are
tyTical of the Low temperatures met in Am.y operations. On the other
hand, extremes of ground temperatures may reach 120cF while 1000OF is
a common temperature encountered in operating components of military
equipment.
Experience has shown that comercially available rubbers, both
natural and synthetic, are unsatisfactory in many cases. One specific
requirement for improved elastomers is that of low temperature flexibility and petroleum fluid resistance. Elastomers are not commercially
available that have the combined properties of low temperature flexibility and gaszl-_ne or oil resistance. Elastomers having these combined properties are required for many military items such as fuel lines,
pump diaphragms, rubber covered cables and wire, chemical warfare protective clothing, gas masks, gaskets, flexible containers and liners.
Additional properties required in elastomers in addition to those
already cited are ozone resistance, flame resistance, resistance to
h .gh the:mal flux and radiation and both acid and oxidizer resistance.
In short, elastomers are required having combinations of properties
that will maintain their integrity in a wide range of temperature and
corrosi-ve environments.
The development of new elastomers with the best possible combination of properties has thus been the goal of the U. S. Army Natick
Laboratories research program since its inception some years ago.
Nitroso rubbers were recognized to belong to a unique system both as
a generalized chemical structure and as a material with desirable
combinations of properties that have potential use in military operations. This report is the story of the development of nitroso.ruhber
to its present state. Many people have contributed to the nitroso
rubber program that has been carried out by the U. S. Army Natick
Laboratories. It "s hoped that recognition of indi'idual efforts have
been made within the text of this report,

II.

Terminology and Nomenclature

The terminology for the class of polymeric structures now commonly known as nitroso rubber has evolved primarily as a result of
convenience.
In one sense this is unfortunate since the implication
is to a single structure. In reality, it is a generalized class of
structures. Nitroso rubber is derived from material having a co-on
structural denominator, namely a repeating trivalent nitrogen-oxygencarbon sequential atomic arrangement of the following type:

-o-(c~
n

As currently known, it is highly or completely fluorinated. However,

many structural variations are theoretically possible and a large
variety of structures have been prepared all having in common the repeating nitrogen-oxygen-carbon linkage.

Many structures containing this repeating unit are not elastomeric.

Depending upon other incorporated structural features, these products
may range from viscous oils to resinous plastics. From a structural
point of view nitroso elastomers are unique as the only known example
of a nitroso group entering into a polymer chain as an integral entity.
III. Historical Development
The history of the d velopment of nitroso rubbers began in 1955
when Barr and HazeldineI - reported the discovery of a reaction between tetrafluoroethylene and trifluoronitrosomethane. One of the
reaction products was reported to be a viscous polymeric oil. Subsequent work established the elastomeric nature of one of the reaction
products4 and extended the scope of the reaction.
In 1956 the first patent was issued to Rose 5 for the product
resulting from the reaction of tetrafluoroethylene and trifluoronitrosomethane.
A summary report by Fitt 6 was also published in 1957 on both the
preparation of nitroso compounds and the addition reactions of nitroso
compounds to olefins.

Published reports in the early literature described nitroso

elastomers as having novel combinations of properties. Resistance to
the action of corrosive chemical environments such as solvents,
oxidizing chemicals and ozone coupled with good low temperature properties were typical of the properties that created the initial interest
for Army scientists. In 1957 the U. S. Army Natick Laboratories (then
the Quartermaster Research and Development Command) funded its first
2

contract to investigate the possibilities of developing these nitroso

polymers into useable or practical elastomeric materials for military
use. Complimentary interest in these unique elastomers has resulted
in further investigations by Hazeldine 7 ,8 and Rose 9 . Since that time
to the development of the present state of the art the following
industrial and academic laboratories under contract to the U. S. Army
Natick Laboratories, have contributed considerable data toward the
development of these nitroso containing elastomers: The Central Research Laboratories of the Minnesota Mining and Manufacturing Companyl
Thiokol Corporation' Peninsular Chemical Research Corporation;
Monsanto Research Corporations University of Florida and the University
of Colorado. Throughout this report repeated references will be found
relating to these contractors and the results obtained under their
research programs with the U. S. Army. For convenience these references
have been abbreviated using a sequence of a capital letter indicating
the company, a number indicating the report number and finally a page
reference thus: T7-p-32 indicates Thiokol Corporation, Report #7,
page 32.
Contractors referenced in this report are as follows:
1. U. S. Army Contract DAl9-129-M-1043, 15 October 1957 15 August 1960.
Minnesota Mining and Manufacturing Company, Arctic Rubber,
G. H. Crawford, -t. al. Final Research Report 1960.
2. U. S. Army Contract DAl9-129-QM-1684, 24 August 1960 23 December 1962.
Minnesota Mining and Manufacturing Company, Arctic Rubber,
H. A. Brown, et. al. Final Research Report 1962.
3. U. S. Army Contract DAl9-129-AMC-69(X)0.19044, 27 February
1963 - 28 February 1965. Nitroso Rubber, Research Development and Production, Thiokol Chemical Corp., Trenton, N. J.
J. Green, et. al. Final Research Report 1965.
4. U. S. Army Contract DAl9-129-AMC-151(N) 0.1. 9115, Physical,
and Rheologic-1 Properties of Nitroso Rubbers, Monsanto
Research Corp., Everett, Mass., G. L. Ball, et. al, 1963 present; 9 reports.
5. U. S. Army Contract DA19-129-AMC-152(N) 0.1. 9116, Synthesis
and Polymerization of Fluorinated Sulfur Modified Nitroso
Rubber, Peninsular Chemical Research, Inc., Gainesville,
Florida, G. Stump, et. al. 1963 - present; 8 reports.
6. U. S. Army Contract DA19-129-QM-1926 0.1. 6028-62, Synthesis
of Special Fluorine Containing Monomers, University of Colorado,
Boulder, Colorado, J D. Park and J R, Lacher, 1964 - 1966
period.
3

7.

U.S. Army Contract DA19-129-ANC-79(N) Research on Synthesis

of Unsaturated Fluorocarbon Compounds, University of Florida,
P. Tarrant, et. al. April 1 1963 - 1966 period.

Abbreviations:

a.
b.
c.
d.
e.
f.
IV.

Minnesota Mining and Manufacturing Company

Thiokol Chemical Corporation
Monsanto Research Corporation
Peninsular Chemical Research, Inc.
University of Florida
University of Colorado

3M
T
M
P
F
C

Nitroso Rubber Chemistry

In 1957 the U. S. Army Natick Laboratories funded a program with

the Central Research Laboratories of the Minnesota Mining and Manufacturing Company to begin to investigate the potential of nitroso
polymers as a military elastomer.
Early work was substantiated that trifluoronitrosomethane, CF3 NO,
reacts with tetrafluoroethylcue to form an oxazetidine as the main
product,
CH3 - N - 0

CF2 -CF2
at temperatures above 100 0 C. At temperatures below OC a linear polymer
predominates containing alternating CF3 NO and CF2 CF2 groups.
N

CF3

CF2

F
n

Both the polymer and the oxazetidine were found to be stable towards acids
as well as oxidizing and reducing agents.

Table I
SYNTHESIS OF NITROSO MONOMERS
MONOMER
1.

p-BrC 6 F4 NO

METHOD

REFERENCE

H 6 F4 NH2 + D2 CH-COOH)

BrC 6 FNH2

BrC6Fr4 NH2 + HCOOOH H2-i BrC6 F4 NO

2.

