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Патент USA US2136028

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Patented Nov.
2,136,028
1938 I
UNITED s'rn'nazsv PATENT OFFICE
2,136,028
PROCESS FOR PRODUCING POLYIVIERIC
COMPOUNDS
Robert Dewey Snow, Bartlesville, 0kla., as
signor to Phillips Petroleum Company, Bar
tlesville, 0kla., a corp oration
of . Delaware
No Drawing. Application January 26, 1934,
Serial No. 708,522
(Cl. 260-2)
This invention relates to the production of product already formed in the reacting mixture
1'7 Claim.
compounds of high molecular weight by the re
action' of sulfur dioxide with unsaturated com
pounds; and more speci?cally to the provision of
5 means and conditions for carrying out such reac
tions with a rapidity and yield not hitherto
obtainable.
v
_
at lower temperatures would decompose when
heated above the threshold temperature, but this
is not the case. For example, when one mol of
butene-2 and two mols S02 are exposed to sun
' 5
light until 50 percent of the butene-2 is converted
to reaction product, and the temperature is then
raised to 45° C., the quantity of reaction product
A further object of the invention is to describe
means whereby sulfur dioxide may be caused to_ remains unchanged over a period of days nor is
there any appreciable change in the quantity of ‘
10 react with certain ole?n hydrocarbons hereto
fore considered non-reactive, and to the new and reaction product when such a mixture is heated
,
useful products produced thereby; all as more to 100° C.
Contrary to Example 3 of the previously cited
fully hereinafter set forth and claimed.
The reaction between some of the simple ole-_ Matthews and Elder patent, it has been found
15
?nic hydrocarbons, such as~ ethylene, propylene,
and pseudobutylene ,(butene-2), and S0: to form
ethyl ethylene, and pentene-2 will undergo no
resinous bodies has been described by Matthews
and Elder, British Patent 11,635, 1914. In their
detectable reaction with sulfur dioxide in the
temperature range of 20-100° C., either in sun—
light or in the presence of catalysts. The same
‘patent, however, nothing is said regarding the
that trimethylethylene, unsymmetrical methyl 1‘
is true of many other unsaturated compounds and
their oxides; for example, isobutylene, hexene-2,
hexene-3, and cyclohexene. Ethylene oxide and
or atmospheric temperatures, except that they‘ propylene oxide do not undergo the reaction
above 30° C.
state in Example 3: “Amylene (trimethyl ethyl
25 ene or any of the isomeric amylenes) and liquid
I have found that the reason why certain of
$02 which may conveniently be taken in equal these ole?ns will not react with sulfur dioxide in
molecular proportions are mixed together in a the expected manner is that the threshold tem
perature above which the reaction will not take
closed glass vessel and the combination acceler
place lies below those temperatures commonly
ated either by warming in a water bath at a suit
30 able temperature, say at 50° C.‘, but preferably by used,‘ and generally referred to as room temper
exposing to bright sunlight as in the previous ature, say 20° C. to 30° C. I have reacted, for ex
20 temperature range in which the reaction will take
place, but judging from their disclosure they car
ried out most of their reactions at ordinary room
examples.” Perkins, Can.'Pat. 329,043, 1933, de
ample, isobutylene, pentene-2, hexene-2, cyclo
scribes the reaction of S0: with diole?ns at tem
peratures near 100° C. When temperature was
35 mentioned at all in past reference in connection
hexene, ethylene oxide and propylene oxide with
sulfur dioxide to form products of high molecular
weight, at temperatures below +10° C., and in the
- with the reaction of S0: with ole?ns or diole?ns,
presence of sunlight, or of catalysts such as silver
or lithium nitrate.
I have also found the use of these lower reac
it has been an elevated temperature.
However, I have found that the' reaction of
'
butene-2 with sulfur dioxide, whether promoted tion temperatures advantageous for accelerating
40 -by catalysts, sunlight or other source of actinic
light, takes place more slowly at 37° C. than at
25° C., and stopped entirely at temperatures of
40° C. and- above. In other words, there is a
limiting or threshold temperature above which
45 the reaction does not take place.. While these
threshold temperatures have not been deter
mined for all hydrocarbons, they a'reknown to
be'higher for propylene and ethylene than for
' butene-2. ‘This behavior near the threshold tem
50 perature is, of course, contrary to the ‘usual ex
the reaction of mixtures of ole?ns containing
branched chain, or tertiary ole?ns. As pointed
out elsewhere (application Ser. No. 628,449, Pat
ent No. 2,045,592), small quantities of isobutylene
or other tertiary ole?nes inhibit or slow down the
reaction of sulfur dioxide with normally reactive
ole?ns at temperatures of 15 to 40° C.
