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Патент USA US3058970

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United States PatentO ’
3,058,961 -
Patented Oct. 16, 1962
1
(v) '
3,058,961
POLYMERIZATION OF VINYLIC NITROSO COM
POUNDS AND PRODUCTS THEREOF
Robert N. Haszeldine, Windyrldge, Lyme Road,
.
Disley, England
No Drawing. Filed Oct. 17, 1960, Ser. No. 62,839
Claims priority, application Great Britain Oct. 27, 1959
Polymers of this type, having a skeletal chain consisting
of alternating carbon and nitrogen atoms are a result of
34 Claims. (Cl. 260-875) .
oxazetidine ring formation.
It will be understood that a given vinylic nitroso com
This invention relates to new chemical compounds con
taining carbon and nitrogen. In particular it relates to
compounds obtained by the polymerization of vinylic
nitroso compounds.
7
' pound may upon polymerization give two or more homo
polymers of different structures. Molecular weights may
- range from say 1000 to 500,000 or higher.
I
Nitrogen containing polymers have been prepared by
In its broadest aspect, the invention therefore com
the copolymerization of compounds such as tetra?uoro 15 prises homopolymers of vinylic nitroso compounds; to
gether with a method for making polymeric compounds
ethylene and tri?uoronitroso methane. Generally speak
containing carbon and nitrogen which comprises polym
ing these polymers have a chain formed of repeating units
erizing vinylic nitroso compounds.
of the type
The vinylic nitroso compounds of choice which are
20 used to form homopolymers in accordance with the in
l I
vention may be represented by the formula
They show good, thermal stability and can be used for
-ri-o-o-o
?ame resistant coatings and the like.
The present invention is based upon the discovery that
where X is ?ourine or chlorine and Y and Z each repre
vinylic nitroso compounds can be polymerized to form 25 sents hydrogen, ?uorine, chlorine or a poly?uoro- or
poly?uorochlorohydrocarbon usually containing not more
high molecular weight materials. The structure of these
than 10 and preferably not more than 5 carbon atoms
materials will depend on the formula of the monomer.
and which may contain non-interfering substituents.
In physical appearance they vary from mobile liquids to
When Y or Z represents a poly?uoro or 'poly?uorochloro
greases and elastomers and are useful as solvent resistant
gaskets and tubing and as temperature resistant greases 30 group, such group is typi?ed by per?uoro- or per?uoro
and lubricants.
‘ .
-
'
chloroalkyl, e.g. per?uoromethyl.
'
The invention therefore further comprises homopoly
Thus if the vinylic nitroso monomer, polymerized in
mers of vinylic nitroso compounds having the formula
accordance, with the invention, be considered to have the
skeletal structure
.
35
where X is ?uorine or chlorine and Y and Z are hydrogen,
?uorine, chlorine or a poly?uoro or poly?uorochlorohy
drocarbon group containing not more than 10 carbon
atoms; as well as a method for making polymers con
the following skeletal chainscan be distinguished.
‘”
~_é_é__<B-e-
v
taining carbon and nitrogen whichcomprises polymeriz
40
ing a monomer of the formula
' 11m ' I'm r
This structure arises from normal vinyl polymerization
through the —C=C-— linkage in the monomer.
(II)
‘ -
Preferably, the vinylic nitroso compound has the
formula
N0
45
CF2=CXNO
where as above, X is ?uorine or chlorine. In this case
This structure,lin which vinyl and nitroso groups alternate
as side chains, arises from formation of the
the polymeric product is that of Formula V above and
more speci?caly ‘has a chain characterized by repeating
50 units of the type
(VD
.-:—-N—'0—.C-.-C—
chain by reaction of the nitroso group of one molecule
(III)
an t l ,
[O—(lJF:
It will be observed that in the polymeric compounds
55 of Formula VI, the skeletal chain has alternating carbon
> . with the vinyl group of a second.
'
and nitrogen atoms. Such chains are thus quite different ‘
vfrom those of the known copolymers identi?ed above.
In a further aspect the invention therefore comprises
.~
‘I
_
HN-‘oi
Highly cross-linked polymers of‘ this structure are formed
,
by inter-reaction of the side chains of “II.
,(YW) "
.
‘ ~
.
