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Патент USA US2138192

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2,138,192
Patented Nov. 29,1938
‘Q UNITED. STATES ‘PATENT- oF-Fici: ~
Emil on, wummmn, net’,- assignor‘ toll’ierc'ules
_ VREISSUED
Powder Company, Wilmington, ,Del., a corpora
tion, of Delawalfe ,,
‘ No Drawing.
g‘ ‘SEP 17 1940
Application January ‘'31, 1936;
_. Serl‘al‘NVo. 61,759
‘
y’
r
. 11, Claims. (01. 105-42,)“ a:
My invention relates to a synthetic rubber‘ com
position and more specifically to a synthetic rub
containing compoundaias, ‘wood rosin, pinetar,
etc.,.vulcanization accelerators, sulfur, etc., they
ber composition“ comprising polymerized chloro
may-contain rubber anti-oxidants, such as‘, a
phenyl-naphthylamine, for ‘' example,. phenyl
prene'and chlorinated para?‘in.
“ 1,
5 I Synthetic rubber compositions including poly
alpha-naphthyl‘amine (Neozone A), phenyl-beta
merized chloroprene as a base, show considerable ‘ naphthylamine (Neozone D), etc. ; they may con
advantage over a. similar compositions including
tain reinforcing‘pigments, such as, carbon, blacks, . '
natural rubber as a base‘, in that‘ they possess
higher resistance to solvents, particularly gasoline
10 and mineral oils, and showless loss of desirable
physical properties on exposure to solvents; For
this‘ reason, such synthetic rubber compositions
have found wide ‘application in the manufacture
of gasoline hose, gaskets and other articles which
15 come into contact with solvents; Such composi
tions are,»however,' not entirely resistant to swell
ing in solvents and further improvement is desir
clay, blanc ?xe, etc.; they‘may contain ?llers
and/o‘r diluents, such as’ “whiting? barytes, as
bestine,‘ factice, rubber, various synthetic plase, 10
tics?glue, etc,;*.they may contain softeners, such
as, para?lnrwax, fatty .acids, oils,v tars, cumar
resins, etc.;v and they. may contain deodorants,
such as terpene compounds, etc.
'
.
~ ’
"Thecomposition in accordance with my inven 15
tion may contain chlorinated para?ln wax. .in
amount within the ‘range of about 1% to about
100% by weight based on the amount of polymer
I have invented a ‘synthetic rubber composition‘ ized ‘chloroprene present, and will preferably con
a which is highly resistant to the swelling action of tainlchlorinated paraiiinwax in amount within 20
the range of about 30% to about 70% byweight
gasoline ‘and mineral oils‘, which comprises es
sentially polymerized chloroprene and a chlor of the polymerized chloroprene present. ‘ ' . ,
able.
‘
'
'
inated paraffin wax having a chlorine ‘content’
sufficiently highto render the said‘ wax insoluble
The chlorinated paramn ‘wax-polymerized
chloroprene composition may be vulcanized by
heat alone with no additional ingredients present. 25
, It will be found, however,- that the properties of
‘ positions, in accordance with my invention, will this composition will be enhanced bycompounding desirably have ‘a chlorine content of not less ‘than it with other ingredients. Thus for example,
:3
in gasoline.
,
I
“
-
' The chlorinated para?in wax used inthe com
about 52% by weight, and may havevas high ‘a
& chlorine content as canbe obtained.
The prac
tical upper limit appears to be about 62%’ by
. weight.
The chlorine content of the chlorinated
parai?n wax, used in accordance with this inven
tion will, then, bewithin the range of about 52%
l as, to about 62% by~weight." ‘The chlorinated paraf
rosin, abietic acid vor pine tar will be found‘to be
highly
desirable.
,
-
,
.v
I
_
_
~ The wood rosin or abietic acid maybe ‘added
in amounts up to about, 5% of the weight of the 35
?n wax will, desirably, be stabilized‘by treatment
polymerized chloroprene present, and they pine tar.
with aqueous alkaline solutions, as more complete
may» be. ‘added in amounts up to about 10%.