C6 F5 NO

C6F 5NH2 + HCOOOH

3.

C6 HsNO

owkrcally available

4. CH3 CF2 NO

CF2 z CH2 + HI

70%

T7,pIO

64%

- C6 F5 NO

T3, p11
G.M. Brooke et. al.
Chem & Industry
1961, 832
Chemical Procurement
Laboratories

CH3 CI

CH3CF2 I + NO Hg
U.V.

CH3 CF2 NO

3H Final Report 1962

5.

H(CF 2 )4 NO

H(CF 2 )41 + NO Hg
U.V.

H(CF 2 ),NO

3m Final Report 1962

6.

CICF 2 CF2 NO

F 2C a CF2 + NOCI -

& ClCF 2 CF2NO

31MFinal Report 1962

Pierce Chemical Co.

NCCFO 0
02NCF2CF2N

7. NO2 CF27.N2r3NO
CF2NO

C2F4

8. C8H 17 NO

C8 FI71 + NO Hg

9. C3 H7NO

C 3F7 I + NO

33M0

3M Final Report 1960

C8 H17NO

HS

3 N Final Report 1960

C3 H7NO

3m Final Report 1960

UVo

10. CF 2 CICFCLNO

CH302C(CF2 )2 N0

CF2 - CFCI + NO Fe1

CF2 -

CF2 C1CFC1NO

3m Final Report 1960

Pierce Chemical Co.

c.00
+ CH3 NO2

CF2 -

CH 3 0 2 C(CF2 )2 COONO

c%

CH3 0 2 C(CF 2 )2 COONO pR2olysi

CH3 0 2 CCF 2 CF2 NO

P8,p7

p.

The rate of decomposiion Qas increased at higher temperatures. Varying conditions did not result in improved yields which were in all cases
very low.

6.

1
-itoserfluorobutric Acid, HOOC(CF 2 )3 NO 4
The photlysis of di Utrosyl perfluoroglutarate,

(CF2 ) (COONO) 2 , derived from the reaction product of perfluoroglutaric

anhydride and N 200, Proceeded at a much faster rate with less reversion
to N20 3 o The reacticn product 1fnitrosoperfluorobutyric acid,
HOOCCF2 CF2 CF2NO, could be purified by distillation.
7.

Misceilanecus

Alteratve methods may also e used for the syntheses

of nitros -containing cocpourds such as those described by Andreadesi 5
and Park1 g utilizing additiao reacticns cf nitrosyl halides to fluoroolefins and fluoroketones.
B. Polymerizations
Nitroso elastomers ray he prepared using standard bulk
water emulsion polymerization techniques. Hazeldinef79,
or
solvent
has also reported the formation of hi.gh molecular weight elastomers
containing the nitroso group as an integral part of the elastomer.
Both bulk and solution polymerizations of CF3,NO/C 2 F4 have the disadvantage of poor heat transfer (leading to uncontrolled reactions)
or low molecular weight product when used on a larger scale. Methods
of carrying out these polymerizations in aqueous medium indicated
that satisfactory conditions could be obtained when using low temperatures. Thus an aqueous suspension system employing an organic suspending agent such as magnesium carbonate and a soluble inorganic salt
such as lithium chloride or lithium broei-de as a freezing point depressant was found to be a good polymerizing medium. Using this
system the polymer is obtained in the fon of small particles. The
polymer is separated from ths water phase by filtration and freed of
suspending agent by acid treatment. The resultant molecular weight
of the product compares favorably with that obtained by small scale
bulk polymerizations. As will be seen (IVC) this polymerization system
was found to be the most advantageous for "scale-up" and was used in
the pilot plant facility when larger quantities of nitroso rubber copolymers were being prepared, Materials obtained via this method
have been shown to have intrinsic viscosities of greater than one,
indicating molecular weights over one million.

l..

Kinetics and Postulated Mechanisms

The mechanisms involved in the copolymerization of
8

nitroso monomers have as yet not been resolved to any degree of

certainty. The dependence of initial polymerization rate on the concentration of CF3NO and C2 F4 was determined approximately by polymer
isolation techniques. The rates obtained best fit a reaction which
is first order in CF3 NO concentration and one-half order in C2 F4 concentration. Experiments have shown rather conclusively that mechanism
of initiation is not due to impurities being present in the monomers.
Rather, the initiation is probably due to the radical character of the
nitroso compound itself.
A partial scheme for this mechanism might be:
1. CF3 NO

CF3 N-O
ko.

2. CF3 N-O " C2 F4

.N-O-CF2 -CF2 .

I
CF3

or
.O-N-CF2 -CF2.

3.

N-OCF 2CF2 . + CF3NO

CF3

CF3

4. .N-OCF
I
2 CF2 N-O. + C2F4
CF3

B
CF3
-_ N-OCF2CF2N-O.

CF3

-_h-- N-OCF
CF2 -N-OCF 2CF.
22
I

CF3

CF3

CF3

Termination steps might include:

-,-,CF2 CF2 . + -*--CF2CF
2 . -+

k
-F -N- . k
CF3

A biradical mechanism is reasonably plausible based on existing

data, the stability of CF3 NO and the formation of oxazetidine under
conditions of elevated temperatures. (3M-Final Report 1960).
A number of interesting features concerning the nitroso copolymers have been observed that are of interest. As shown in reaction step No. 2 there are theoretically two different ways in
which the nitroso group can attach to the C2 F4 . In a polymeric

species one might expect to find either a random sequence or a

regular preferred orientation. W. T. Flowers 1 9 has done considerable work having to do with the thermal degradation of nitroso
polymers and in particular the CF3NO/C 2F4 copolymer. Inside a mass
spectrometer volatile fragments with molecular weights up to 6000
have been produced. There is nothing to suspect that the structure
is other than a regular one. These mass spectrometric results also
show a repeating regular pattern for every molecular weight of the
monomer, that is 199. If one were to have a unit in the reverse
sequence with fragmentation occurring at the N-0 bond (which it
does being the weakest link in the polymer) then one would get
molecular weights which do not correspond to the 199 difference and
these have not been seen.
Another interesting feature, also having to do with the direction of addition of the nitroso group to an olefinic carbon bond,
has been noted by Sutcliffe 20. Using unsymmetrical olefins the
direction of addition of the N=O group of CF3NO to a C=C bond in
oxazetidine formation is opposite to that involved in formation of
the predominant copolymer. This can be explained by postulating
that copolymerization occurs by a free radical mechanism and that
oxazetidine is produced by either a free radical or molecular process
preceded by formation of a 1:1 complex of nitroso compound with
olefin 21
Finally, the effect of small amounts of chain transfer agents
on the polymerization rate and molecular weight were determined.
The transfer agents used had no significant effect on the polymerization rate, which is normal for a radical type polymerization provided
the radical formed after transfer is capable of initiating new chains.
In all cases the transfer agents significantly lowered the molecular
weight of the polymer. Initial polymerization rates in CF2 CICFCl 2
solutions were determined and found to be lower than in (C4 F9 )3N.
The rate dependency on monomer concentrations was found to be the
same in CF2 ClCFCL 2 as in (C4F 9 )3No These results also seem to be consistent with the polymerization mechanism already proposed earlier in
this section (3M-Final Report 1962).
2. Copolymerizations
A variety of nitroso copolymer systems have been studied
under a variety of conditions. Both laboratory scale and pilot plant
scale procedures have been worked out in considerable detail. The
pilot plant copolymerizations are described in section IVC of this
report. Typical laboratory procedures for bulk polymerizations are
described by Crawford 22 and Brown (3M-.Final 1962) for trifluoronitrosomethane and tetrafluoroethylene,
t1.