60
polymeric compounds ‘having skeletal chains comprising
alternating carbon and nitrogen atoms; togetherl_.with a
process for making such compounds comprising polym
erizing a monomer of the formula
j
, r
-<:>-t':=N-o-<li-$=N-o_'
Polymers of this structureiarise ‘Iby‘the reaction of the
to give alinear chain
containing
65
More speci?cally the invention additionally ‘comprises
polymeric products having chains characterized by the
' repeating unit
v ,viiiylienitroso monomer ‘as a diene
‘ IEZEF’L
70 and to a method for making such products by polymeriza
‘ groups.
tion of monomers having the formula
8,058,961
The mechanism by which this is obtained may be de
picted as follows:
In general, the reaction to give a homopolymer of a
, vinylic nitroso compound is carried out by subjecting the
compound to conditions conducive to the formation of
0-b
free radicals. This may involve subjecting the‘ starting
material to energization by heat, ultra-violet, infra-red,
_+_ i Eli
X, 'y or high energy electron radiation or by utilizing an
initiator such as peroxide or azo-type initiator. Both
temperature an‘ pressure are important factors in the 10
reaction and should be appropriately chosen for the par
ticular vinylic nitroso compound subjected to polymeriza
Where the oxazetidine polymer was made from a mono
tion. In general, temperatures from —50 to 150° C. and
mer CF3=CXNO, the product obtained has a chain
pressures from 5 to 300 atmospheres will be used. Re
action time will vary from 95 to say 48 hours depending 15
-cX=N_cx=N_cx=N-;
‘
on other reaction conditions, especially pressure. By
In the speci?c case of a polymer having the structure
way of guidance, it may be stated that to prepare a
C—OF,
homopolymer of formula VI from tri?uoronitrosoethyl
cue, the polymerization may be effected at a pressure of
say 5 atmospheres to 200 atmospheres, at a temperature 20
in the range from about 20 to about 200° C. and in the'
The chain
presence of an initiating agency such as ultra-violet light;
preferred temperatures range from about 50°C. to about
(VII)
100° C. and preferred pressures range from about 20 to
is obtained.
about 60 atmospheres.
-
——OF—N— F-N-O-N
-—
F:
v
-
F2
25
These products and the pyrolysis process by which
they are made comprise a still further aspect of the in
vention.
elastomers. For example, the homopolymer of tri?uoro
In general the pyrolysis is conducted at say 150° C.
nitrosoethylene is an elastomer which has good low
to 600° C., with time adjusted to temperateure so that
temperature characteristics, which is insoluble in organic 30 the
C—N bond is not broken. For example, at around
solvents to which rubbers might commonly be exposed
The polymers prepared as described above may take
the form of mobile liquids, viscous liquids, greases or
400° C. times on the order of 5 seconds to 5 hours are
in use but which is soluble in a ?norinated solvent such
satisfactory. Pressure is not critical and is desirably
as per?uoromethylcyclohexane thus enabling it to be
about
atmospheric. It may, however, range from say 1
formed into ?lms by applying asolution thereof to a
to 300 atmospheres.
substrate and evaporating the solvent.
35
The unsaturated polymers just described exhibit great
The products of most interest and utility, e.g. as lubri
thermal stability which makes them useful where such
cants used at high temperatures or as elastomers, are
stability is necessary, e.g. in the manufacture of labora
those prepared from per?uoro vinylic nitroso compounds.
tory ?ttings for apparatus to be used at high tempera
The homopolymers of Formula VI may be isotactic,
tures.
atactic, or syndotactic and the formulae used herein are 40
It has further been discovered that the vinylic nitroso
not intended to denote any particular stereospeci?c
compounds which produce homopolymers as described
polymer structures.
above also form copolymers with ?uoroalkenes. Thus,
In preparing oxazetidine type homopolymers (Formula
for example, useful chemically resistant oils, greases,
VI) from compounds of the type
45
there may be obtained in addition to the polymer de
scribed above, a fused ring dimer of formulav
waxes and, in some cases, elastomers may be prepared
by copolymerizing a per?uoro- or per?uorochloro-vinylic
nitroso compound with a poly?uoroalkene. If the tin
oroinated vinylic nitroso compound be represented as
R;NO and the recurring unit present in the copolymer
and which is derived from the ?uoroalkene be represented
50 as R',, then copolymers having a repeating unit of the
following type may be produced, viz.
