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Patented Nov. 5, 1946
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2,410,775
UNITED STATES PATENT OFFICE
COLOR STABILIZATION OF VINYL
HALIDE RESINS
Fred W. Cox, Cuyahoga Falls, and James M.
Wallace, Jr., Akron, Ohio, assignors to Wing
foot Corporation, Akron, Ohio, a corporation of
Delaware
1
No Drawing. Application June 22, 1945,
.
1
Serial No. 601,060
9 Claims.
(01. 2s0_7s)
This invention relates to the stabilization of
though any other salt of amino-guanidine may
vinyl halide resins, and particularly the vinyl
be used. The quantity of stabilizer used will
halide resins which are polymers of» at least 70
depend upon the conditions of heating to which
percent of vinyl halide, including the polymers
the vinyl resin is to be subjected. If only mild
of 100 percent vinyl halide and the copolymers 5 heating is encountered, small amounts or even
of vinyl halides with other polymerizable monotraces of the agent will yield an improved prod
ole?m‘c compounds.
uct. Although the incorporation of from 0.05 to
‘.‘inyl halide resins generally will discolor when
10 percent by weight, based on the polymer con
heated, for example at a temperature of 100°
tent of the resin, will produce useful composi
C. or higher, and especially in the presence. of 10 .tions, generally the best results are obtained
iron or iron salts. It has been discovered that
from the use of from 0.5 to 5 percent of the
the addition of a small proportion of aminoguanidine or salt thereof.
guanidine or a salt of amino-guanidine will enThe stabilizing agent may be incorporated by
able the resin to resist the discoloration e?’ect
any of several methods. It may be added to
I for substantial periods of time.~
15 the solid resin and mixed therein by means of a
The vinyl halide resins which may be stabilroll mill or other mixing machine adapted to
ized in accordance with this invention include the
blend solid plastic materials. The ,mixing ma
polyvinyl halides, made by the polymerization
chine may be heated during the mixing oper
of any compound of the group consisting of
ation to render the compositions more plastic.
vinyl chloride, vinyl bromide, vinyl ?uoride and 20 Alternatively, the stabilizing agent may be dis
vinyl iodide without the presence of other polysolved in any suitable solvent and the solution
merizable mono-ole?nic compounds. The inven~
then mixed with the resin. The vinyl halide
tion is also useful in the prevention of discolorresin may be dissolved in a solvent, such as
ation upon heating in copolymers of from 70 to
ethylene dichloride, and the stabilizing agent
100 percent of a vinyl halide with from 0 to 30 25 added to the solution and dispersed therein by
‘percent of another polymerizable mono-ole?nic
means of any stirring device. If the polymers
compound. Although any polymerizable monoor copolymers are prepared by polymerization in
ole?nic compound which is compatible with the
an aqueous emulsion, the stabilizing. agent may
Vinyl halide in polymeric form, i. 8-, which forms
be added and distributed through the polymer
copolymers therewith, may be stabilized, the in- 30 prior to coagulation. Any other method which
vention is particularly Useful in the treatment Of
permits a uniform distribution of the stabilizing
copolymers of monomeric mixtures of vinyl halide
agent throughout the polymer may be used.
and up to 30 percent of Vinyl acetate, vinylidene
The stabilized resins may be used in theprepa
chloride, Styrene, the alkyl fumarates, the alkyl
ration of cast ?lms or in the fabrication of
maleates. the alkyl chloromaleates, the alkyl 35 molded or extruded shapes, which uses are well
chlorofumarateathe alkylacrylates. or the alpha
known to the art. The stabilized vinyl halide '
substituted alkyl acrylates. The copolymers
resins are particularly useful in the preparation
which are of particular importance are those of
of transparent or light colored articles in which
70 to 98 percent of vinyl halide and from 2 to 30
discoloration upon heating is undesirable.
percent of said other mono-ole?nic monomer- A 40
preferred class of copolymers are those of 80 to 95
percent of vinyl halide and from 5 to 20 percent
of the other monomer.
Further details of the invention are set forth
with respect to the following speci?c examples.