10

The monomers are condensed into pyrex ampoules, sealed and the
reaction carried out at subambient temperatures. Unreacted monomers
are vented and the sol-rent, if any, removed.
Copolymerization systems that have been prepared are noted in
Tables II and III and are referenced within the table for source information.
3. Terpolymerizations
In contrast to copolymerizations the experimental procedures for terpolymerizations are relatively undeveloped. Terpolymerizations studies to date have been primarily bulk polymerizations using nearly molar equivalent quantities of comonomers with a
relatively small molar proportion of added termonomer. Experimentally the reaction conditions are essentially similar to copolymerization
conditions. Table IV describes and references the variety of terpolymer systems that have been studied thus far. Termonomers are
usually selected as participating members of the polymerization based
on structural considerations for subsequent compounding studies.
The termonomet selected must have a reactivity such that the
reactive groups will be distributed randomly along the polymer chain.
Very few olefinic compounds then qualify as termonomers. Nitroso
compounds containing functional groups in the side chain are suitable
termonomers since all nitroso compounds have about the same reactivity
towards C2 F4 provided the nitroso group is adjacent to a -CF2- group.
C. Pilot Plant Scale-Up
The requirement for extensive compounding studies concomitant
with the requirement for relatively large quantities of the trifluoronitrosomethane/tetrafluoroethylene copclymer suggested a need for a
pilot plant facility, In 1963 the U. S. Army funded an extensive
program with Thiokol Chemical Corporation (T-Final 1965) to produce a
sizeable quantity of this copolymer for the purpose of carrying out
extensive compounding evaluations. Thiokol reports to the U. S. Army
reflect this effort.

11

~-

One of the main efforts in this work deal with the scale-up

*these

synthesis of the trifluoronitrosomethane as well as determining the

hazard involved in the synthesis and handling of this relatively
unexplored chemical compound. Thiokol's past experience in propellants was recognized as being somewhat unique as a result of the many
procedures that have been developed for the evaluation of potentially
hazardous materials. Both the art and the science of those skilled in
safety tests were made available tc the program.
The preferred route for trifluoronitrosomethane production was
through the formal-ion and decarboxylation of :rifluoroacetylnitrite,
CF3 CO2 NO1 5 . Nothing to date has been uncovered that has resulted in
any change in this approach. Trifluoroacetylnitrite can be prepared
by the interaction of dinitrogen trioxide, N2 C3 , or with nitrosy!
chloride, NOCI, with the former method being preferred because of
superior yields.
(CF3CO) 20+ N 20 3 --

2CF 3 CO2 NO

The N203 was obtained from the Matheson Company, Inc., and used as
received. The purity was greater than 99 percent. Since N203 dissociates readily it was removed from the storage cylinders as the
liquid phase. Trifluoroacetylnitrite was decomposed to CF3 NO by
pyrolytic techniques. In Trauzl block tests trifluoroacetylnitrite
could be detonated although the detonation was not very brisant.
Additional detonation testing by a card gap test to ascertain
whether or not this material will propagate a detonation wave (and
at what rate) showed that the critical diameter of trifluoroacetylnitrite is greater than 11/16 incn with metallic confinement.
Ignition limits of the vapors were determined over the range of 25100 0 C as a function of concenzration in nitrogen. No detonations
were experienced. The data from these tests indicated that CF3 CO2NO
ignites on initiation at concentr-ations greater than 50 percent up
to about 650C and at lower concentrations at higher temperatures.
The lower temperature limit for the ignition of CF3CO2NO vapor
appears to be about 400 C. Thermal decomposition rate of CF3CONO
were determined up to 1840C at which temperature the time required
for complete decomposition is of the order of 5 - 6 minutes. Spark
tests indicated that dilution of the CF3CO2NO vapors by FC-43
(3M producz-perfluorobutyl tertiary amine isomer mixture) had resulted in a process operable without undue hazard (Thiokol Reports
Nos. I and 3)
Satisfactory completion of the safety test- along with studies
of the pyrolysis of CP3CO 2 NO resulted in a unitized operation capable
of producing one pound/hour of the deep blue gaseous CF3 NO which
could ultimately be stored in gas storage bottles. Thus it became

i.',

-0

Z.

A.

Ch C%

CD

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C.0

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possible to continuously produce CF NO of at least 99 percent purity

by metering trifluoroacetylnitrite into a reactor containing an inert
diluent at reflux. Decarboxylation is affected in the vapor phase and
the CF3NO swept continuously from the reactor zone through a purification train into traps at liquid nitrogen temperature where it is condensed. The inert diluent (triperfluorbutylamine-FC-43) is returned
to the reactor by a condenser. CF3 NO purification is affected by a
5 percent caustic scrubber to remove CO2 and N02, a drying tower and
finally a molecular sieve column at -10COC to remove non-acidic nitrogen oxides and CF3NO 2 . This unitized operation was capable of producing one pound per hour of pure CF3 NO which could be stored in gas
storage bottles for extended periods of time at -200C without change
or detrimental effect on its use in polymerizations.
Figure 1 illustrates the equipment flow chart for CF 3MO production.
Tetrafluoroethylene, C 2F 4 , for the scaled up production of nitroso

rubber was manufactured in the Thiokol TFE facilities in Moss Point,

Mississippi. For the initial polymer program tetrafluoroethylene was
prepared by the debromination of tetrafluorodbromce-hane. This was
accomplished by a refluxing suspension of activated zinc in methanol.
The efficient vapors were precooled by a cold water condenser and then
passed through a -350C condenser to remove any dimethyl ether which
might have been produced by the reaction of zinc and methanol. The
product was then condensed at liquid nitrogen temperatures under a
slight helium pressure to preclude contamination by atmospheric oxygen.
When the reaction was complete the condensate was warmed to -760 C
transferred in vacuum to a stainless steel storage cylinder containing
an inhibitor. The Equipment Flow Chart for the tetrafluoroethylene
preparation is shown in Figure 2.

IS 1"

Col.

