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Патент USA US2114292

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ilœcitented Aps. lid, E93@
.sur orties
Frederick E. Frey, Louis Henry Fitch, Jr., and
Robert Dewey Snow,
iesvilie, ûkla.; The
First National Bauli in Bartlesville, adminis
trators ci said Eloois Henry Fitch, deceased, as
signora to Phiilips Petroleum Company, a cor»
poration of Delaware
No Drawing. Application January
Serial No. W852i
3 G in; tu
(El. 26d-2)
This invention relates to the’manufacture of
new and useful products.,- generally of high molec
ular weight, or poleric in nature, by causing
sulfur dioxide to react with unsaturated ccm
or conjugated di
5. pounds other than the` ole
oleñn hydrocarbons, and to processes by which
such reacticnscan be made to take place.
A further object of the invention is to pro
duce high molecular weicht compounds contain
ing sulfur dioxide and having incorporated in
the molecule, radicals such as the hydroxyl or
ze, 193.4,
The vinyl chloride forms a white solid which is
insoluble in S02, but which can be molded by
'heat and pressure. The allyl .chloride forms a
water white, classy product somewhat soluble in
SO2. After molding by heat and pressure, the
resin exhibits high mechanical strength. The
unsaturated alcohol, allyl alcohol, reacts readily
with 80a in the presence of catalyst or light.
The solid resin obtained has a. very high tensile
The unsaturated ether, allyl ethyl ether, reacts
carbonyl, capable of undergoing further reaction >readily with. sol m the presence or catalyst or
light. The solid resinous product can be molded
with suitable chemical agents.
Other objects will appear as theA invention is
more fully described.
by heat and pressure.
The olefin oxides, or innerethers, ethylene ox
Prior literature references to the reactions of
SO2 with unsaturated compounds are conñned
to the olefin and dioleñn hydrocarbons. Mathews
ide and propylene oxide react relatively more
slowly'with SO: in the presence of catalyst or
light at temperatures hup to 40° C. but preferably
and Elder, Brit. 11,635, 1914, claim the reaction , at about 0° C. The products are viscous fluids
of liquid SO2 with olec hydrocarbons, such as -useful as softening agents. plasticizers, and sol
ethylene, propylene, and butylenes in sunlight
The unsaturated ester, ethyl acrylate, reacts
or ultraviolet light. De Bruin, Chem. Abs. 9,623
(1915) found that the conjugated diene, isoprene, readily with SO: in the presence of light or cata
when allowed to stand with liquid SO2. forms a lyst to form a soft, rubberyfproduct solublev in
crystalline compound. Mathews and Strange, SO2 and many organic solvents.
When SO2 is passed into'an unsaturated amine
U. S. 1,196,259 (1916), react isoprene and other
conjugated dioleiìns with Si): in the presence ofv compound such as allylamine, the ñrst energetic
halogen compounds such as HáCl, iodine or acetyl reaction is evidently between the '--NHz group
chloride, which pro/¿mote the formation lof the and the SO2. If after this reaction is complete,
sulfoxide. Badische Aniline and an excess of SO2 is added and the mixture is ex 30
Sodafabrik, Ger. 236.3% (lull) , Staudinger, G-er. posed to light.~ a further reaction takes place,
506,839 (1930) , and Fermes, Can.' 329,043, (1933) , forming a compound of high molecular weight._
Diallyl, a dioleñn not having conjugated dou
disclose-the reaction oi' 80s with oleilr'is having '
conjugated double bonds. Ieopold Singer in ble bonds and consequently not 'being capable of
~ French Pat. 515,59@ (iuulidiscloses a process for
the production of lacquers, varnishes, etc., by’ re
acting suliurous acid with mineral oils. ln these
references to the prior art, no mention is made
of the reaction of'îêiûu with unsaturated com
pounds other than vsimple ol
and conjugated
hermore, since methods for the re»
action of many oi the simple oleo hydrocar»
bons are ~still unknown, it does not necessarily
follow from the previous disclosures that unsatu
rated compounds other than hydrocarbons would
react with Sdi. We have found, however, that
many compounds other than simple oledns and
" conjugated dioleñn hydrocarbons react with SO2
to. form lush molecular weight polymers of a
resinous nature.
‘We have reacted the following materials with
The unsaturated 'halogen derivatives, vinyl
undergoing 1_4 addition of SO2, was found to re 35
act rapidly with S02 to form ya _white insoluble
dimcultly fusible solid.
\ The unsaturated aldehyde, acrolein, reacts
slowly with 80a in the presence of light or cata
lyst’. The reaction can best be carried out at tem 40
peratures below atmospheric. The product is a .
solid insoluble in $62.
The unsaturated acids, acrylic, allylacetic, and
undecylenic react readily with SO2 in the pres
ence ci a catalyst or light.' The products are in 45
soluble in the excess Soi.l 'I_‘hey are softer than
the products obtained from oleiinic hydrocarbons
of the same number of carbon atoms, the product
of undecylenic acid being very soft and pliable.
The acetylene derivatives, ethyl acetylene and
phenyl acetylene, react with SO2 in the presence
of light or a catalyst.
