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Патент USA US2411276

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"2,411,276
Patented Nov. 19, 1946
UNITED STATES PATIENT = OFFICE ,
ORGAN OPOLYSULFIDE RUBBER
4
Ivar H. Kinneberg and Charles L. Thomas, River
side, 11]., assignors to Universal Oil Products
Company, Chicago, 111., a corporation of Dela
ware
No Drawing. Application March 172, 1943,
' _-
Serial No. 478,9“
'
_
'9 Claims. (0]. 260-79)
2
An object of this invention is the conversion
of oleiinic hydrocarbons and halo~ole?ns into a
rubber-like material having elastic and tensile
.
Sulfur monochloride, which is generally repre
sented by the formula S2Cl2, is producible by the
properties and other desirable characteristics of
natural rubber.
'
purity resulting from catalytic dehydration. of'a
propyl alcohol.
f
action of chlorine on sulfur or of chlorine on a
Another objectiof this invention is the produc
metal sul?de. As sulfur monochloride is now a
commercial product, further details of its manu
tion of a synthetic rubber from a hydrocarbon of
the ole?n or ethylene series and chloro-ole?n by
facture are not described herein.
a process comprising the treatment of said ole?n
The reaction of sulfur‘monochloride with an
and halo-ole?n with sulfur monochloride to form 10 ole?n results in the formation of a dihalo dialkyl
a mixture of polychlorodialkyl sul?des and the
sul?de. When propylene is the ole?n ,so treated
condensation of said polychlorodialkyl sul?des
with sulfur monochloride, the principal reaction
with an aqueous solution of a water-soluble poly
product is beta,beta’-dichlorodipropyl sul?de, the
sul?de.
'
'
chemical structure of which may be expressed by
A further object of this invention is the use of 15 one or more of the following formulae :1
s
propylene and a chloro-ole?n as starting mate- -
rials'for the production of a synthetic rubber
havingnot only good rubber-like properties but
also a high degree of resistance to oxidation and
'
20
to swelling when in contact with oil.
In accordance with the present invention we
are able to produce a rubber-like material hav
ing high tensile strength, good elasticity, and
other desirable characteristics of natural rubber '
by a series of reactions in which propylene or a 25
propane-propylene fraction is treated with‘sul
fur monochloride preferably in the presence of an
alcohol and the resultant reaction product is re
acted further with a water-soluble inorganic pol
ysul?de in the presence of a polyhalodialkyl sul
a6,
The condensation of beta,beta'-dichlorodipro- ,
pyl sul?de with an inorganic polysul?de, such as
sodium tetrasul?de, results in the formation of a
long'chain polymer or linear polymer, the struc
tural unit of which may be expressed as follows:
CH:
- ?de having more than two ‘halogen atoms per
molecule.
-
CH:
When beta,beta'-dichlorodipropyl sul?de is con
densed with sodium polysul?de under preferred
40 conditions of operation which include a tempera
-
One speci?c embodiment of the present inven
tion relates to a process which comprises react
ing a dichlorodipropyl sul?de and a polyhalodial
' kyl sul?de having more than two halogen atoms
per molecule with a water-soluble inorganic poly
sul?de to form a rubber-like material.
ture of from about 60° to‘about 100° C., and in
the presence of a dispersing agent such as mag
nesium hydroxide, the resultant ‘product is a ' '
‘ somewhat plastic rubber-like material with phys
ical properties resembling those of natural rub
Propylene which is the hydrocarbon preferably
ber.