(CF,
CO,NO)

Col.
Fi

Ei

nf

tf

catfobbl-

Zi1

48V",4

1..,

,
.
Itlo 9 W1

pit

T~flloB- o

Pm,

tIt

Figure 2. Equipment flow chart for

C2 F4 production

Figure 1. Equipment flow chart for

CF3 NO production
24

7111.I

g4

Thiokol's copolymer facility consisted of two reinforced ccncrete

bays in which the glass monomer production equipment and the 25 gallon
stainless steel polymerization reactor were housed. A circulating brine
system cooled by direct injection of CO2 furnished refrigeration for the
polymerization and necessary cold traps. This was accomplished by a 100
gallon tank equipped with a stainless steel 7-1/2 HP brine pump. A 12 kw
oil heating system was piped to the pyrolysis unit. The equipment flow
chart is given in Figure 4.
In evaluating the reaction variables which could have significant
effect upon the product it was found that the purity of the CF3 NO was
critical. In addition certain solvents could act as chain transfer agents
as for example, carbon disulfide or those containing hydrogen or chlorine.
The optimum polymerization time at -25 0 C was found to be abcut 24 hours.
The purity of lithium bromide used as a freezing point depressant was found
not to be critical. The quantity of magnesium carbonate used did not particularly effect better suspensions or yield significantly variable products.
The heat of polymerization was determined to be 74.8 + 0.5 K cal/mole using
the CF3 NO/C 2 F4 monomer ratio.
Since the nitroso monomer is itself the initiator in the polymerization
of the nitroso rubber, very special polymerization conditions are required
to assure the formation of a high molecular weight polymer. Suspension,
bulk and solution polymerizations have been investigated. The suspension
procedure described herein is typical of one that has consistently produced
high molecular weight nitroso rubber: a 150 cc. stainless steel cylinder
is charged with 70 cc. of Li Br solution (53g. Li Br/10Og. H2 0, freezing
point -450C), 2.0g. MgCO 3 and 8.0g. each of CF2 CF2NO. The cylinder is
agitated at a temperature of -250 C for 20 hours. At the end of this time,
the unreacted monomers are vented and the contents of the cylinder removed.
The resulting suspension is allowed to settle and the supernatant liquid
decanted. The precipitate is washed in water and then stirrad in concentrated HCl until no further reaction is noticed. The conversion may be as
high as 86 percent of the expected high molecular weight polymer. The
material flow chart for the scale-up of this process is given in Figure 3.
Two hundred pounds of CF3 NO/CF2 CF2 copolymer have been produced in this
facility in lots of approximately 30 pounds. Yields run as high as 85
percent.
D.

Basic Polymer Property Studies

In 1962 the U. S. Army Natick Laboratories began funding a program

with Monsanto Research Corporation to carry out certain physical and
rheological properties on the CF3 NO/CF 2 CF2 copolymer gumstock. The goal
of this program was to obtain basic information about the chemical structure
of this polymeric systems in order to have a fuller understanding of its
potential.

25

Table V
NMR SPECTROSOOPY CF NITROSO RUBBERS*
Sample No

Chemiz.=-

Shift of Peaks, ppm

2

-11.iL
-11o4
-ll,3
-11.5

XP5675
XP5702

XP5812
XP5887

r24 C
-242

3.0

19

3 0

2,0

-2i,8

3,0
3 0

1.9

2.G
1.9
2 0
1.9

: E
+.i.
1l -

.2!0

--" 5

Area Ratio of Peaks

-N(CF, )-

2.0

-N-CF2CF 2 -

-OCF2CF_*F19 Resonance @ 40 MC

Reference trifluoro acet-: acid

4.

X-ray Diffract on

All samples of CF3 NO/CF 2 CF2 were found to be noncrystalline as shown by the;r diffuse diffrac cn patzerns
5. Glass Transi.:cn Texrera-_re ,rebo-.nd methcd,
Figure " shows the rebz-nd tester used to determine the
glass transiticn of a materia_ at 1000 cps by measuring the rebound
The perof a small ball bearing fromi. the s-.rfaze cf the specimen
cent rebound correlates to the logarithhmic deoremen-: sinze this
decrement goes through a maximum where :he elast:c modulus deData of
creases rapidly from a glassy state to a :ubbery s:ate
percent rebound versus temperature for a typical CF3NO/CF 2CF2 copolymer is shown in Figure 8. The specimen was tested from -0C"C
up to 400 C, The minimum rebound region cf -16C is the 000 cps
Using an equ.'aler:e of 70 C per
glass transition tempera-ure
decade of frequency kapproximati:.r' the 0.1 ops giass transition
(such as determined by the zorsion pendulaxm, wcid be -460 C,
6. Thermogravimerric Anaiyses
A TGA in helium and in air was conducted on cured
CF3NO/CF 2 CF2 samples, the results of whizh are shown in Figure 9.
In air the rubber violently decomposed at 270 C

28

Automatic ball lifter

Bell Jar,

1/8" diameter ball-

Retaining
Specimen Ring
Anvil Base

Thermocouple

Temperature Controller

Figure 7. Rebound tester for 1000 cycles per second modulus

29

100

V. 90
Rebound Tester
Sample YP-5675
0.5 mil Al covering
Temperature Rate 6.8oF/min

80

60

r-50
.0

4o0

30

20

10

01
-100

-80

-.60

-4J0

-20

Temperature,

+20

OC

Figure 0. 1000 cycle per second modulus by rebound on sample XP5675

30

.%

mm~

L.

0
0\

00

00

C.
6

-3

00

o0
'Sul

4SS0

31E

I
7. Linear Thermal Expansion Coefficients (apparent)
Coefficients of linear thermal expansion by means of a
dynamic modification of ASTM-D696-44 were conducted on samD!es of
used. The dynamic
3NO/CF 2CF2 gumstock. A quartz dilatometer was
of expansion as a
determinations
modification consisted of periodic
function of temperature at a rate of 1C/min. The term "apparent"
is used because of the non-equilibrium nature of these determinations.
A temperature range of -75C up to about 100 C above the glass transition temperature was covered. Glass transition temperatures Tg,
where (Oah/0i:O were determined as a result of expansion measurements and is shown in Table VI.

PCF

Table VI
APPARENT LINEAR THERMAL EXPANSION COEFFICIENTS
OF CF3NO/CF 2 NITROSO GUMS

Sample

Apparent Linear
Expansion Coefficient OC-1

Temperature Range

TgOOC

Tg,cOoC

XP56 75d

(7.2 x 10-5)
(1.2 x 10-4)

-67 to -52
-52 to Tg

-46

-60c

XP5702

(8.2 x 10-5)
(1.2 x 10-4)

-67 to -52
-52 to Tg

-46

-45

XP5812

(7.6 x 10-5)

-72 to Tg

-49

XP5887

(5.7 x 10-5

-72 to -62

-48

(8.8 x 10-5)

-62 to Tg

a.
b.
c.
d.
e.

"Apparent" due to temperature use of 1C/min.

From thermal expansion data
From Clark-Berg determinations
Devolatilized 16 hr at 800 C and 3 mm Hg
Sample contained volatiles

V. Properties of Nitroso Rubber

For the great majority of nitroso elastomers prepared to date
only mininal data has been compiled. Certain selected systems have
been subjected to intensive investigations and considerable data has
been accumulated. This is particularly true for the CF3NO/CF 2CF2
copolymer system and to a lesser extent the CF3 NO/CF 2CF2 /NO(CF 2 )
(3 or 4) COOH terpolymer systems. The properties of fluorinated
elastomers have received considerable attention and reviews by
Montermoso 2 2 ,23 and others 24 -26 describe their, properties in some

32

Tt

detail. Summations of various phases of the U. S. Army sponsored

Nitroso Rubber Program have been described in publications by
Montermoso 27- 29 . Recent results describing the chemical and physical
properties of nitroso rubber co- and terpolymers have been reported
by Griffis and Henry 30 ,31 .
A. Copolymers
The properties of the raw polymer of nitroso rubber obtained
from the reaction of CF3 NO and CF2 =CF 2 are described in Table VII.
As an equimolar copolymer it is a colorless, transparent rubber that
can be processed on regular rubber compounding equipment. The rubber
is completely nonflammable. When directly exposed to a flame, some
gas is evolved which tends to put out the flame; however, no charring
of the rubber takes place.
Table VII
NITROSO RUBBER (raw polymer)
-+CF2 CF2 N-O+n

Structure

CF3
Amorphous
Crystal structure
Approx. 1.3X10 6
Mol. Wt.
1.93
Specific gravity
2.41 @ 60 cycles
Dielectric constant
-510 C
Tg
Solubility - soluble in - fluorocarbons, FC-43, Freon 113
insoluble and unaffected in hydrocarbons
Reaction:

aliphatic and aromatic amines degrade or crosslink.