When‘ using pine tar in amounts above 5% by
weight‘ of the chloropre‘ne present, it is usually
necessaryto reduce the amount of softener con 40
ly described in the copending application for Unit
ed States Letters Patent of William, T. ‘Bishop,
40 Serial No. 15,505, ?led April 9,1935, and/or stabi
lize‘d by'the addition‘ of organic bases, as‘ more.
completely described in my copending application
?led jointly with ‘William T. Bishop, Serial No.
19,468‘, filed May 2, 1935.
45
wood rosin, sulfur, metallic oxides, etc. may be ad
vantageously compounded. into the composition 30
before vulcanization. The?“ addition of wood
~
'
The polymerized chloroprene used in the com
position, ln'accordance with my invention is the
tained in‘the composition,.as the pine tar has a
softening action on the composition. '‘ ,
,
l- Sulfur may be added in amountsup to about
‘3% by weight of the polymerized‘chloroprene
"present. When added in excessive amounts the 45
sulfur tends to “bloom” out of‘the composition.
unvulcanized, chloroprene polymer having phys
The exact amount that may be added depends on ‘
‘the, various ingredients present in the‘composi- .
rubber. Such polymerized chroroprene is known. tion. The metallic oxide added to the compositionfmay be, for example, magnesia, zinc oxide, 50
50 to the art by the trade name of Duprene.
. ical properties very’ similar to those of natural
meriz'ed chloroprene, the compositions in accord‘
ance with my invention may include vulcanizin‘g
lead oxide,‘ ‘or combinations‘ of ‘these materials...
Such oxides are valuable additions to the com
position in that they improve the physical‘proper
agents, for example, metallic oxides, as, magnesi
ties of the composition‘ and, in addition, act as
In addition to'chlorinated paraffin and poly
58 um oxide, zinc oxide, lead oxide, .abietic' acid , acceptors for any‘ hydrochloric ‘acid which may 55
2,188,192
' 2
be evolved from either the chlorinated parai?n
wax or the polymerized chloroprene. Metallic
oxides may be added to the composition in
amounts up to about 10% based on the total
weight of chlorinated para?ln and polymerized
chloroprene
present.
. '
’
for a period of about 20 minutes to about 2 hours.
It will be understood that the details and ex
amples hereinbefore set forth are illustrative
only, and that the invention as herein broadly
described and claimed is in no way limited
'
‘An organic vulcanization accelerator ‘may. if
What I claim and desire to protect by United
desired, be added to the composition. Such ad {States Letters Patent is:
‘
dition is not essential. The resistance of the
*1. A synthetic rubber composition including
10 composition to aging is improvedby the addition'
of anti-oxydants, suchas, for example, phenyl
polymerized chloroprene and a gasoline insoluble 10
chlorinated para?ln wax, the said composition
alpha-naphthylamine and I .phenyl-bet‘a-naph;
thylamine' in amounts within the range of about '
being characterizedby high resistance to swelling
1% to about ‘5% by weight ‘of the polymerized
' 2. ‘A synthetic rubber composition including
15 chloroprene in the composition.
Carbonblacks, -
in gasoline. '
V
p
polymerizedchloroprene and a chlorinated par
15
such as, for example, channel carbon black or ..a?in wax having a chlorine content of not less
“soft blacks may be advantageously added '-to
the composition. Such carbon blacks may be
added in amounts up'to 100-200% byweight'of the
20 total weight of chlorinated para?in wax and-polyq
merized chloroprene, depending upon the exact
carbon black used.
Glue may be addedv in
‘amounts up to about 25% by weight. .
gasoline.
~
‘
_
-
3. A synthetic rubberfcomposition including 20
polymerized chloroprene and a chlorinatedpar
a?in wax having a chlorine content within'the
the. said compositionbeing characterized by high
wax,‘ fatty acids, oils, tars, waxes; cumarone
resistance to swelling in gasoline.
resins, etc., may, if desired, be added to the com
position. Such additions are usually not desira
,4. A synthetic rubber composition‘ including
polymerized chloroprene, a vulcanizing agent,
ble, since they tend to decrease the resistance of
the composition tov gasoline andoi1s.<,. Chlori;
and- chlorinated para?ln wax having a, chlorine
30 nated para?in wax acts as a softener ‘for the
composition, and any desired softnessmay'be
‘ obtained by increasing the percentage of. chlori
nated para?ln contained in the composition, with
out decreasing the oil and gasoline resistance.