utilized ‘as a starting material for the process of I
this invention may be obtained from any source
including the catalytic dehydration of a propyl
alcohol,_the separation of a propaneepropylene
fraction from cracked gases, the catalytic or ther
mal dehydrogenation of propane to propylene,
'
'
'
In accordance with the process of this‘invem
tion, we propose to reduce the plasticity and also ‘
50
improve the other rubber-like properties of thé
above indicated reaction product by commingling
with the beta,‘beta’idichlorodipropyl vsul?de a -
etc. 'It is not to be inferred that the different -
propylene-containing fractions mentioned above
are necessarily equivalent to ‘propylene of high
CH:
55
relatively minor amount of a more highly halo
genated dialkyl sul?de _so that ‘this '‘ mixture on
treatment with ‘an inorganic polysul?de will yield
a polymericmaterial in which long chains of
2,411,970 i
3
_
-
carbon and sulfur atoms are cross-linked with
other carbon and sulfur atoms so as to form,
what may be termed a spatial polymer. For
example, the reaction of sulfur monochloriderwith
allyl chloride may produce beta,gamma,beta',
gamma'-tetrachlorodipropyl sul?des. The struc
ture of different chloropropyl sul?des producible
from allyl chloride and sulfur monochloride. may
‘be represented by one or more of the following
formulae:
-
_
C1-CHr-CH-CHr-Cl
CI-OH-CHr-Cl
Ha
-
the beta,beta'-dichlorodipropyl ‘sul?de. is herein'
referred to as containing beta,gamma,beta',gam
ma'-tetrachlorodipropyl sul?de, it may also con
tain in part or wholly instead of the latter a tri
chlorodipropyl sul?de which will function sim
ilarly in producing cross-linking between chains
of carbon and sulfur atoms.
'
In accordance with the process of the-present
' invention, substantially pure propylene or a pro
10 pane-propylene mixture and a halo-ole?n are
' contacted with sulfur monochioride at a tem
perature of from about 0° to about 150° 0., but '
‘ preferably at a temperature of from about 40°
i
to about 50° C., and under a pressure up to about
éHa
15 10 atmospheres in a reactor provided with good
agitation or mixing; The charging stock con
taining propylene and the halo-ole?n is gen- '
01‘
Gl-CH-CHrCl'
'.
erally introduced ‘gradually to the well-stirred
.
sulfur monochioride as care is needed to prevent
H:
20 the reaction temperature from becoming too high
due to the exothermic nature of the reaction
between the unsaturated materials and vsulfur
monochloride. The propylene or propylene-con-_
When allyl chloride and propylene react with sul
taining gas is sometimes introduced at such a
fur monochioride, certain amounts of beta,beta’
dichlorodipropyl sul?de containing up to about 25 rate that a small amount of this ole?n is not
25 mole per cent of beta,gamma,beta',gamma'
absorbed and escapes from the reaction zone with
tetrachlorodipropyl sul?de, but preferably‘ not
the eiiiuent gases. The reaction. product so
formed from propylene, a halo-ole?n, and sulfur
monochioride may be distilled at reduced pressure
more than from 5 to 10 mole per cent of the
latter material, is reacted with sodium tetrasul
?de, a rubber-like polymer is formed consisting 30 to separate dichlorodipropyl sul?de and polychlo- _
of cross-linked long! chain polymers, the struc
rodialkyl sul?des from relatively small amounts
of higher boiling materials, or the total product
. tural unit of which y{may be represented as fol
may be treated with an aqueous solution of 'a ‘
CH:
H:
Ha
Ha
H:
Thebeta, gamma, beta’, gammaf-tetrachloro
n
water-soluble inorganic polysul?de such as so
dium polysul?de, of which sodium tetrasul?de, ,
which may be expressed, by the general formula
NazS4, is representative. In order to simplify the
description, the mixture of dichlorodipropyl' sul
?de and polychlorodipropyi sul?des, the latter
containing more than 2 chlorine atoms per mole
cule, is hereinafter referred to by the term “chlo
dlpropyl sul?de or other tri- or tetrachlorodi
propyl sul?de referred to above may be prepared
by the reaction of allyl chloride with sulfur
monochioride. In effecting this reaction the
allyl chloridemay be added drop-wise to the
reaction ‘mixture during absorption of ‘propylene
in sulfur monochloride; or vaporized into the
' stream of'propylene prior to reaction with sulfur
. rodipropyl sul?des.”
monochloride; or, when the absorption of propyl
Although sodium polysul?de is the ‘water-solu
ene‘ in sulfur monochloride has reached some de
ble polysul?de generally employed for treating A
sirable point below 100% consumption of sulfur.