For ex
ample, a mixture of 25 percent isobutylene and 75
percent butene-2 in two equivalents of sulfur
dioxide, will react very slowly at 20-40“ C., only
15 percent of such a mixture being converted into
perience of chemistry that the reaction rate high molecular weight polymer in 20 days of
increases with rising temperature, approximately, exposure to sunlight. A 'mixture of pure butene-2
doubling for a rise of 10° C.
Were it a case of
the shift of an equilibrium toward the side of
55 decomposition, we should expect that the reaction
and sulfur dioxide reacted completely in less thanv
one’ day under similar conditions. However, I
have found that mixtures of ole?ns containing 55
2
2,136,028
considerable quantities of tertiary 'olefins react
quite readily with sulfur dioxide at lower temper
atures. For example, mixtures of 50 percent
butene-2 and 50 percent isobutylene, or 25 per‘
cent butene-2 .and '75 percent isobutylene react
from the same material at ordinary or higher
temperatures.
'
Example I.—One mol of isobutylene, two mols
rapidly at 0° C. in the sunlight, or in the pres
ence of catalysts such as silver nitrate.
In the commercial scale production of the sulfur
of S02, and one cc. of'saturated alcoholic AgNO:
solution are thoroughly mixed in a pressure vessel 5
and are allowed to stand 24 hours at 0° C. After
removing the excess $02 the product is obtained
as a white brittle solid, which is practically insol
dioxide resins, it would .be highly desirable to
uble in $02.
10 use as raw'materials such mixtures of ole?n,
para?in and cyclic hydrocarbons as are obtained
as products of oil cracking,; carbonization of
coal, or equilibrium dehydrogenation of para?in
hydrocarbons. Typical propane-propylene frac
15 tions of cracking still vapors will contain from
20 to 40 percent propylene. Butane-butane frac
tions from the same source usually contain from
'
Example II.—One half mol of isobutylene, one .10
half mol of butene—2 and two mols of SO: are
sealed in a glass tube and are exposed to sunlight
at 0° C. The reaction is practically complete in
two days.
Example III.—-Three pounds of a butane-butane 15
fraction of cracking still gases, two pounds of S02,
and 30 cc. of saturated alcoholic AgNOa are mixed
30 to 80 percent of butenes. Products obtainable
and allowed to stand in a pressure vessel sur
by the catalytic dehydrogenation of the lower
rounded by a bath of ice water or cold ‘brine. The
solid resin is obtained by evaporating the un 20
changed hydrocarbons and S02.
I do not limit my claims to the proportion of
$02, the nature of quantity of catalyst or the
source of light speci?ed in the above examples.
What I claim and desire to secure by Letters 25
20 para?ins, such as n-butane and n-pentane, will
contain 10 to 30 percent of ole?ns, depending
upon the temperature and pressure conditions of
dehydrogenation.
Furthermore, the dehydro
genated n-pentane will contain important quan
titles of pentene-2, which does not react with
, S0: at, or above, room temperature.
The isola
tion or concentration of ole?ns from such mix
tures by ordinary methods such as fractional
distillation is very di?icult and costly; hence it
30 would be highly desirable to react the S02 directly
Patent is:
_
1. The process of producing polymeric products
of high molecular weight which consists-in re
acting sulfur dioxide with mono-ole?ns at tem
peratures below +15° C.
30
2. In a process of producing polymeric products
with the olefins in such mixtures, without ?rst
concentrating or isolating the oleflns. However, > of high molecular weight from sulfur dioxide and
the large quantities of paraf?ns present tend to mono-ole?ns, the improvement which consists in
slow down the reaction by dilution and by de , reacting the sulfur dioxide with the said mono
olenns at temperatures between —30° C. and 35
creasing the solubility of most catalysts in the re
+15° c.
action mixture. The result is that with such mix
3. The process of producing polymeric com
tures at, or above, room temperature the reaction
pounds
of sulfur dioxide and unsaturated hydro
is usually slow.
carbons of the group consisting of; isobutylene,
I have found that the use of the low tempera
40 tures has a further bene?cial e?ect in the case
pentene-2, hexene-2, and cyclohexene, which 40
of mixtures containing large proportions of satu-' consists in reacting any of the said hydrocarbons
rated hydrocarbons, or other diluent materials, with sulfur dioxide at temperatures between
in that the reaction mixture with S0: tends to —30° C. and +15° C.
