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Patented Dec.‘ 17, 1946
UNITED STATE 5‘ PATENTOFFICE.
OLYMER on time‘
msowmtmimor
OLEFlN
AN _UNs ATUBAfl-‘EDYEIHER ,
William -J.1‘ Sparks,‘ ' canon, ‘and :Robert 1
Thomas, Union, N. J ., assignors to Standard Oil
Development‘companma corporation otDela-w '
, ware
v No Drawingx‘ ‘Appli cation‘J‘ul‘y 9,1943,
'
~ ~
Serial No.‘494;,020 ‘
.
sclainis.
(o1. ace-#86) ‘
i‘ “ther ethers of ' higher molecular “weight, are
This application relates to hydrocarbon‘poly
similarly usable,“ including ,such :asubstances, was" i ,
mers; relates‘ particularly to interpolymers ‘for
‘ ~dlvinyl ether,i‘vinyl methallyllethergetcurwhich‘ ‘7 ‘
heteropolymers of an isoole?nwithL-an oleflnic ‘
contain a two , double, “bonds,
ether and relates particularly‘ a‘: heteropolyiners
adiole?ns.‘
as inqalkadienes-gor
"
i
i
‘
objecteoi the present invention-is ‘to _ i ‘ “
prepare a heteropolymer of ant isoolefln such as ‘
- "of isobutylene with an olefl‘nic ether,‘ ‘
‘ “Thus an
As is well known to those ‘skilled in ‘the art, ‘it
has been found pos‘sible‘toproduce a heteropoly- ‘ ' ‘ ' isobutylenewith .an olefinic
ether‘ i'such J ‘ as, di- ‘ ‘
mer of an iso‘ole?n such as isobutylen‘e ‘with a
»methallyl ether or methallyl-allyl‘ ether and their
conjugated diole?n such as butadien or isoprene
lhomolog‘ues to produce a new ‘and useful hetero
10.
or the like, utilizing‘an active metal halide, or
‘polymer. Other objects and details oi the inven- , i
Frie'del-Crafts type catalyst dissolved ine‘e‘a ‘low
tion will be apparent‘ from the following des'crip- I ‘
‘freezing, inert solvent. The resulting polymers ,
tion;
‘
i
have molecular weights ranging from ‘15,000 to I
i In practicing this invention‘;anoleflnic‘miirture
‘
150,000
and they are reactive with sulfur “in _a e , is prepared consisting of thesimple ole?n, pref- ’
' curing reaction by which the ?uidity. of the poly- ‘
erably isobut‘yleneg“ with a .dioleflnic ether, the
mer is modi?ed and replaced by an elastic limit ‘ ‘isoole?n being present in anykde'sired proportion;
C
at which the material has a relatively hightensile
but‘preferably the isoole?n is present insthe ratio "1 ,
strength and a high elongation. This reaction» ‘of
fromi60 to 99 ‘parts with‘thediole?'nic ether
‘
has been found‘ to be very sensitive to added sub- 1
present in the‘ proportion of 40 to ,l'part. This
20
other
olefins
‘being’
strongly‘
stances, many of the
‘ole?nic‘ mixture may be polymerized at the de
poisonous‘ to the reaction, including ‘such ‘sub-‘ ;, sired temperature as prepared, only the catalyst
, stances as isobutylene dimerand‘various other‘ ‘ i being added; but it is preferably diluted‘ with a
higher unsaturates. Likewise, acid, alkali, alde-;
been found to be immediately destructiveto the,‘
diluent-refrigerant such asliquid ethylene or, liq
uid ethaneV or liquid methane or‘ mixtures‘ of-one or
reaction to such an extent that it has been con,
‘gethermwith other‘ inertediluents s‘uch'asliquid"
hyde, ethereal and alcoholic ‘substances _, have
more of these, several‘ ,dilueiité'refrlgerants, to- ,
sidered that the presence‘ of oxygenated com
propane, liquid butane‘, liquidvethyl or methyl
pounds of any kind is fatal to vthe reaction; even ‘
such substances
the “like, the‘f“diluent-relfrigerant ‘ the aliphatic ‘ethers being,‘ ,chlorides‘a‘nd
as ‘
being present in thep‘roportio‘n of ‘fro'm‘Z to 5 or
“ the cause of immediate cessation of the polymer-i
ization
reaction.