‘monochioride, the introduction of propylene is
discontinued and allyl chloride is added in suffi
cient amount to react with the unconsumed sul
fur ‘monochioride.
chlorodipropyl sul?des to produce rubber-like
materials, other polysui?des utilizable similarly, -
although not necessarily under the same condi
tions of vcpe'ration, include calcium polysul?de
Alternatively, when the ab- .
;sorption 'of propylene by sulfur monochloride is
of the general formula Case or potassium
polysul?des of the general formula KzS? wherein
completed, a further desired amount of sulfur 60 n may vary from 2 to about 5, and polysul?des
‘of basic nitrogen compounds, particularly am-‘
‘monochioride is added to the reaction product
and the equivalent amount of allyl chloridev is
monium polysul?de and tetraalkyl ammonium
then introduced.
'
Although allyl chloride is herein mentioned as ‘
polysul?des.
The treatment of chlorodipropyl sulfides with,
66 an'inorganic polysul?de, such as sodium tetra
linking between the long chain parts of a spatial - sul?de, is generally carried out by adding slowly
, a suitable material for introducing the cross
polymer, other halo-ole?ns may-beutilized sim
the chlorodipropyl sul?des to an aqueous solution
of sodium tetrasul?de containing a dispersing
ess comprise particularly vinyl-, allyl-, and meth
agent such as magnesium hydroxide so’ as to
allyl- chlorides and, bromides as well as other 70 effect a substantially‘ complete reaction between
ilarly. The halo-ole?ns so utilized in the proc
halo-ole?ns, principally chloro- and bromo-ole
?ns. It should be understood that the different
halo-ole?ns are not necessarily equivalent ‘in
their action. Furthermore, although the poly
the chlorodipropyl sul?des and the sodium poly- '
sul?de and to form a latex-like suspension of a
high molecular weight polymeric organic poly
,
sul?de.
The resultant reaction product herein '
halogenated sul?de which is commingled with 76 referred to as a rubber and existing as a latex
2,411,276
5
6
like suspension may be washed with water by set
tling and decantation to ‘remove substantially all
water-soluble salts.
The resultant washed latex-like suspension
which case the magnesium hydroxide was freshly
precipitated by successive additions of solutions
of sodium hydroxide and magnesium chloride;
pounded in the same manner as crude rubber
chlorodipropyl sul?des was completed, the result
bringing the reactor contents to a reaction tem
which may contain upwards of 80% or better by 5 perature of 60° 0., and adding slowly, over a a
weight of a rubber, may be treated with small
period of 3-hours, 0.45 molar proportion of the
amounts of an acid, generally a mineral acid
chlorodipropyl sul?de mixture to the reaction
such as hydrochloric acid, in order to coagulate
mixture containing sodium tetrasulflde. The re
the latex-like suspension and to form a coagulum
action of the chlorodipropyl sul?des with sodium
of the rubber-like material which may be com 10 tetrasul?de is exothermic. When addition'of the
with reinforcing pigments such as carbon black,
?llers, plasticizers, and a vulcanization agent
ant reaction mixture was heated under total re
flux for 3 hours at a temperature of 100° C., and
such as zinc oxide with or without sulfur and
a latex-like product was formed. The latex-like
cured by heat and pressure, Alternatively, the 15 product was washed by pouring the total reaction
latex-like suspension may-‘be compounded vby
mixing before coagulation. The raw rubber-like
synthetic produced andjocompounded in'accord
ance with the process of the present invention is
suitable for use in the production of tires and 20
many types of mechanical goods‘heretofore man
ufactured generally from natural rubber as well
mixture into water, the product was permitted to
settle, and the supernatant solution was decant
ed. Five suchwashings were used in order to
obtain a latex-like material substantially free
from water-soluble salts, and the resultant latex
like 'material was acidified with dilute hydro
chloric acid to form a coagulated mass of a rub
ber or rubber-like material which after milling
yielded a crumbly, dry sheet of relatively low
as in special applications where oil resistance not
possessed by natural rubber is desired. It may
also be compounded with natural rubber or hy 25 plasticity. Press-molding of the sheeted material
drocarbon synthetic rubbers to impart oil resist
at 70° C. produced a brown sheet of rubber-like
ance to them.‘
‘~
‘a
product with a toughness and elasticity similar
The latex-like dispersion obtained as herein; ‘ to those properties of soft gum rubber,
.
above set forth may also be utilized assuch for
The condensation of the crude di- and tetra
impregnating fabrics and other materials or it 30 chlorodipropyl sul?des with sodium. tetrasul?de
may be separated by means of a centrifuge into
solution was repeated in a larger batch and the
a more highly concentrated latex. The latex-like
washed aqueous. suspension was compounded
material so obtained by centrifugation, may be
before coagulation to give a composite with the
utilized as a paint or lacquer for applying a rub
ber-like coating to metals, fabrics, and other 35
materials.