For example, when tri?uoronitrosoethylene is polymer
ized, there results in addition to an elastomer, the fused
55 where n and m are integers of l to 30. While the values
of n and m depend upon the ?uoroalkene used, it is gen
erally the case that the copolymers consist either pre
dominantly or exclusively of a 1:1 copolymer, i.e. a
copolymer in which n and m in Formula VHI each have
60 a value of one. The copolymers may range in molecular
weight from say 5000 to 500,000.
By virtue of the vinylic R; side chains which ‘distinguish
the
copolymer of Formula VIII from previously known
These fused dimers are produced under the same condi
copolymers having a -—N—
repeating unit
tions which giverise to the oxazetidine type homopoly 65 but no vinylic unsaturation in the side chains,
the copoly~
mers. They are new materials, useful as solvents and they
mers can be cross-linked to give insoluble infusible
and their preparation comprise yet further aspects of
products. Cross-linking may be effected by means of
the invention.
peroxides or by reaction of the copolymers with poly
It has further been discovered that polymers of the
functional compounds such as diamines and diols. The
type identi?ed by Formula VI above can be pyrolyzed 70 vinylic R; groups in the copolymers may also be con
to give, as a pyrolysis product, an unsaturated polymer
characterized by a chain of the type
verted into other functional groups, e.g. to carboxylic
acid groups by reaction with an oxidizing agent such as
potassium permanganate.
Preferred ?uoroalkenes used to form copolymers with
75 vinylic nitroso compounds are those of the formula
8,058,961
\.
6
RBRhCQCF-Q, where Rgand Rb represent ?uorine, chlorine,
hydrogen, alkyl and ?uoroalkyl, chloroalkyl and fluoroy
Formula VIII or an oxazetidine compound of the type
represented'by'Formula X. initiators such asultra-violet
chloroalkyl groups having not more than say 10 carbon
atoms. Typical ?uoroalkenes are the compounds
light or a chemical initiator, such as a peroxide or use
CF,=CF,, CFg=CClg and CF,=CFCI. Theselatter com- ‘
pounds copolymerize with vinylic nitroso‘ compounds of
the type CFQ=CXNO where X is ?uorine and chlorine,
to form 1:1 copolymers having the characteristic repeat
ing unit
-
where X is fluorine or chlorine. .
v
compound, may also be employed. The use of chemical
initiators is, however, not preferred because of the trouble
of removing fragments of the initiator from the product.
As regards the ?uoroalkenes which may be used in the
copolymerization reaction with the nitroso compound,
the compounds CF,=CF,, CF¢=CFCL CFFCCIQ and
10 CF,CF=CF, have already been speci?cally mentioned.
Other compounds are CF,=CH,, CF§==CHF and com
pounds of the series CF,(CF,),,CF=CF, where n is an
integer of not more than 20. For chemical stability and
,
The invention thus further comprises copolymers of
vinylic nitroso compounds and ?uoroalkenes, together with
a method for making polymeric products containing ?uo
solvent resistance, per?uoro- or per?uorochloro- alkenes
are preferred. On the other hand, when a hydrogen
containing poly?uoroalkene is used, the hydrogen enables
vthe copolymers to be cross-linked by peroxides, amines,
- rine, nitrogen and carbon which comprises copolymeriz
etc. and the copolymers, before cross-linking, are more
ing a vinylic nitroso compound with a ?uoroalkene.
solublein conventional solvents such as acetone. Mix
In the reaction between a vinylic nitroso compound
and a fluoroalkene, an oxazetidine compound can also be 20 tures of poly?uoroalkenes may be used, if desired. Where
asymmetrical poly?uoroalkenes are used, and reaction
produced. For example, reaction of a nitroso com
takes place by addition of the N--O group of the nitroso
pound CFFCXNO with a ?uoroalkene of the formula
compound to the C=C groups of the alkene, there exists
CF,='CX, yields an oxazetidine compound of the formula
the possibility that the direction of the addition of the
25 N—-O group is not always the same. When the vinylic
' or.=ox.N--o
(X)
OFI
nitroso compound is CF3=CFNO or'CFF-“CCINO and
X:
elastomers are desired, alkenes of ?rst choice are
The invention therefore further includes oxazetidine
compounds of this general formula and the method by
which they are made. ,
It may bepointed out that copolymers of Formula VIII
CF,==CF,, CFFCHF, CFFCFCI, and CFaCF==CF=;
the poly?uoroalkene CFFCH, may also be used al
though in this case cross-linking of the copolymer is indi
cated in order to obtain an elastomer.