Thus far, the only successful cure has been with triethylenetetramine
and even this cure requires extended periods of time at temperatures
near the decomposition temperature of the copolymer. Higher molecular weight copolymer samples are definitely more difficult to cure,
using the amine treatment, than lower molecular weight materials.
Above 212 0 F. sponging occurs rather rapidly.
The properties of the compounded rubber and the recipe used for
compounding is given in Table VIII.

33

Table VIII
NITROSO RUBBER (compounded)
Recipe:
Polymer
Hi Sil 303
TETA
HMDA
Properties:
Tensile strength, (Psi)
Stress at 300% Elongation, (Psi)
Ultimate elongation, %
Hardness, Shore A
Tensile set at break, %
Low temperature properties:
Temperature retraction, TR50
Gehman stiffness, T 5

100
15
1.25
2.5

1230
410

640
60
34
-360 C
-410C

Chemical resistant properties, volume swell, % in following:

70/30: isoctane/toluene
2
MEK, ether

Perchloroethylene
Nitrogen Tetroxide

3
1

Ozone resistance: after 24 hrs @ 175 ppm @ 1500F.

Flammability: will not ignite

No cracks

In its uncompounded state nitroso rubber copolymer is a white

to amber colored dense elastomer with a fluorine content of 66.8%.
Its low glass temperature results from the low attractive forces between chains and to free rotation about the -N-O bonds in the repeating unit. A study of the glass transition temperatures for
various nitroso and fluorocarbon

Table IX
GLASS TRANSITION TEMPERATURES FOR VARIOUS NITR

AND FLtKO-C-ARBON POLYMERS

Polymer

Tz. OC

1. -!NOCFiC4.

Comments

-51

literature

-9

literature

2.

-OCFzCF

rF, CFTJ
I

3. {cjFCFz

so

literature

16S

literature

5. -

,
F

-108

calculated
based on
I and Z

-51

Assumption

6. --FNOCFZiFCFJ

LF

same as 1
x

7. -NO

-184

calculated

-95

calculated

-90

calculated

-86

calculated

-91

calculated

-86

calculated

8 .{-NOCFZCFz

Ti

9. ..[NOCFzCF].

L , T
_F .fOCFzCF]

0.9*

10. -{,OC FZC FZ-

0.1*

{NOCFZCFZ
7 0.75

l1-NOCFCFz--

0.25

-fOCF

F-

0.9

12. -OCFZC

Ti

Fj-"

0.75

0.1

-OCF

LF

--

:F,
0.25

weight fractions

35

B.

Properties of Nitroso Rubber Terpolymer (carboxyl-nitroso

rubber)
Properties of the carboxyl-nitroso raw polymer are given
in Table X.
The beginning of a family of these terpolymers have been
synthesized, in which nitrosoperfluoropropionic acid and nitrosoperfluorobutyric acids have been used in varying mole ratios of 0.5 to 2.

r:

Table X

CARBOXYL-NITROSO RUBBER
Chemical Structure:

-NO-CF

2 CF2-NO

L(CF 2)3COO

Mole Ratio: 48/50/2

Crystal Structure: Amorphous
0.62 (FC43); - 0.81 X 106
Molecular Weight:
Solubility: Soluble in fluorocarbons, FC43 and Freon 113
The compounding recipe and the properties of the vulcanized carboxylnitroso rubber are given in Table XI. The incorporation of the acid
termonomer into the nitroso polymer has resulted in decided improvement
of tensile strength properties, while retaining the excellent chemical,
low temperature and flammability characteristics. It is interesting to
note the increased volume swell of this compound in methyl ethyl ketone
over the copolymer.
Nitroso rubber gumstock appears to be resistant to chlorine trifluoride ClF 3. Amine cured vulcanizates of nitroso rubber copolymer and
metal salt vulcanizates of carboxyl-nitroso rubber terpolymer, are converted by chlorine trifluoride, to substances resembling the original gumstock, with losses of weight approximately corresponding to the amount
of curing agent present. The rate of degradation appears to depend upon the
metal salt used in the vulcanization and upon the temperature3 4 .
Nitroso elastomer gumstocks containing no hydrogen atoms (completely
fluorinated) are extremely resistant to corrosive environments. Of
particular note are the resistance to strong oxidizing agents such as N 20 4
or fuming acids. In the presence of strong bases the elastomer degrades.
Table XYA indicates the stability of nitroso elastomers to a variety of
atmospheres.

36

Table XI

CARBOXYL-NITROSO RUBBER (compounded)

Polymer - 100
Silstone 110-20
Chromium triperfluoroacetate 8

Compounding Recipe:

Properties of compounded polymer:

Tensile strength, psi
Ultimate elongation, %
Set at break (10 min.), Z
Hardness, Shore A

2170
720
30
57

Low temperature properties:

Temperature retraction, TR-50
Gehman stiffness, T 5
Chemical resistance:
Volume swell, %, in following:
70/30: isooctane/toluene

-41C
-44"C

52

MEK

4
6

Dichloroethane
Nitrogen tetroxide
Flammability - *ill not ignite
C.

Properties of Special Interest

Storable Oxidizers:

Nitrogen tetroxide, N 20 4 , has no

effect.*
Elemental Fluorine: unaffected by
fluorine at room temperature.

Ozone Resistance:

No cracks after 24 exposure to 175 ppm

@ 150*F.
Sunlight Resistance: No cracks after 2 months of exposure
@ 20% elongation.
*Various nitroso elastomers have been evaluated for N204 resistance.
The nitroso rubber copolymer gum has shown no indication of degradation
after 60 days immersion in liquid N204 at 150*F. Carboxy-containing nitroso
terpolymers cured with chromium triperfluoroacetate appear to be unaffected
after three weeks in liquid N204 at 100"F 35 . A summation of t'..se results
with carboxyl nitroso elastomers is shown in Tables XIB, C and D. It was
noted that although the cured carboxyl nitroso elastomers swelled in many
liquids, in most cases the liquid was a solvent of the curing agent
(CF3COO) 3Cr. It was thus possible to speculate that the solvation of the
(CF COO) 3 Cr caused the swelling.

37

L
:qI.

Table XIA
NITROSO RUBBER COPOLYMER CF2 NO/CF 2 CF2
(Unvulcanized Gumstock)
Solvents and chemical agents having no significant affect,
solvation, swell or degradation.