Exam le 1
p
'
a
The stabilization against discoloration upon
Each of three 10 gram samples of a copolymer of
heating is e?ected by the incorporation of amino- 45 90 percent vinyl chloride and 10 percent diethyl
guanidine or any salt of amino-guanidine. For
fumarate were milled with 2 ml. of dibutyl seba
obvious economic reasons the most useful salts
‘cate. Two of these samples were blended'respec
of amino-guanidine are those made by the retively with 0.2 gram of amino-guanidine sulfate
action of amino-guanidine with inexpensive readand with 0.2 gram of guanidine sulfate. The
ily available acids. Thus, the most useful salts 50 third sample wasused as a control for the pur
are the hydrochloride of amino-guanidine, the
pose ofcomparison. The copolymer samples were
bicarbonate of amino-guanidine, amino-guanidine sulfate, amino-guanidine nitrate, aminoguanidine acetate, amino-guanidine carbonate,
and the hydrosulfate of amino-guanidine, al- 55
milled separately on a laboratory-size chromium
plated roll mill for 5 minutes at 140° F. and then
for 5 minutes at 212° F. The copolymers were
rolled into sheets 1 mm. in thickness and Spegi
2,410,775
3
4
mens were cut therefrom for heat stability tests.
The specimens were introduced into an oven
heated at 135° C. and every half hour for 4 hours
discoloration upon heating which comprises a co~
polymer of 70 to 98 percent of vinyl chloride and
2 to 30 percent of diethyl fumarate, said resin
containing from 0.05120 10 percent by weight based
one of each type was withdrawn. It was found
that the copolymer containing amino-guanidine
on the polymer content, of a salt of amino-guani
dine.
sulfate was stabilized to the e?ect of the ele
4. A vinyl chloride resin capable of resisting
vated temperature, while the copolymer contain
discoloration upon heating which comprises a
ing guanidine sulfate and the control specimen
copolymer of 80 to 95 percent of vinyl chloride
containing no modifying agent were discolored to
10 and 5 to 20 percent of diethyl fumarate, said resin
about the same extent.
containing from 0.05 to 10 percent by weight based
Example 2
on the polymer content, of amino-guanidine.
Using the procedure described in Example 1 i
5. A vinyl chloride resin capable of resisting
the same copolymer was blended with 2 percent
discoloration upon heating which comprises a
of amino-guanidine bicarbonate and another
copolymer of 80 to 95 percent of vinyl chloride
sample with guanidine carbonate. The effect of
and 5 to 20 percent of diethyl fumarate, said resin
containing from 0.05 to 10 percent by weight
the addition of these modifying agents upon the
heat stability of the copolymer was determined
based on the polymer content, of a salt of amino
guanidine.
,
in the manner described in Example 1. After
6. A vinyl chloride resin capable of resisting
one hour of heating at 135° C. the specimen con 20
taining guanidine carbonate was discolored even
discoloration upon heating which comprises a
copolymer/of 70 to 98 percent of vinyl chloride
more than the control specimen, containing, no
modifying agent, while the specimen containing
and 2 to 30 percent of diethyl fumarate, said
resin containing from 0.5 to 5 percent by weight
25 based on the polymer content, of amino-guani
This application is a continuation-in-part of
dine.
7. A vinyl chloride resin capable of resisting
application Serial No. 502,314 ?led September 14,
discoloration upon heating which comprises a
1943.
copolymer of '70 to 98 percent of vinyl chloride
Although the invention has been described with
respect to speci?c examples, it is not intended 30 and 2 to 30 percent of diethyl fumarate, said
resin containing from 0.5 to 5 percent by weight
that the details thereof shall be construed as lim
based on the polymer content, of a salt of amino
itations upon the scope of the invention except
guanidine.
to the extent incorporated in the following claims.
8. A vinyl chloride resin capable of resisting
We claim:
discoloration upon heating which comprises a
1. A vinyl halide resin capable of resisting dis
copolymer of 80 to 95 percent of vinyl chloride
coloration upon heating which comprises a poly
and 5 to 20 percent of diethyl fumarate, said
mer of from 70 to 100 percent of a vinyl halide
resin containing from 0.5 to 5 percent by weight
and up to 30 percent of another polymerizable
based on the polymer content, of amino-guani
'mono-ole?nic compound, said resin containing
from 0.05 to 10 percent by weight based on the 40 dine.
9. A vinyl chloride resin capable of resisting
polymer content, of a compound of the group
discoloration upon heating which comprises a
consisting of amino-guanidine and salts of amino
copolymer of 80 to 95 percent of vinyl chloride
guanidine.
and 5 to 20 percent of diethyl fumarate, said
2. A vinyl chloride resin capable of resisting
discoloration upon heating which comprises a co 45 resin containing from 0.5 to 5 percent by weight
amino-guanidine bicarbonate was in perfect con
dition.
based on the polymer content, of a salt of amino
polymer of '10 to 98 percent of vinyl chloride and
guanidine.
2 to 30 percent of diethyl fumarate, said resin
containing from 0.05 to 10 percent by weight based
FRED W. COX.
on the polymer content, of amino-guanidine.
3. A vinyl chloride resin capable of resisting 50
JAMES M. WALLACE, JR.
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