'
and oxazetidine compounds of the type exempli?ed by
The varoius aspects of the invention described above
Formula X are not necessarily the only products which
are illustrated by the following examples. In the pro
cedure described the reactants were carefully puri?ed and,
can be formed by the reaction of a vinylic nitroso com
pound and a ?uoroalkene. In particular copolymers of
other structures may result. For example, when vinylic
nitroso compounds other than those of formula
CFFCXNO are used, saturated copolymers may result
from normal vinyl polymerization through the C=C link
ages in the vinylic nitroso compound and the ?uoro
alkene.
‘
'
In accordance with the invention the reaction of the
vinylic nitroso compound and a ?uoroalkene will, in gen
in particular, steps were taken to exclude air and moisture.
Temperatures are in degrees centigrade.
EXAMPLE 1
Dimerization and Homopalymérization of Tri?uoro
m'rrosoethylene
Tri?uoronitrosoethylene (20.1 mole) was sealed in a
thick-walled, narrow-boresilica tube of 5 ml. capacity,
eral, be conducted at temperatures from ---50'‘’ C. to
together with chlorotri?uoromethane to give a maximum
150° C., at pressures from I'to 300 atmospheres, with 45 pressure at room temperature of 40 atmospheres. Pre
?uoroalkeneznitroso compound molar ratios of from
1:10 to 10:1, preferably about 1:1 and at reaction times
of say V: to 48 hours. Obviously, however, the optimum
temperature and pressure to be used will depend upon
the identity of the nitroso compound and the ?uoroalkene
reactants and the nature of the desired, product. For .
example, a copolymer of the structure of Formula IX
results when per?uoronitrosoethylene and tetra?uoro
ethylene and/or trichloro?uoroethylene are polymerized
at a temperature from —30" C. to 30° C., particularly
around 0° C., and a pressure of from l—50 atmospheres;
in contrast the formation of an oxazetidine compound is
favored when these compounds are reacted _at higher
cautions weretaken in manipulating the tube which could
cause serious damage on explosion.
As soon as the tube
reached room temperature, it was exposed first to infra
red radiation to raise its temperature to approximately
80° and then, whilst still exposed to infra-red radiation,
to ultra-violet radiation from a‘ Hanovia lamp for 30
minutes. The tube was re-frozen in liquid nitrogen,
opened, and the colorless gaseous products were distilled
to give the dimer;
'
-
temperatures of about 50° C.-100° C.
When a more
diliieultly polymerizablc ?uoroalkcnc is used, e.g. per 00 (56%) (Found: C, 21.4; N, 12.4%; mol. wt.=222.
C,O,N,F¢ requires C, 21.6; N, 12.6%; mol. wt.=222).
?uoropropene, in conjunction with a vinylic nitroso com
The compound had a boiling point of 45 ° C. and was a
pound of formula CF,=CFXNO, copolymer formation
colorless liquid. A mixture of a carbonyl ?uoride, silicon
will be favored by higher temperatures, e.g. in the range
from 40--80° C. in conjunction with higher pressures of, 65 tetrachloride and carbon-dioxide was also obtained. There
was no evidence for the formation of hexa?uorobutadiene
say, 5-40 atmospheres.
or its dimers etc. Ultra-violet and infra-red spectroscopic
Whether an elastomer can be produced will depend on
examination failed to reveal absorption associated with
' the nature of the comonomers used. If the comonomers
-N:O, -N0,, --N:N—,
'
used are those capable of yielding an elastomer, then
careful puri?cation of reactants is a factor conducive to 70
elastomer formation.
.
The reaction of the vinylic nitroso compound and the
?uoroalkene may also, in certain cases, be catalyzedvby
small amounts, e.g. 1%, of NO, and by glass wool or
other surfaces. The use of such catalysts is particularly
indicated when the desired product is a copolymer of
“ONO, --ONO,, >N.0.N0, >N.NO, >N.NO,, etc.
groups; the weak general absorption in the ultra-violet
spectrum in the 200-250 my region in particular, sug
gests that only the N--0 single bond is present, as in
the compound (CF;),N.O.CF,.