4. The process of producing polymeric products
form two phases, the lower of which is rich in
of high molecular weight, which consists in react 45
S0:
which
tends
to
selectively
extract
olefins
from
45
the mixture. Resin is generally formed more ing pentene-2 with sulfur dioxide.
5. In a process of manufacturing polymeric
rapidly under such conditions than at tempera
tures at which only one liquid phase exists. This compounds of sulfur dioxide and mono-olefins,
is important in the reaction of such products as the improvement which consists in, reacting the
mono-olefins with sulfur dioxide in the presence 50
fractions of cracking still vapors, partially de
hydrogenated para?in hydrocarbons, etc. Also, of catalysts and in the dark, at temperatures be
tween -30° C. and +15° C.
the fractions of cracking still vapors and dehy
drogenated paramns containing compounds of
five carbon atoms or more contain considerable
55 proportions of 2-ole?ns which will react with S0:
only at low temperatures. Consequently the use
of low temperatures increases both the reaction
rate and the quantity of resin from such mix
tures. Of course, the reactionis virtually arrested
50 at extremely low temperatures, but temperatures
down to 30° below zero, centigrade,'may on some‘
occasions be found useful.
Inasmuch as pentene-2, hexane-2, and prob
ably also the higher 2-ole?ns will react with S0:
6. In a process of manufacturing polymeric
compounds of sulfur dioxide and mono-ole?ns,
the improvement which consists in, conducting 55
the reaction at temperatures below +15° C. but
above those temperatures at which the reaction
is virtually. arrested.
7. A process of producing polymeric products
of high molecular weight, which consists in re 60
acting sulfur dioxide with a mixture containing
mono-ole?n and paraffin hydrocarbons substan
tially all of which contain the same number of
carbon atoms per molecule, at temperatures be
low +15" C.
_
at low temperatures, products obtained by dehy
8. The process of producing polymenc products
drating the corresponding secondary alcoholsv of high molecular weight, which consists in re
with 60-65 percent H2804 or by extracting ole?ns
from cracked products with concentrated H2804,
diluting the acid to 60-65 percent strength and
70
generating the 2,-ole?ns by heating can now be
converted into resins.
'
Products obtained by reacting the 802' with the
unsaturated compound at low temperatures are
15 generally of better quality than those obtained
65
acting sulfur dioxide with those fractions of
hydrocarbon pyrolysis products containing monof
olefin hydrocarbons of from three to six carbon 70
atoms to the molecule, at temperatures between
-30° C. and +15° C., in the presence of a cata
lyst.
.
9. A high molecular weight polymeric com
pound conslating of sulfur dioxide and a hydro
3
2,136,028
carbon of the group consisting of; isobutylene,
pentene-2, hexene-2, and cyclohexene.
10. The process of manufacturing polymeric
compounds of high molecular weight from the
gases and volatile liquids produced by the pyroly
sis of hydrocarbons, which consists in reacting
suitable fractions of such gases and volatile liquids
containing mono-ole?ns without separation of
their saturated aliphatic constituents, with sulfur
10 dioxide at temperatures below 15° C. ‘~
11. The process of producing hetero olymeric
compounds of high molecular weight, w ch con
sists in reacting sulfur dioxide with a 2 (beta)
mono-ole?n at temperatures below +15° C.
12. In the process of producing polymeric com
pounds of high molecular weight from sulfur
dioxidev and mono-ole?ns having an upper thres
hold temperature substantially below room tem
perature, the, improvement which consists in cool
ing the mixture to, and carrying out the reaction
at, a temperature substantially below the said
threshold temperature.
.
13. The process of producing polymeric prod
ucts of high molecular weight, which consists in
reacting isobutylene with sulfur dioxide.
14. The process of producing polymeric prod
ucts of high molecular weight, which consists in ca
reacting hexene-2 with sulfur dioxide.
15. The process of producing polymeric prod
ucts of high molecular weight, which consists in
reacting isobutylene with sulfur dioxide at a
10
temperature of about 0° C.
16. The process of producing polymeric com
pounds of high molecular weight, which consists
in reacting pentene-2 with sulfur dioxide at tem
peratures between -30° C. and 15° C.
17. The process of producing polymeric com
pounds of high molecular weight, which consists
in reacting hexene-2 with sulfur dioxide at tem
, peratures between -30° C. and 15° C.
ROBERT DEWEY snow.
20
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