The acetylene polymers. vinyl acetylene, di
_ chloride and allyl chloride react readily with lici-a l vinyl acetylene, and poly-divinylacetylene. react
55 uid S02 in the presence oi a cat or in light. slowly in liquid BO: in the lig-ht or in the pres'
ence ci' a catalyst to form an rie.,v hlm@ brßwm.
:f alcohol7 reacts y urated
in either and
ci tw
in thederivative,
light or in the presence 'or a cata»
lyst. A iet black solid material which is practi
cally insoluble and can loe molded only at high
temperatures and pressures is formed.
he ac
ways; the unsat-a
urated polyiunctlonal compound may be mixed
with the unsaturated hydrocarbon and SO2 lee
iiore reaction; in which case opportunity is aft
¿forded for molecules oi’ both types of unsaturated
' compounds to build into the same resin molecule;
Other compounds which we have converted to
or the resins of the two types of compounds may
resins 'by >reaction. with S0: are: allyl cyanide,
10 allyl isothiocyanata allyl thiourea, yand allyl urea.
@ther materials which should react with SO2
he formed by reacting separately with S02, and
then be blended in the desired proportions after
are: crctonyl alcolici,- chloroprenen bromoprene..
We have produced useful resinous products by
unsaturated vegetable oils such as tung oil, and the reaction of S02 with unsaturated compounds
partiallychlorinated olenns such as the cilchlo-4 . other than simple olehnic hydrocarbons and con
ride of diallyl.
-iugated dioleñnic hydrocarbons, have blended
in most cases We‘have found that the treat
the resins so obtained with resins formed by the
ment ci the unsaturated product to remove any :reaction of SO2 with simple oleíins and/or di»
absorbed oxygen and oxidation products .prior olefins in order to’modiiy the properties of` the
to reaction is desirable. f
latter and have also mixed such unsaturated
Although the reaction involves approximately
equimolecular proportions of SO2 and unsatu
' ' rated compound„- the reaction product usually
compounds with the simple oleiìns and dioleñns
and reacted the mixture with S02 under the
proper conditions.
removes excess SO2' from the reaction phase
in the adsorbed or dissolved form. It is, there
tore, generally, desirable to use more than the
‘ The following examples will illustrate the proc~
ess oi’ the present invention:
molecular equivalent oí SO2.
ride are sealed in a glass tube and exposed to
Any of the catalysts for these reactions previ
ously discovered and disclosed can be used, in
sofar as they are compatible with the unsaturated
30 compound to be converted to resin.
Resinous products formed from mixtures oi.'
simple oleilnic hydrocarbons and other unsat
urated compounds appear to have properties
which are generally intermediate between those
formed from the individual constituents.
2i. Equal volumes of liquid S02 and allyl chlo 25
sunlight or artificial light, preferably of short
wave length. After tire reaction has gone to com
pletion, as indicated hy the conversion ofthe
ñuid reactants to a stiff gel,.the excess S02 is
allowed to evaporate, leaving a white solid resin.
As a variation of the above, suitable for larger _
scale operation, the mixture of SO2 and allyl
chloride is placed in a bomb or autoclave pro
vided with a suitable source ofv internal illumi
In many ways the production of resins from . nation and the reaction is promoted photochem
such _compounds as unsaturated halogen deriv
II. Equal volumes oi' liquid S02 and allyl al
atives, alcohols, .ethers, esters, acids and alde- '
hydes, or materials contaminar them. by reaction ' cohol are placed in a bomb or autoclave contain
with S02 is'highly desirable and advantageous.
It would permit the production of resins having
ing 0.01-0.l per cent of silver nitrate, or other
suitable catalyst and. are allowed to react after
thorough mixing. After the reaction has gone
special properties; for example the allyl .alco
hol-S02 resin has unusually -high tensile strength. ‘ to completion, the excess SO2 is allowed to escape
while the undecylenic acid-SO2 and ethyl ac-j' and the solid resin is removed from the vessel.
Having described our invention, what we claim 45
45 rylate-SOz resins are soft and rubbery. Then,
too, a resin in which is tied up such a compound is:
l. The process oi' producing high molecular
of multiple. functions should be capable of fur
ther modiiication of properties hy other chemical weight polymeric products which comprises rer
reactions‘aiter formation of the SO2 complex. acting sulfur dioxide with unsaturated com
.Apparently only the carbon to carbon double
bond is involved in the resin reaction, leaving the
pounds selected irom the group; vinyl chloride 50
and allyl chloride.
e process of producing high molecular
weight polymeric products which comprises re
acteristic reactions. Thus, an allyl alcohol resin acting sulfur dioxide with vinyl chloride.
3. The process of producing high molecular
55 or an acrylic acid resin might be esterified in the
usual manner with acid anhydrides or alcohols, .weight polymeric products which comprises re 55
respectively, to >produce resins with a wide range acting sulfur diomde with allyl chloride. .
of properties. Still another advantage of the
use of these compounds is that they can he used
60 to modify the properties of resins from >unsat
otherl functional groups, such as hydroxyl or
carhoxyL'more or less free to undergo its char
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