8,058,961
8
terial was apparent, and all the nitroso-compound had
The residual material in the reaction tube was a color
less, translucent elastomeric gum, the homopolymer of
disappeared.
tri?uoronitrosoethylene,
In a parallel experiment carried out at 0° for two days
the oxazetidine was not formed and the lzl-copolymer
_
an}
(|)—O Fa
‘
‘
[-N_(CF:CF3)-O-CF,1-CFCl-]n of the nitroso-compound
and chlorotri?uoroethylene was isolated (53% yield)
I
(Found: C, 21.2; N, 6.3%. [C.,,NOClF¢,]n requires C,
(28%) (Found: C, 21.7; N, 12.8% (C2ONF3),, re
quires C, 21.6; N, 12.6%). It was soluble in per?uoro
21.1; N, 6.2%) as an elastomer with good “snap."
The tri?uoronitrosoethylene used in the above examples
methylcyclohexane but not in the common organic sol 10 is representative of an entirely new class of chemical com
vents,‘and had a molecular weight of approx. 100,000.
pounds and-is a vivid deep blue gas (B.P. -——23.7°) that
Examination of the ultra-violet spectrum of a saturated
shows no'indication of association in liquid or vapor
solution in per?uoromethylcyclohexane, and of the infra
phase. Its ultra-violet spectrum shows the broad band in
red spectrum of a ?lm on rock salt failed to reveal ab
the 665-685111/4. region shown earlier to be characteristic
sorption associated with multiple carbon-oxygen, carbon 15 of the >CF-NO group. Its infra-red spectrum shows the
carbon, carbon-nitrogen, nitrogen-nitrogen, nitrogen
typical CF2=CF—absorption at 5.55pcf.
oxygen, etc. bonds, eliminating the structures I-IV above
and establishing the cyclic structure indicated immediately ,
above.
5.5a together with the N:O stretching vibration at 6.2511.
In contrast to the above experiment, when tri?uoro~ 20
(cf. CFs- [CF?n-NO, 6.23”).
nitrosoethylene (2.1 mole) was irradiated with ultra
violet light in a 20 ml. Pyrex tube for 78 hours at 20°,
As regards the thermal stability of the compound, heat
ing at 100° for 150 hours produces little degradation.
On the other hand, the compound was totally destroyed
no homopolymer or dimer was formed and the products
were unchanged nitroso compound (3%), CO2, SiF4,
when heated at 100° for 48 hours, then at 110° for 24
hours and ?nally at 125° for 48 hours.
N20, and hexa?uorobutadiene. Comparison of this ex
periment with that described above indicates the marked
and surprising e?‘ect of pressure upon dimer and homo
polymer formation. Indeed from the low pressure ex
periment it ‘might well have been concluded that tri?uoro
Tri?uoronitrosoethylene may be prepared by the photo‘
chemical reaction of nitric oxide with tri?uoroiodoethyl
ene.
nitrosoethylene would not undergo homopolymerization. 30
Starting with tri?uoroethylene, the nitroso com
pound may be synthesized by the following route:
ICl
.
CF3=CHF
EXAMPLE 2
————-r
KOH
CFzClCHFI ——>
CFFCFI
NO-h'
Pyrolysis of Tri?uoronitrosoethylene Homopolymer
CFFCFI —» CF,=0FNO
Es
A 0.15 g. sample of the tri?uoronitrosoethylene homo<
polymer prepared as in Example 1, was placed in a sealed 35
A typical preparation of tri?uoronitrosoethylene by
silica tubeand heated to 400°. The heating was con
the photochemical reaction of nitric oxide with tri?uoro
iodoethylene is given in the experiment reported below:
tinued for 2 hours. At 310° the polymer had become
pale yellow and at 400° some shrinkage could be de
EXPERIMENT
tected, although there was little further. change in color. 40
Examination of the volatile products revealed the pres
Tri?uoroiodoethylene (5.45 g., 21.4 mmole), nitric
ence of carbonyl ?uoride (66%),‘and small amounts of
oxide (1.61 g., 53.5 mmole) and mercury (100 ml.) in a
silicon tetra?uoride and carbon dioxide. The residue was
a pale yellow solid without elastomeric character, but
was still soluble in per?uoromethylcyclohexane; the solu
tion showed absorption at 5.65# in the infra-red, to be
associated with the -—CF=N—CF= group indicating
the product had the structure of Formula VII above. Its
molecular weight was approx. 50,000.