50:50 xylene hexafluoride:chloroform

2-Butanone (MEK)
Trichlorobenzene
1,4-Dioxane
3:1 Heptane:MEK
Chlorocyclohexane
3:1 MEK:Heptane
50:50 MEK:Heptane
Xylene Hexafluoride (XHF)
1,4-dichlorobutane
Benzotrifluoride (BTF)
Trifluoroethanol (TFE)
Carbon tetrachloride
Diethyl Ether
n-Butyl Chloride
Tetraethyl orthosilicate (TEOS)
para-chloro-benzotrifluoride
Chlorobenzene
Trichloroethylene
Chloroform
Methyl chloroform

Temperature
steam bath
steam bath
steam bath
steam bath
steam bath
steam bath
steam bath
steam bath
steam bath
steam bath
steam bath
steam bath
steam bath
steam bath
steam bath
steam bath
steam bath
steam bath
steam bath
stea.n bath
steaw; bath

6,0 -dichloroethyl ether

steam bath

Methyl Perfluoro Butyrate (MFB)

Distilled water
Conc. ammonium hydroxide
Furfural
Skydrol
Skydrol 500
JP6 Fuel
ASTM ref. oil #1
ASTM ref. oil #3
MIBK
Xylene
10% aq. acetic acid
10% aq. sulfuric acid
Conc. hydrochloric acid
Conc. nitric acid

steam bath
212OF
reflux
212OF
212OF
212OF
212OF
212F
2120F
212OF
212OF
212OF
212F
158OF
158 0 F

38

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C)

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C)

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(A~
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0,.

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to -4
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Table XID
FLUID RESISTANCE OF CARBOXYL-ITITROSO ELASTOMERS()
CURED WiTH Cr(CF 3 COO)3
(8 p. by wt. Cr(CF 3COO) 3 /100 p. by wt. ELASTOMER)

Original Properties

Appearance

Dk. Green

Strength
330 psi

Elong.
600%

Aging Conditions: Samples (small dumbells) were placed in 50 ml. of liquids in

100 ml. single neck flasks fitted with the reflux
(* *) condensers. All flasks
ll0OC.
at
days
7
for
bath
oil
an
were kept in
Testing:

Aged samples were tested wet (ASTM D471-57T)

Liquids
(Samples were aged in)

Appearance

Weight
Change, %

Strength
Elong.
Retained, % Retained,

Distilled water

No change

Skydrol-500

Swollen

JP-4 Fuel

Brown

4
5

FC-43 Solvent, Tech.

NH4OH, 10% aq. soln.

Swollen
Degraded

6
7
8
9
10

DMF Solvent, Tech.

Xylene, Tech.
Carbon-Tetrachloride, Reag.
Heptane, Tech.
Trifluoro-Ethanol, Tech.

Bleached
Bleached
Sl. Bleach
Brown
Swollen

Swollen
Swollen
+4
0
+39

72
110
78

ii
12
13
14
15
16
17
18

H2 S04 , 30% aq. soln.

NaOH, 10% aq. soln.
DMSO solvent, Tech.
Phenol, 5% aq. soln.
Ethylene Glycol, Reag.
1,2-Dichloroethane, Reag.
Ethyl Alcohol, 50% aq.
Acetic Acid, 10% aq.

No change
No change
Bleached
Swollen
No change
No change
No change
Swollen

-2
+6
Swollen
+25
0
+4
+8
+33

285
164
Weak
58
141
83
73
39

132
130
73
125
87
88
S2

19
20
21
22
23

Ethyl Acetate, Tech.

MIEK, Tech.
Benzene, Tech.
HC1, 10% aq. soln.
1940 3 , 10% acL. soln.

Swollen
Swollen
No change
No change
No change

+53
+52
+3
+12
+15

36
142
64
71
79

66
65
60
88
95

1
2

N 204, at room temp.(l)

N2 04, at 5-15 0 C

No change
No change

+6

194
186

131
136

UDMH, at room temp.

Degraded

Notes:

+26
+109

0
+500
-

(*) Terpolymer: C2 F4 /ONCF 3 /ON(CF 2 )3 COOH, mole ratio

(1) Under pressure.
(*~) Liquids boiling at lower temperatures refluxed.

70

92

109

107

Weak
Weak
67
.27
5C

J00/99.5/0.5
1

41

'Auk-mo

7
VI.

Compounding Studies

Although nitroso elastomers have interesting combinations of

properties it was clear from the initial studies that certain
physical properties, ipertD1646-63 /F9 1 Tf 10.7 0 0 12 122 718 818. Tm 35263 741.6ET35

of 1000 psi or more had readily been obtained from the earlier
rubber (3M), tensile strengths of 300 psi represented the maximum
obtainable from the Thiokol rubber. There were differences in
curing characteristics (scorch time, time of cure, and cure index)
as well. To compensate for these differences, a series of amine
cure studies were made.
The compounding and curing recipes, cure times and temperatures, and subsequent physical properties of various compounds of
batch 5702 are given in Tables XII and XIII, and of batches 5702
and 5675 in Tables XIV and XV. Table XII gives the test results
of amine-cured, HiSil 303-filled vulcanizates and Table XIII the
results with amine-cured, carbon black-filled vulcanizates.
Table XIV lists the vulcanizates with amine cures and amine and
filler variations, and Table XV those with other than amine cures.
In the Table XII series (HiSil 303 filler) the triethylenetetramine (TETRA) was varied from 1.25 to 5 pphr (parts per hundred
rubber) and the hexamethylenediamine carbamate (Diak #1) from 1
to 2.5 pphr. Press cure temperatures varied from 2200 to 2600F.
The Thermax black filler (MT), which had been found to increase the
rate of cure of the Thiokol rubber, was tried in combination with
the HiSil 303 in compound 57. This vulcanizate proved to be too
weak to test. Compound 79, which had the smallest amount of TETA
(1.75 pphr), was the best of this series but even this showed a
tensile strength of only 245 psi.
In the second series using the amine cure Table XIII, various
carbon black fillers were used: medium thermal (MT) furnace black
"Thermax", an easy-processing channel (EPC) black, and a highabrasion furnace (HAF) black. Press cure temperatures varied from
1800 to 250 0 F. None of the black fillers gave vulc3nizates that
were superior to those using HiSil 303 Table XII or to those using
Linde silicone-treated HiSil 233 or Silstone 101. When the curing
time was kept below 250"F, only the HAF black among the black-filled
compounds did not sponge but it failed to cure.

143

OLf)0

U,

0
HH

N>

Otf

.- 1 tn

L
cc

O*

HL

H(N

C\JC
to-

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Table XV
COMPOUNDING RECIPES A14D TEST RESULTS
OTHER THAN AMINE CURES
Compound Number
Ingredient
Parts by Weight ...
.