The following example is given to illustrate the
process of the invention, although with no inten
tion of unduly limiting its generally broadscope.
A solution equivalent to 10 mole per cent of 40
following composition:
_
Barts by weight
Polymer _____________________________ __ 100
Zinc oxide
_______ _s_________________ _.
Stearic acid _________________________ -_
Benzothiazyl disul?de ________________ __
beta,gamma,beta',gamma' - tetrachlorodipropyl
Diphenylguanidine ___________________ __ ’
sul?de in beta,beta'-dichlorodipropyl sul?de was
Carbon black ______________________ __.__
20
0.7
0.4
0.13
27
The well mixed compounding ingredients were
stirred into a smooth slurry with the dispersed
ed at a rate of 1.5 cubic feet per hour into a re 45 polymer and the resultant mixture was then co;
agulated to an easily ?lterable, crumbly mass by
actor containing 150 cc. of sulfur monochloride
and provided with good agitation and cooling so ‘the addition of‘ dilute hydrochloric acid. The
wet product so produced was aggregated to some
as to maintaina reaction temperature of between
extent by cold working in a rubber mill and then
45° and 50° C. After the propylene-allyl chloride
mixture was so charged during a period of about 50 oven-dried at 75° C. to remove water. Samples
thereof were cured by heating at 110° C. for 1, 2,
6 hours, the sulfur monochloride was completely
4, and 8 hours and press molded into test sheets.
consumed'and a clear yellow oil resultedwhich
The sample treated for 8 hours gave a tough,
contained little or no precipitated sulfur and had
a speci?c gravity of 1.225 at 27° C. The yield of ,
elastic rubber-like material and seemed some
prepared by vaporizing 30 cc. of‘allyl chloride
into a stream of dry propylene which was direct
this yellow oil was 92.5% of the theoreticalbased
upon the amount of sulfur monochloride charged.
what superior to samples heated for shorter
times.
'
‘
For the purpose of determining oil resistance,
A sodium polysul?de solution which was re
acted with the chlorodipropyl sul?des as herein- - strips of 0.25 inch width were cut from molded
after set forth, was prepared by dissolving tech- ' ' 'test sheets of raw polymer and compounded
nical fused 60% sodium sulfide and a stoichio to polymer cured for 1, 2, 4, and ,8 hours. The
metric quantity of sulfur in su?icient boiling
hardness index and thickness of the samples were
- water to give a 25 molar concentration of sodium
measured before and after immersion in Final, a
para?inic lubricating oil, during periods of 24
tetrasul?de. This aqueous solution. was heated
and 192 hours. These data, given in the table,
‘at boiling for about 20 hours,‘ cooled and ?ltered
through asbestos to give a ?ltrate with density of 65 were obtained as follows: The hardness index
about 1.28 at 20°C.
~
,_
The reaction of the chlorodipropyl sul?de mix
ture, with the sodium“ tetrasulflde solution was
was measured by a Shore “A” Durometer on the
test-strips backed by glass. The hardness at“
initial contact and after 10 seconds sustained
carried out in an electrically heated reactor pro-‘ I contact are indicated-thushl, D1/D1o sec. ’ 'I‘lie lat
vided with a mechanically driven stirrer, a‘ re?ux 70 ter value is an index of the plasticity. The thick
condenser, and a thermometer. The general pro
ness, in inches, was measured by a Randall
cedure followed in a typical run consisted of plac- ‘ Stickney dial gage designed for use on rubber.