EXAMPLE 3
2.1 silica ?ask were irradiated for 48-76 hours with a 250
watt Hanovia ultra-violet lamp. The ?ask was shielded
so that the surface of the mercury was not directly il
luminated. The course of the reaction could be followed
by the development of a faint blue color. The excess of
nitric oxide was removed by admission of oxygen to the
?ask and agitation of the mercury to remove ?nal traces
50 of dinitrogen tetroxide, and the volatile products were
Reaction of Tri?ttoronitrosoethylene With Tetra?uoro
ethylene and chlorotri?uoroethylene
(A) Tri?uoronitrosoethylene (7.2 mmole) and tetra
?uoroethylene (7.2 mmole) heated in a 20 ml. Pyrex tube
at 85° for 10 hours gave per?uoro-2-(tri?uorovinyl)-l:2
oxazetidine (69%) (Found: C, 22.7; N, 6.5%; mol.
wt.=211. C4ONFq requires C, 22.8; N, 6.6%; mol.
wt.=211), B.P. 41-43“ (micro).
In a second experiment, triu?oronitrosoethylene (7.4
mmole) and tetra?uoroethylene (7.4 mmole) reacted
during 48 hours at 0° in a 50 ml. Pyrex tube with disap
pearance of the blue color to give the 1:1-copolymer
slowly pumped (1 hr.) through two traps in series cooled
by liquidnitrogen. Distillation gave unchanged tri?uoro
iodoethylene (1%), tri?uoronitrosoethylene (0.219 g.,
1.99 mmole; 9%). (Found: C, 21.8; N, 12.3%; and mol.
wt.=lll. C2ONF3 requires C, 21.6; N, 12.6%; mol.
wt.=111), and a mixture of carbon dioxide, carbonyl
?uoride, and silicon tetra?uoride (21.0 mmole).
I claim:
1. Polymers of vinylic nitroso compounds said poly
mers having a chain of which the nitrogen atom of the
nitroso compound is an integral part.
~
2. Homopolymers of vinylic nitroso compounds, said
compounds having the general formula
[-(CF:CF,,)-O-CF2CFz-]n (71%) (Found: C, 22.9; N,
6.4% . C4ONF7 requires C, 22.8; N, 6.6% ). ‘The molecu 65
lar weight was about 100,000. The polymer was a thick
colorless gel, which when triturated with ether gave a
tough translucent elastomer, insoluble in the common
where X is selected ‘from the group consisting of ?uorine
and chlorine and Y and Z are selected from the group
consisting of hydrogen, ?uorine, chlorine and poly?uoro
organic solvents.
and poly?uorochlorohydrocarbon groups having not more
chlorotri?uoroethylene (4.0 mmole) were heated at 90°
for 7 hours, the product was 4-chloro-2-(tn'?uorovinyl)
chain of which the nitrogen atom of the nitroso compound
(B) When tri?uoronitrosoethylene (4.0 mmole) and 70 than 10 carbon atoms, and said homopolymers having a
is an integral part.
'
3:3:4-tri?uoro-1z2-oxazetidine (57%). (Found: C, 21.0;
3. Homopolymers of vinylic nitroso compounds hav
ing a skeletal chain of alternating carbon and nitrogen
6.2%; mol. wt.=227.5) B.P. 73-75". No polymeric ma 75
atoms.
N, 6.2%; mol wt.=226. C4NOClF6 requires C, 21.1; N,
-
16. Polymeric products having a chain characterized
4. Homopolymers or vinylic nitroso compounds, said
compounds having the formula
by the repeating unit
;
'
--N-0—CFs-CFG1
. F=OF|
where X is selected from the group consisting of ?uorine
and chlorine and said homopolymers having a chain, of
which the nitrogen atom of the nitroso compound is
17. Compounds having the general formula
OFFOXHNWO
an integral part.
' 5. A polymeric product having a chain characterized
by the repeating unit
"
Fsq' . Xs
18. A compound having the formula
'
OFFOFwNwO
I
where X is selected from the group consisting of chlorine
and ?uorine.
.