Nitroso, Thiokol 5675

82

84

85

86

,_87

88

100

100

100

100

100

100

15

15

15

15

1
1

100

Nitroso, Thiokol 5702

83

Chromium triperfluoroacetate5
2

CaO

15
.1
2
5

Cab-O-Sil
Hexamethylenediamine Carbamate
Diethylthiourea
IMAPO
HiSil 303
B

SN C12

15

9
3

DiCup 40c
Trimethylolpropane trimethacrylate
Pyrometalicanhydride
14DI

5
3

MgO
Cadox BSG Paste

Press Cure, Time, min/Temp OF

Tensile Strength, psi

60/24_0 60/250 60/300 60/300 60/250 60/250 60/250

XV

Ultimate Elongation,

Stress @ 300% Elong, psi

a b ma
Hardness Shore Ai

Tr-t-oirpn

Pyoeaianyrd

iu4c48

tiehcrlt

$:4

0
0

100

100
0

Table XIV describes the compounds made with a variety of amine

crosslinking agents, fillers, and stabilizers. It had been found
that the addition of more than 2 pphr of triethylenetetramine usually
produces-sponging and this always lowers the tensile strength. Sponging often is not readily discernible; sometimes it can be detected
only by means of a microscope. To ensure against sponging, compound
14 was made using only 1 pphr of triethylenetetramine and 0.33 pphr
of hexamethylenediamine carbamate. To achieve maximum cure with th s
low level of curative, the compound was press-cured for 240 minutes
at 210OF and then oven-cured for 24 hours at 195 0 F. The tensile
strength of this compound (300 psi) was the highest obtained with the
Thiokol nitroso rubber. Compound 14 showed no signs of sponging.
None of the other variations produced a vulcanizate with more than
200 psi tensile strength.
Table XV shows the results when compounds were vulcanized with
other than amine crosslinking agents. None of these vulcanizates
could be tested; from visual examination none appeared to have been
cured.
To determine the curing characteristics of the nitroso rubber,
the viscosity, not only of batches 5702 and 5675 but also of the remaining four batches, was determined on the Mooney viscometer Table
XVI. Batch 5675 gave the lowest result, a viscosity of only 22.
The curing characteristics of a variety of compounds are given in
Table XVII. Compounds 12 and 13, which represent 3M and Thiokol
nitroso rubbers, respectively, showed great differences in curing
characteristics. Compound 7 is a compound in which 1 pphr of 1.4
cyclohexane bis (methylamine) replaced 1 pphr triethyletramine and
then 3 pphr of zin oxide stabilizer was added. This compound gave
the best curing characteristics, hence the same formula was used in
a series of compounds (8,9,11, and 12) in which the fillers were
varied by the use of different carbon blacks and the effect of zinc
fluoride was investigated.
Table XVI
MOONEY VISCOSITY OF VARIOUS
BATCHES OF NITROSO RUBBER
Thiokol Chemical Corporation
Batch Identification

Mooney Viscosity (ML-4+l

5702
5812
5812 (9/14/64)
5812 (9/15/64)
5812 (Part #3)
5675

35
35
36
35
36
22
49

212 0 F)

v)4

r-

Mfu

0
C%4

,r

*4

In'

tJ

-*

9-4

0.

ri

cr)

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CN

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anC'

Lo

L1,

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x

(7~) Lf) Ln CV

-*4
_r

CN

W)

C.:4

PACOLA

C)

E- E:-

O HL
H
C1
r_4
H-

C r4

C/30j

0)

C-)
:e.U

LA

c
r

-i

U)L
N1

LA

>4C)

YNH

H_

')

ulA!

HHLC

HHr-

Ni

HN

O 00

LA

to

0'

HqL

CNHOO

4J

0
4J

LA

OH

4j

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H.- LA
T
CV

4) C/3O0E

+1

;4-HV (L). 0('r..

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O co

r H- .

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l r-4

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(NH.,

1
r

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cjE

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0Jr

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(0

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1 1

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mr.0r.

Q)>1
X

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0LA(Y

tH 4
ol

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4

4-

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.a10

-4

4-'
o

51

) r )0
r -0
>

*
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4

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04

00

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0C:.

.,q~cv

02

94 4

With Thermax black as a filW-v, compeund 9, the zinc fluoride

iproved the curing chatracteristics of the nitroso rubber, as is
shown belou.
Time for Cure (beyond 35 min)

NO.
8

9
12
13.

No filler,

no zinc r1hcAd;e

no cure

Thermax black with zinc flucxrai

No filler with zin1fluoride
Therax black, no zinc f-laoride

5.5
no cure
14.5

Zinc fluoride in HAF black filler systems (compounds 13, 14,

and 15) did not change the curing characteristics of these compounds
to the same degree that it did with the Thermax black and it did not
improve the physical properties of the vulcanizates. In compounds
38 and 41, 2.5 pphr of triethylenetetramine and mixtures of carbon
black and silicone-treated fillers were used and the temperature was
reduced to 210OF (to eliminate sponging). The cure characteristics
produced were excellent but the physical properties were poor ,
Results of attempts to identify crosslinking of the nitroso
rubber by the use of differential thermal analysis techniques are
given in Table XVIII. Triethylenetetramine was the only material
tested that indicated crosslinking, and this occurred at 600 C. Using
this method of analysis, the second order transition of -500 C compares
with that previously reported on the 3M rubber. Table XVII shows that
the addition of triethylenetetramine reduced the temperature for the
onset cf deterioration from 220 0 C to 200 0C. The addition of Diak #I
(hexamethylenediamine carbamate) significantly reduced the temperature
for the onset of deterioration. This was also true when other amines
were used, and when d; umylperoxide was added.
Table XVIII
DIFFERENTIAL THERMAL ANALYSIS RESULTS
T&OC
Sample Identifi 3tion
Thiokol 5702

Thlokol 5702 with TETA

Thiokol
Thiokol
Thiokol
Thiokol
Thiokol

5702
5702
5702
5702
5702

with Diak #1
with H2N F F NH2
- TETA and UROTROPIN
- dicumylperoxide
- TETA, Diak #1, DPG, CAB-O-SIL

Tg = Second order transition temperature

Tc = Onset of crosslinking temperature
Td = Onset of degradation temperature
52

-50

--

220

-49

60

200

..
..
..
..
..

155
168
137
133
138

..
..
...
..
-.

&

C. Conclusions
The Thiokol Chemical Corporation nitroso rubber has different
curing characteristics from that made by the Minnesota Mining and
Manufacturing Company.
The phLsical properties of the compounds made and reported here,
using the Thokol Chemical Corporation nitroso rubber, were extremely
poor.
The reinforcing fillers HiSil 303 and the silicone-treated HiSil
233 were superior to the'medium thermal furnace blacks, the highabrasion furnace blacks, and the easy-processing channel blacks.
VII

Future and Potential Uses of Nitroso Rubber

The future of nitroso rubbers depends upon the types of uses that
can be developed for this unique elastomer. These uses, in turn, are
largely dependent upon the specific combinations of properties that
can be evolved from this architecturally unique molecular system. Undoubtedly nitroso elastomers are to be considered specialty rather than
general purpose elastomers.
Nitroso rubbers appear to have potential utility for applications
where corrosive environments are found, such as in the aerospace
ndustry, use in expulsion bladders and for valves exposed to rocket
uels and oxidizers. As a low temperature elastomer whose petroleum
resistance is required, nitroso elastomers may also have practical
utility. As a metal coating material nitroso elastomer may have
practical advantages in certain areas where extremely corrosive environments predominate.
VIII Summary
The syntheses of nitroso monomers and the practicability of carrying out pilot plant syntheses of nitroso polymers has been demonstrated.
Nitroso elastomers have unique combinations of properties not held by
an elastomer to date. These elastomers are the only completely fluorinatad
"rubber" materials known and indeed the only known case where a nitrono
group enters into a polymerization reaction to yield a -N-0-chain secuance in a Unear polymer. Tc retain these desirable properties and
a' the same time develop yet new elastomer systems with high tensile
strengths is the goal of the present effort. Current applications require materials having tensile strength superior to those now currently
known in the nitroso elastomer systems.
53

~IX

Acknowledeents
The authors would like to acknowledge their appreciation to
Dr. Stephen Kennedy, Director, and Dr. George R. Thomas, Associate
Director of the Clothing and Organic Materials Division for their
continuied support of this program;-also the authors appreciation is
expressed-to the National Acadenrj of Sciences and its Elastomer

iiAdvisory Panel which followed the progyeg-, of the work from its
earliest conception.