,
,
x
‘
?‘volumes vper‘volume‘ of mixed ole?ns. Alter
natively, an excess ‘ of solid , carbon‘ dioxide ‘ may
e
The present invention presents a ‘new high
“be utilized either with or‘ without an auxiliary
molecular weight heteropolymer and polymer
ization process involving the interpolymerization
, diluent such ‘as propane,
of an ole?n, preferably a hydrocarbon ole?n such
of an‘activemetalhalid‘e such asalu‘minuniL chlo
ride,‘ bromide or iodideor uraniumlor titanium
desirable alternatives,‘ such substances as alpha
chloride, dissolved in a'low‘ freezing solventsuch
methyl styrene and alpha-methyl paramethyl
‘ ‘as‘rethyl or methyl chloride‘ or‘ carbon-dioxide or ‘ ‘
styrene, indene, coumarone, and the like‘; with
‘an ole?nic ether containing two isolated ethylenic
40
,
-
,
,
Substantially ‘ e ,
printed in' the issue of‘ “‘Cheni-‘
theAme‘rican‘Chemi- 1,
a
cal‘ Society‘at Baltimore in
‘A suitable ole?nic ether for the present re
action‘is dimethallyl ether, having the
homologous f’s'ubstances.‘
Crafts
Synthesis,”
y
‘y
-' ical Reviews” published for
of a dissolved active metal halide, catalyst, ‘pref,- ,
‘erably below 0° C.
‘similar
any of the Friedel-Crafts ‘catalysts as disclosed
b N. 0. Callowa in‘ his article on “The Frledel
'
tures to the mixture.
“
‘The catalyst preferably consists of a solution ' ‘
as isobutylene or propylene, or the normalpbw‘
tylenes, or the amylenes; and, in addition, as‘
double bonds, by the application‘
‘ ethyl ‘or methyl ‘ chlo
‘ ride or similar inert,;1ow" freezing substances.
formula:
I
1935 in volume XVIII,‘ ‘ e
the ‘article beginning on page 327, the list being“ I
particularly well shown on page 375, may be‘ used. ‘
The simple halide compounds may be used or
Alternatively, other diolefinic ethers' such ‘as
‘methallyl-allyl ether
‘Ha CH3 H2
are usable in ‘the polymerization reaction, still
various-forms oi doublesalts such as thechloro
bromide and the like-maybe usedl
‘
As the‘ catalyst‘solvent, with the‘ simple Fieclel
Crafts halides‘, the preferred‘ solvent‘ is a lower
‘alkyl halide, such as‘ethyl ‘or methyl chloride,
55 the alkyl mono or‘ poly halides up to 5 or‘6 carbon‘
2,412,921
‘ atoms per molecule which have‘ freezing points
depending upon the temperature, of polymerize’, '
tion and the proportion of dimethallyl ether
present. :It is substantially insoluble in hydro
jcarbon solvents ‘generally and shows only a
below about 0° C., thereby being low-freezing sol
’ [ ‘vents, may be used,‘ Alternatively, carbon disul
?de in ‘its various forms and homologsmay alsov
_
be used as ‘catalyst solvents. With the modi?ed ~
‘ or double ‘ salt vFriedel-Crafts ‘catalyst particu-'
.7 nominal amount of swelling in the lower molec- .
_ ular Weight hydrocarbon solvents. It is likewise
larly, a considerable number of the loweiyhyclro
insoluble in ether, alcohol or acetone, and in fact,
I -' carbons such as liquid propane, liquid butane and I
> {the like may be used as solventspapproximately- ' -
'7 or:8 carbon atoms compounds being the upper
;
:-J'limit.'
.
»
.
l
I
o.
.' ‘ , ‘ The temperatureof the reaction for the ‘poly
"'most}._oxygenated solvents, although again it
swells somewhat'by absorption of these solvents.
~'I“hisupartiicular polymer is poorly reactive with
sulfur and does not undergo any curing reaction
:
readily.v
,
Q -' 'merization preferably lies’ between 0° C. .and
,- about —164° C.;l and the most convenient teme ‘j " I
‘p'eratures are ~78” CL, asset by solid carbon di-m
’
l
'
;
r
‘Y
-
[Example II
‘a A similar polymerization reaction is foundto
oxide, or —95 to ‘—103° C., as set by liquid
“ ethylene.
‘
'occur with methallyl-allyl ether, using similar
proportions of ‘the isobutylene and methallyl-allyl
'
Y , The catalyst solution may be applied to the
ether and a similar polymerization procedure to
reaction/‘mixture in any. desired ‘manner. It
' _' maybe poured in and'stirred, vigorously, provid
‘ "inggithe- stirring‘ equivalent ,is_,suiiiciently power
“ ful. Ittmay be delivered into-the rapidlystirred
reaction mixture as a rapid stream, or by otherv
l. methods which will be obvious;'but the catalyst
solution is preferably applied 'in the form of a
that abovedisclo'sed'in Example I. ,In this in
stance also, a high‘ molecular weight polymer is
produced which, however, diifers from‘the poly
‘ mer of Example I in beingreactive with sulfur
spray or'mist'on to ‘the surface of. the rapidly
; stirred niixtureof. the‘ole?ns and diluent-refrig
erant. "I'he'reaction-proceeds rapidly to produce
for a‘curing reaction to develop'an elastic limit,
a relatively high tensile strength and a high
elongation, togetherwith insolubility in both hy
; 'dr'oc'a'rbon and. oxygenated solvents.