{their
7. A polymeric product having a
NwOF
-
chain characterized
by the repeating unit
___N,-_=(;X__
Fl
OFF-CIL-NWO
15
6. A polymeric product having a chain characterized
by the repeating unit
Fr'
19. A compound having the formula
Fr- E61
20. A method for forming polymeric compounds con
taining carbon and nitrogen atoms as integral parts
of a main polymer chain which comprises subjecting
20 vinylic ‘nitroso compounds to conditions conducive to the
,
formation of free radicals, said conditions including a
temperature of between about -50 and about 150' C.
and a pressure of between about 5» and about 300 atmos-j
phcres.
where X is selected from the group consisting of chlorine
25
21. A method for forming polymeric compounds con
and ?uorine.
taining nitrogen and carbon atoms as integral parts of
' 8. A polymeric product having a chain characterized
a main polymer chain which comprises subjecting a
by the repeating unit
vinylic nitroso compound having the general formula
9. Compounds having the general formula
80
where X is selected from the group consisting of ?uorine
and chlorine and Y and Z are selected from the class
consisting of hydrogen, ?uorine, chlorine and poly?uoro
and polytluorochlorohydrocarbon groups having not more
where X is selected from the group consisting of ?uorine v 35 than 10 carbon atoms, to conditions conducive to the
formation of free radicals, said conditions including a
and chlorine;
temperature between about ---50 and about 150° C. and a
pressure between about 5 and about 300 atmospheres.
10. A compound having the formula
22. A method for‘forming polymeric compounds hav
40 ing a skeletal chain of alternating carbon and nitrogen
atoms which comprises subjecting a vinylic nitroso com
pound having the general formula
11. Copolymers of vinylic nitroso compounds and
?noroalkenes. said copolymers having a chain of which
the nitrogen atom of the-nitroso compound is an integral 45 where X is selected from the group consisting of chlorine
part.
and ?uorine to conditions conducive to the formation
of free radicals from said nitroso compound, said con
ditions including a temperature between about —50 and
about 150° C. and a pressure between about 5 and about
>
12. Polymeric products having a chain characterized
by the repeating unit
50
300 atmospheres.
23. A method for making a polymeric product having a
chain characterized by the repeating unit
where R, is selected from the class consisting of perfiuoro
alkene and per?uorochlorovinyl groups, R’, is a ?uoro
alkylene group, and m and n are integers from 1 to 30.
13. Copolymers of vinylic nitroso compounds having
the formula CF,=CXNO and ?uoroalkenes having the
formula R,,R,,C=CF, where X is selected from the group
consisting of ?uorine and chlorine and Ru and Rh are
selected from the class consisting of ?uorine, chlorine,
hydrogen, alkyl and ?uoroalkyl, chloroalkyl and ?uoro
chloroalkyl groups said copolymers having a main chain
of which the nitrogen atom of the nitros'o compound is
an integral part.
.
'
14. Polymeric products having a chain characterized
by the repeating unit
-N--o-»01r,—0Xi
X=0 1":
'
O—-O F]
55
'[in-hr M
which comprises subjecting the compound
CF,=CFNO
to conditions conducive to the formation of free radicals,
said conditions including a temperature between about
~50 and about 150° C. and a pressure between about 5
and about 300 atmospheres.
24. A method for making polymeric products having
a chain characterized by the repeating unit
{2:221
which comprises subjecting a vinylic nitroso compound
having the formula
where X is selected from the group consisting of ?uo
CF2=CXN°
70
rine and chlorine.
where X is selected from the group consisting of ?uorine
15. Polymeric products having a chain characterized
by the repeating unit
._Nw()—-OFg—~CFs-—
ANTI-01H
.
and chlorine to conditions conducive to the formation of
free radicals said conditions including a temperature be
tween about -—50 and about 350° C. and a pressure be
75 tween about 5 and about 300 atmospheres.
3,058,961
-
11
30. A method‘ of making polymeric products having
25. A method for making compounds of the formula
a chain characterized by the repeating unit
0-0 F,—<I;>r—N-ox—-N-o-0Fi
L____l L____l
which comprises subjecting a mixture of compounds hav- .
which comprises subjecting a vinylic nitroso compound
having the formula
ing the formula CF2=CXNO and compounds having the
formula CX3=CF2, where X is selected from the group
consisting of ?uorine and chlorine, to conditions con
ducive to the formation of free radicals, said conditions
including a temperature between about —50 and about
CFz=CXNO
where X is selected from the group consisting of ?uorine
and chlorine to temperature between about ~50 and about
150° C. and a pressure of between about 5 and about
150° C. and a pressure between about 1 and about 300
300 atmospheres.
26. A method for making a compound of the formula
atmospheres.