Each of the results given in the table is the
ing 0.5 molecular proportion of sodium tetrasul
average of 3 ‘measurements made on-each prop
‘?de solution in the reactor; adding thereto a dis
»
persing agent suchv as magnesium hydroxide, in 75 erty.
is
2,411,976 A ‘
,‘E?ectl of Final on‘. polymeric prom/Z sul?des
'3- A process whi '11 comprises ' reacting a
branched chain dic orodipropyl sul?de and a
' polyhalo dialkyl sul?de containing at least three
Thickness of test
Hardness index
4 ship'mches
but not more than four halogen atoms per mole
' cule with an aqueous solution of a polysul?de of
-
After oil
88mph
Alter oil
immersion
Initial
1°" hm
24
an alkali metal to form an elastomer.
4. A process which comprises reacting
immersion
Initial
102
a
branched chain dichlorodipropyl sul?de and a
1"" hrs24
polyhalo dialkyl sul?de containing at least three
192
10 but not more than four halogen atoms per mole
Raw polymer ....... __ 38/33
cured lholln.
cule with an aqueous solution of a calcium poly
31/30
37/33 0.0751 0.0760 0.0759
>_. 42/37
39/31
45/40
.0813
.0813
.0812v
45/38
46/38
42/35
44/38
45/40
46/42
.0777
.0776
.0776
.0778
.0775_ .
.0775
47/42
44/40
48/42 .0860
.0859
.0858
compounded polyme
__
sul?de to form an elastomer.‘
v
'
'
5. A process which comprises reacting a
branched chain dichlorodialkyl sul?de and a poly
15
halo dialkyl sul?de containing at least three but
not more than four halogen atoms per molecule
with an aqueous solution of a,‘ water-soluble poly
sul?de in the presence of a dispersing agent to
These results show that Finol had practically
no swelling e?ect on the raw and compounded
polymers during immersion in said oil for a period
an elastomer.
.
of up to 192 hours. In general, the samples 20 form
6. A process which comprises reacting a,
tended'to shrink very slightly in thickness due
branched chain dichlorodipropyl sul?de and a
probably to a leaching out e?ect of the oil; dis
polyhalo
dialkyl sul?de containing at least three
coloration of the oil was also least here for the
but not more than four halogen atoms per mole
raw polymer. The Durometer hardness of these
samples dropped somewhat at ‘24 hours but ap 25 cule with an aqueous solution of a water-soluble
pears to be nearly restored after immersion for
inorganic polysul?de in the presence of a dis-'
192 hours. It-vis therefore concluded that the
raw rubber-like polymer and cured compounded
a
persing agent to form an elastomer.
'
7. A process which comprises - reacting
branched chain dichlorodipropyl sul?de and a
polyhalo dialkyl sul?de containing at least three
of a para?lnic lubricating oil.
The ‘character of the present invention and 30 but not more than four halogen atoms per mole
- polymers are resistant to swelling in the presence
cule with an aqueous solution of a Water-soluble
‘inorganic polysul?de in the presence of a dis
' type of results obtained are evident from the pre
ceding speci?cation and example, although they
persing agent comprising magnesium hydroxide
are not to be considered as imposing undue limi
-
tations upon its generally broad scope.
We claim as our invention:
1. A process which comprises
reacting
35
va
branched chain .dichlorodialkyl sul?de and a poly
halo dialkyl sul?de containing at least three but
to form an elastomer.
8. The process of claim 1 further characterized
in that said water-soluble polysul?de includes a
polysul?de of an alkaline earth metal.
9. An elastomer formed by reacting a branched w
‘chain dichlorodipropyl sul?de, a polyhalodialkyl
not more than four halogen atoms per molecule
with an aqueous solution of a water-soluble poly 40 sul?de containing at least three but not more
than four halogen atoms per molecule, and an
sul?de to form an elastomer.
aqueous solution of a water-soluble inorganic
2’. A process, which comprises reacting a
polysul?de.
.
branched chain dichlorodipropyl sul?de and a
polyhalo dialkyl sul?de containing at least three
but not more than four halogen atoms per mole 45
cule with an aqueous solution of a water-soluble
inorganic polysu'l?de to form an elastomer.
IVAR I-I. KINNEBERG.
CHARLES L. 'THOMIAS.
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