, As examples of compositions, in accordance
with this invention, the following may be cited:
Example I
‘
f
'
,Parts
3
Chlorinated para?in wax (50% chlorine)";
1
a
i
,
>
'
v
i
,
i
4
Parts
Polymerized chloroprene ____________ _.._.._V_
4
45 Chlorinated para?‘ln wax (50% chlorine)";
1
The compositions according to the above exg
amples may be dissolved in an aromatic hydro
carbon solvent, such as toluol, to iform a cement
which is highly resistant to gasoline and mineral
oils.
-_
'
‘
"
The following examples are given as‘illustra
tions of compositions, in accordance with my -in- ' ’
vention, which are suitable for vulcanization.
55
25
. .
content of not less than about-52% :by weight,
the said composition being characterized by high 60
resistanceto swelling in'gasoline.
,
.
'
' I
A synthetic rubber composition including
polymerized chloroprene,,a.metallic» oxide,= and .
chlorinatedpara?in wax‘having a chlorine con
ten_t.of not less ‘than about 52% by weight, the 35
said composition being characterized by high
‘
6.};A synthetic rubber composition including ~~ *
‘
Example II
.
resistanceito swellingin gasoline.
_
Polymerizecl chloroprene _______________ _l__
‘
'50
ing in
range of about 52% to about 62% ‘by: weight,
,
‘ Various softeners, such as, for example, paraffin
35
than about 52% by weight, the said composition
being characterized by high resistance to swell
polymerized chloroprene, magnesium oxide, and
chlorinatedv para?in having a chlorine content of 40
not less than about‘ 52%, the said composition
being characterized by high resistance to swelling
in gasoline.
>
_7. A,-_synthetic -;rubber composition including ‘
polymerized chloroprene, an anti-oxydant, and 145
chlorinated para?inwax having a chlorine con,
tent of not less than about 52% by weight, the
said composition being characterized by high
resistance to swelling in gasoline.
'
r .
.
8. A synthetic rubber composition including
polymerized, chloroprene, a phenyl-naphthyb‘
amine, and chlorinated paraffin having a chlorine
content of not less than about 52%, the said- com
position being characterizedgby high resistance to
Example 3 Example .4
swelling in gasoline.;.
-
,
.
.
;
,
9. ‘A synthetic rubber composition. including
polymerized chloroprene, phenyl-alpha-naph
.
.
.
Parts
Polymerized chloroprene (Duprene): ____ .. '
153.0
Chlorinated paraffin wax (54% chlorine)...
1
. _.
75. O
197. 5
-
l0. '1
__
Light calcined magnesia
Sulfur ________________ __
Stearic acid ............. _.
_
Phenyl-alpha-naphthylaminc ........... _ .
'
chlorine content of not less than about 52%,; the
287'
15.3
Cumarone-indene resin (Cumar P25)____..
thylamine, and chlorinated paraffin having a >
140‘
369 ,
153.0
Wood rosin (Color FF.)_.._;_ ..... _.
287
Parts
'
28. 7
19:1
l0. 2
19.1
10.2
19.1
15. 3
.,
’ 1.3
’
2. 5
l. 3
28. 7
2.4
4. 8
2. 4
said compositionv being characterized. by high
resistance to swelling in gasoline.
10. A synthetic rubber'composition including
polymerized chloroprene, a; reinforcing pigment
and chlorinated para?in having a chlorinercon
tent of notiless than about 52%, thesaid com 66
position ,being characterized v by vhigh resistance
to swellingin gasoline. .
The compositions shown in these examples may
be vulcanized following the procedure used by
70 theprior art with similar compositions of poly
merized chloropi'ene not containing chlorinated
para?in. Thus, for example, such compositions
may bevulcanized by heating at a temperature
within the range of about 250° F. to about 300° F. '
.60
.
‘
‘I v
,
,
11. Asynthetic rubber composition including
polymerized chloroprene, a carbon black, and
chlorinated para?in having achlorine content
of not less than. about 52%, the said composition
beingcharacterized by high resistance to swelling
in gasoline.
err.
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