54

X. References
1. Barr, D.A. and R.Wo Hazeldine, J. Chem. Soc., 1881 (1955).
2. Barr, D.A. and R.Wo Hazeldine, J. Chem. Soc., 2532 (1955).
3. Barr, D.A. and R.W. Hazeldine, Nature, 175, 991 (1955).
4. Barr, D.A. and R.W. Hazeldine, J. Chem. Soc., 3416 (1956).
5. Rose, J.B. Crosslinked Reaction Production of Tetrafluoroethylene and Trifluoronitrosomethane and Process thereof.
Filed Oc-.
12, 1956, awarded 1962, U.S. Pat #3,065,214.
6. Fitt, PoS. Copolymers of Fluoronitrosoalkanes and Fluoroalkenes, Part I - Literature Survey Royal Aircraft
Establishment, Farnborough, England, 1320 (1957).
7. Barr, D.A., R.N. Hazeldine, and C.J. Willis, Proc. Chem.
Soc., 230 (1959).
8. Griffin, C.E. and R.N. Hazeldine, Proc. Chem. Soc., 369, (1959).
9. Rose, J.B. Rubbery Polymers to ICI Ltd. Brit. Pat #789,254
Jan. 1958.
10.

Gowenlock, B.G. and W. Luttke, Quarterly Reviews, 12, 321 (1958).

11.

Ruff, 0. and M. Giese, Ber., 69, 598684 (1936).

12.

Crawford, G.Ho to Minnesota Mining and Manufacturing Company,

U.S. Pat #3,072,592 Jan, 1963.

13.

Rue, D.N. and GoH. Crawford, J. Org. Chem. 28, 872 (1963).

14.

Brown, H.A. U.S. Army Contract DA-19-129-QM-1684, Minnesota

Mining and Manufacturing Co. Final Report, Aug 24, 1960 to
Dec 23, 1962. p 13.

15.

Andreades, S. U.S. Pat #3,040,085, June 19, 1962.

16.

Park, J.Do and AoPo Stefani, U.S. Pat #3,072,705, Jan. 1963.

17.

Barr, D.A., R.N. Hazeldine, and C.J. Willis, J. Chem. Soc.,

1351, (1961).

18.

Hazeldine, R.N. U.S. Pat #3,083,237, Feb 1963.

55

qi

JAI

X. References (continued)
19.

Flowers, W.T. Manchester University, England private communication.

20.

Sutcliffe, H. Royal College of Advanced Technology, England,

private communication.

21.

Barr, D.A. R. N. Hazeldine, and C.J. Willis, J. Chem Soc.,

1351 (1961).

22.

Crawford, G.H. D. E. Rice, and J. Montermoso, Paper presented at 137th ACS Meeting (1960). Cleveland, Ohio.

23.

Montermoso, J.C. Rubber Chem. & Tech., 34, 1521 (1961).

24.

Barson, G.A. and C.R. Patrick, Brit. Plastics, 36, (1963).

25.

Latlow, J.C. Rubber Plastics Age 39, 33 (1958).

26.

Bartholemew, S. R. et. al., Rubber Chem & Tech 32, 1585 (1959).

27.

Montermoso, J.C. Chem. Eng. Progress 57, 98 (1961).

28.

Montermoso, J.C. et. al., Rubber & Plastics Age 42, 514 (1961).

29.

Montermoso, J.C. et. al., U.S. Dept. of Commerce OTS Pub.

PB 181094, Proceedings of the Sixth JANAF Conference, Natick,
(1960).

30. Griffis, C.B. and M.C. Henry, Seventh National SAMPE

Symposium, Los Angeles, Calif., May 1964, Section 12,
Properties of Nitroso Elastomers.
31.

Griffis, C.B. and M.C. Henry, Rubber and Plastics Age 46,.
63 (1965).

32.

Stump, G. et. al., Polymer Letters 3, 831 (1965).

33.

Boyer, R. Rubber Chem. Tech. 36, 1303 (1963).

34.

Green, J. and N.B. Levine, Elastomeric and Compliant Materials

For Contact with Liquid Rocket Fuels and Oxidizers, ASD
Technical Report Part II, November 1961; Part III, July
1963, Tech. Documentary Report, Part I, March 1964.

35.

Levine, N.B. et. al., Elastomeric and Compliant Materials for

Contact with Liquid Rocket Fuels and Oxidizers, Technical
Report ML-TDR-64-107 Part II, February 1965; RMD Report
5062-Q6, Jan-Mar, 1965; RMD Report 5062-Q7, April-June 1965.
56

Unclassified
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I

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U.S. Army Natick Laboratories

Natick
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REPORT SECURITY

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3 nEPORT TITLE

NITROSO RUBBER HANDBOOK

4

DESCRIPTIVE

NOTES (Type of report and inclusive date#)

January 1957 - December 1965

5 AUTHOR(S) (Lost namie. first name, Initial)

Henry, Malcolm C. and Griffis, Charles B.

6 REPORT DATE

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SUPPLEMENTARY NOTES

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13

ABSTRACT

"Nitroso" rubber is the generic name for a family of rubbery high polymers having
the common structural denominator of a repea+ing nitrogen-oxygen-carbon atomic
sequence as follows:
-N-O-(C-)
I

I x

Architecturaiy these nitroso polymers are the first of a whole new class of
materials. Nitroso polymers, as currently known, are highly fluorinated or completely fluorinated and as such are members of a specialty type of elastomer since
only a limited number of fluorinated elastomers are known. It is becoming in-creasingly evident, however, that the combination of "nitroso" gro,,. - in the
highly fluorinated linear polymer chain is responsible for the introduction of
interesting and novel combinations of properties. Thus, nitroso elastomers have
good low temperature properties, solvent resistance, stability to corrosive environments, and flame resistance.
ANitroso

polymers have been developed to their present state by the cooperative

effort of Army scientists and contractors. Over the past eight years, considerable insight has been gained as to the nature and potential uses of nitroso
rubbers. This handbook is an attempt to asTsemble a summary of this accumulated
knowledge. It is hoped that the contents so compiled will aid in the future development of this new family of specialty elastomers.

DD IJAN4 1473

U
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s
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I..f,

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Unclassified
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KEY WORDS

LINK A
ROLE

Development

Chemistry

Preparation (Formulation)

81

.JINK C

LINK 8
ROLE

WT

ROLE

0T

8
2,9
0

Physical properties
Nitroso rubber
Handbooks

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or short phrases that charactertize a report and may be used as
index entries for cataloging the report. Key words must be
qo that no sdcurity classification is required. Identirs
uhaeqimtmollsintotrenmmlas equinment model esignation, trale name.dntasuch
liers
.!aryproject code name, geopraphic location, may be used -is
K-y words but will be followed bN an indication of technt( al
context

The isstgnment of links. rules, and weights is

optional

_S

Unclassified
ass fi iation

ec-urty -