Ezrample III
the ‘desiredsolid, plastic, elastic‘ polymer.
"Ihe'resulting heteropolymer shows charac
lyl-allyl ether was then compounded according
I The, heteropolymer of isobutylene and methal
teristics depending to a large extent upon the
,}to the following formula:
y; particular diole?nicether- utilized. A hetero
" polymer containing substantial proportions of '
.:
I
7.
Parts
Heteropolymer _________________________ -..~ 100
' dimethallyl etherlireacts with sulfur,_with dif?
culty: and is strongly resistant‘ to hydrocarbon
‘solvents; The presence of substantial propor
tions of‘ oxygen as introduced through the di
:Zlncoxide-.. _____ .._‘ __________ __> ________ _‘_~_-
5
Stearic acid__'______»____________________ __
3
Sulfur ______ __;__‘__'___> __________________ __
3"
.Tuads (tetramethyl thiuram disul?de)___'___ 1
strongly resistant to solution in hydrocarbon’ ,
In preparing this coImpound, ,the'heteropolymer
im‘ethallyl ‘ether makes. the material still more’
solvents.v ‘
'~
' l, ‘I
V
'
‘
>
was, worked brie?y upon the mill for a time in
I
" ‘Example I
mixture of .98 Darts of'liqllid isobutylene was
prepared ,w'ithttwo ‘parts or dimethallyl ether,
and 4Ivolumes of liquid ethylene were added to
,the v'mixture. lThe?mixture was prepared, in _a
“reactor, equipped ‘with a powerful stirring device
and provided with acover to avoid .,loss_.of
volatilized' gaseous constituents. The reactor ’
also, was well heat insulated to reduce the rate,
of volatilization of the'refrigerant by, ambient
heat. The catalyst, was prepared by; dissolving
commercial anhydrous. aluminum chloride in
methyl chloride at'the, boiling point or the methyl
chloride to yield .a saturatedsolution containing
‘0.9% 'of aluminum ‘chloride. ‘This solution was
then diluted withv an additional amount of
methyl chloride to produce a solution contain
ing 0.4% of dissolved aluminum chloride, This ‘
solution was then precooled, to the temperature
of the liquid ethylene, approximately —‘103° C.,
a and sprayed on to the surface of the vigorously
terval
of. approximately 5 minutes. Then the
_
zinc oxidewasadded and thoroughly incorpo
rated into the polymer by further working on
the mill. ‘Thereafter, the stearic acid and sulfur
‘were simultaneously‘ added, the mill temperature
during this portion of the operation being main
tained at approximately 125° C. ' When these
ingredients, were thoroughly incorporated, the
mill was cooled to a temperature of approxi
mately 90", C. and the'Tuads added quickly, the
compound removed, from the mill and cooled.
This prepared, compound was then placed in
a mold and cured at a temperature_of_155° C. for
60 minutes to produce the desired cured rubber
like polymer. '
'
‘
'
'
Example 4
A mixture was. prepared consisting of 970 parts
,lby weight of isobutylene, .30 parts by weight or
divinyl ether and 2000 parts by weight of methyl
chloride. This material was cooled to a temper
ature of approximately --78° C. by the addition
stirred mixed ole?ns through a misting nozzle. ‘ of 4000 parts by weight of ‘polymerized solid'car
The polymerization proceeded rapidly and was, ' bon dioxide.
The material was well stirred and
approximately 80% complete in about 5, minutes.
when the temperature had been lowered to the
When'this stage of polymerization was reached,
the polymerization "mixture was diluted with
_ desired point, a steady, moderately rapid stream
approximately 1/2"volume of propyl alcohol or.
ethyl alcohol‘or ethyl ether or similar oxygenated
hydrocarbon, to quench the catalyst and arrest
polymerization. The solid polymer was then
‘ brought up'to room temperature and was'ready
for furthertprocessing.
'
,
This material, ‘as so polymerized, shows a
molecular weight ranging from ‘10,000 to 100,000,
the polymer was found to contain approximately
12% of‘ copolymerized divinyl ether. The mate
rial showed a good solubility in oil and in light‘
2,412,921
-
s
‘
1
.
naphtha solvents and when dissolved in a good
lubricating oil, produced a substantial improve
ment in the viscosity index thereof.