‘
31. A method for making polymeric products having
15 a chain characterized by the repeating unit
—N-o-cm-or,
‘
F=0F,
which comprises copolymerizing the compound
which comprises subjecting a compound of the formula
20
CF2=CFNO
CF2=CFNO
with CF2=CF2 at a temperature between about —50
and about 150° C. and at a pressure between about 1
and about 300 atmospheres.
pheres.
'
32. A method for making a compound having the
I 27. A method for making a polymeric product having 25
to a temperature between about —50 and about 150° C.
and a. pressure between about 5 and about 300 atmos
general formula
a chain characterized by the repeating unit
CFz=CX—N—O
F:- X:
where X is selected from the group consisting of ?uorine
and chlorine, which comprises subjecting a polymeric 30 where X is selected from the group consisting of ?uorine
and chlorine which comprises reacting a compound hav
product having a chain characterized by the repeating
ing the formula CF2=CFXNO with a compound having
unit
the formula CF2=CXz at a temperature between about
N-OX
_[ (i)-—til F1}
~50 and about 150° C. and at a pressure of between
to pyrolysis at a temperature between about 150° C. and
about 600° C.
35
about 1 and about 300 atmospheres.
33. A method for making a compound of formula
0F,=oF-N—0
I
Fz-CF:
28. A method for ‘making polymeric products having
a chain characterized by the repeating unit
40
which comprises subjecting a polymeric compound having
a ckain characterized by the repeating unit
which comprises reacting the compound CF2=CFNO
with the compound CF3=CF2 at a temperature between
about —50 and about 150° C. and at a pressure of between
tween about 1 and about 300 atmospheres. .
34. A method for making a compound having the
0-013}
{an
formula
'
GFs=CF—N—-—O
to pyrolysis at a tempterature between about 150° C.
and about 600° C.
rz-orol '
_
29. A method of making polymeric products having
a chain characterized by the repeating unit
which comprises reacting the compound CFg-CFNO
with the compound CF2=CFCl at a temperature between
and —50 and about,150° C. and at a pressure of between
—Nv—0—[R’i]n-—N—0—[R’|]m—
t
about 1 and about 300 atmospheres.
'r
where R, is selected from the class consisting of per
?uorovinyl and per?uorochlorovinyl groups, R’; is a
References Cited in the ?le of this patent
?uoroalkylene group and m and n are integers from 1 55
to 30 which comprises copolymerizing a ?uoroalkene
with a compound having the formula at a temperature
between about —50 and about 150° C. and at a pressure
between about 1 and about 300 atmospheres
_ FOREIGN PATENTS
1,159,935
France ...._______________ ___July 3, 1958
OTHER REFERENCES
60
Takeuchi: Chemical Abstracts, vol. 47, page 11,916
(1953).
,
13
v.
n
_
1t
UNITED STATES .PATENT OFFICE
‘CERTIFICATE OF CORRECTION
Patent No. 3,058,961
,
October 16, 1962
Robert N. Haszeldine
It is hereby certified that error appears in the above numbered pat
ent requiring correction and that the said Letters Patent should read as
corrected below.
._
-
Column 3, lines 50V to 53', the formula should appear as
shown below instead of as in the patent:
'same column 3, lines 59 to 61, the formula should appear as
shown below instead of as in the patent:
column‘ 4,’ lines 46 and 47, for "fluoroinated" read —— fluorinated
———; column 6, line32, for "varoius". read —- various -—; column
7, line 60, for "triufloronitrosoethylene" read -— trifluoro
nitroso'ethylene -—-;- line 64, the formula should appear as shown
below instead of astin the patent:
column 8I ‘ lines 16 to l9,~ for "typical CF2=CF——absorption 'at ;
5.55p.cf.
'
5.5p, together with the NzO stretching vibration at 6.25p.“ read
—— typical CF2=CF—-absorption at 5.55p. (cf.v CF3[CF2]n~CF=CF2, ’
5.56p.) togetherywith the N:O stretching vibration at~-6.25p, '——; _
column ll,v line 11, after "to" insert —— a ——; line 46, for
"tempterature" read -- ‘temperature -—; same column 11, line
‘ 60,
strike out "RfNO" and insert the same‘ after "formula" in ,
line 57, same column 11; column 12, line 42,-v strike out "tween";
line 50,
for "and",
first occurrence”
read —— about ——.
'
Signed and sealed this 21st dayof May 1963.
(SEAL)
Attest:
ERNEST w. SWIDER
'
Attesting Officer
Commissioner of Patents
‘ DAVID L.
LADD
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