Example V
A mixture was prepared consisting of 500 parts
of isobutylene and 500 parts or divinyl ether. To
this mixture there were then added ‘2000 parts of
'methyl chloride and the material was cooled to a
temperature of approximately -'l8° C. by the
' addition of 4000 parts by weight 0! pulverized solid
carbon dioxide. As in Example IV, the polymer
ization was conducted by bubbling a stream of
gaseous boron tri?uoride through the ole?nic ma- '
terial. The polymerization proceeded rapidly to
yield a hard polymer which was insoluble in hydro
carbons generally but thermoplastic and suitable
for molding operations. The material showed a
6
50 to 98 parts by weight of an ole?n having 3 to
5 carbon atoms and one ethylenic double bond
‘ per molecule with 2 to 50 parts by weight of an
ether having 4- to 8 carbon atoms and two isolated
ethylenic double bonds per molecule, ‘the ether
having an oxygen link between hydrocarbon
groups containing each of the two isolated
ethylenic double “bonds.
2. A heteropolymer comprising in combination
98 parts by weight of isobutylene with 2 parts by
weight of an ether having an oxygen link between
a methallyl group and a, hydrocarbon group'con
taining 3 to 4 carbon atoms and one ethylenic
double bond.
.
3. A heteropolymer comprising in combination
98 parts by weight of isobutylene ‘with 2 parts by
weight of dimethallyl‘ ether.
4.‘ A heteropolymer comprising in combination
98 parts by weight of isobutylene with 2 parts by
much greater toughness, and a lower brittleness
weight of methallyl-ally] ether. ‘
than is characteristic of polyvinyl ether, and an‘ 20
5. A heteropolymer comprising in combination
absence of the cold flow which is characteristic
50 parts by weight of isobutylene with 50 parts
of simple polyisobutylene.
‘
Example VI
by weight of divinyl ether.
6. A composition of matter comprising in com
bination with sulfur a sulfurizable heteropolymer
A mixture was prepared consisting of 900 parts 25 of 98 parts by weight of isobutylene combined
by weight of styrene, 100 parts by weight of
divinyl ether and 2000 parts by weight of methyl
chloride. This mixture was placedin a reactor
jacketed with liquid ethylene and cooled to a
temperature of approximately --l00° C. When
this temperature was reached, approximately
' 2000 parts by weight of a 0.5%‘ solution of alu
with 2 parts by weight of methallyl-allyl ether.
7. A polymerization process comprising the
steps in combination of mixing 50 to 98 parts by
weight of a mono-ole?n having 3 ‘to 5 carbon
atoms per molecule with 50 to 2 parts by weight
of an ether having 4 to 8 carbon atoms and two
isolated ethylenic double bonds per molecule, the
minum chloride in ethyl chloride were added with
ether having an oxygen link between, hydrocar
rapid stirring of the cold ole?nlc mixture. This
bon groups containing each of the two isolated
procedure yielded a solid polymer which was found 35 ethylenic double bonds, cooling the mixture of
to be soluble in hydrocarbons, thermoplastic and
the monoole?n and the ether to a polymeriza
excellent for pressure molding.
tion temperature between 0° C. and -‘l64° C., and
Many other simple ole?ns such as propylene,
e?ecting polymerization of the resulting mixture
which contains 3 carbon atoms per molecule, the
by adding thereto a Friedel-Crafts catalyst dis
40
various normal butylenes, the amylenes and var
solved in an inert organic solvent which is: liquid
ious of the higher oleiins up to about 8 carbon
at the polymerization temperature. '
atoms per molecule are similarly reactive with the
8. A polymerization process comprising the
ole?nic ether.
steps in combination of mixing 98 parts by weight
Thus the invention provides a new and useful
of isobutylene with 2 parts by weight of an ether
heteropolymer of an ole?n with a diole?nic ether
having an oxygen link between a methallyl group
in which relatively high insolubility in solvents
and a hydrocarbon group containing 3 to 4 car
generally is obtained, together with Sulfurizability,
bon‘ atoms and one ethylenic double bond, cool
high strength, high elongation and so forth.
ing the isobutylene mixed with the ether in the
While there are above disclosed but a limited
presence ,of liquid ethylene at a polymerization‘
number of embodiments of the invention, it is 50 temperature within the‘ range ‘-95° C. to —103°
possible to produce‘ still other embodiments with
C., and effecting polymerization of the_isobuty1
out departing from the inventive concept herein
one with the ether in the resulting cooled mixture
disclosed, and it is, therefore, desired that only
by adding thereto aluminum chloride in an alkyl
such limitations be imposed upon the appended
‘halide solvent which is liquid at the polymeriza
claims as are stated therein or‘required by the 55 tion temperature.
prior art.
The invention claimed is:
l. A heteropolymer comprising in combination
WILLIAM J. SPARKS.
ROBERT M. THOMAS.
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