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Patented Nov. 26, 1946 I
., 2,411,599
\’\2Au’5:91~z rnocass
7 William J. Sparks, ‘Elizabeth, and Anthony H. .
to Standard
Gleason, West?eld, N.~J., assignors
Oil Development Company, a corporation of
No Drawing. Application November 9, 1940,
Seriai No. 365,014
'5 Claims. (01.- 204-162)
2 _
and relates particularly to heteropolymers or in- >
terpolymers of an unsaturated ester of the type
~ of methyl acrylate with an iso-ole?n of the type
ment (under pressure it necessary) at the reaction
temperature by exposure of the mixture to ultra
violet light, or by treatment with peroxides, par
ticularly organic peroxides such as benzoyl per
oxide, or by the use of both ultraviolet light and
This invention'relates to polymeric materials‘
of isobutylene.
Among the'more easily ‘produced synthetic poly
peroxide catalysts.
Thus an. object of the invention is to hetero-1
mers are the polymers of methyl acrylate. These
polymerize together an' unsaturated ester such
polymers are readily produced by heating the
as methyl acrylate with an iso-ole?n such as iso-_
butyiene in the presence of a catalyst such as‘
. catalyst, or by exposure of the monomer to ultra
light or a peroxide, to produce a tough,
violet light. By these means it is possible to pro
duce poly-methyl-acrylates which are hard, clear, " ?exible, strong, transparent, white resin. Other
objects and details of the‘invention will be ap
transparent, thermoplastic resins. Also, iso- > parent
from the following description.
butylene can be readily polymerized by a low >
temperature ,. technique into poly-isobutylenes
methyl acrylate monomer with a peroxide as a
iso-ole?n are mixed in a container under such
which range in character from a heavy oil to a
pressure as is required to keep the iso-ole?n liquid
rubber-like substance, according to the molecu
at room temperature. A small quantity of an
lar weight.’ These polymers are produced by
organic peroxide such as benzoyl peroxide may
cooling theisobutylene to low temperatures, usu
be also incorporated into the mixture, and the
ally below --10° C. and preferably below -40° C., 20 whole
is allowed to stand in the presence of ultra
and thereafter treating them with a catalyst such
violet light for a substantial period of time to
as boron tri?uoride. These two polymers are
produce the desired lnterpolymer.
widely di?erent in their physical characteristics,
and it is very desirable to obtain materials hav
Example ‘I I
ing characteristics intermediate between those
of the respective polymers. To the present, how- '
' A mixture 01' 25 parts of monomeric methyl
ever, it had not been found possible to combine.
acrylate, having the formula
, these two substances.
The respective polymers
are mutually incompatible to mixing at ordinary
temperatures, since neither one dissolves in nor 30
combines with the other. Also at the low tem
peratures required for thepolymerization of iso
butylene, the methyl acrylate is non-reactive,
and at the normal room temperatures, the iso
butylene is substantially nonreactive with boron
tri?uoride and like catalysts to produce a high
molecular weight polymer.
with 25‘ parts 0! liquid isobutylene,_ having the
The present‘ invention provides a simple meth
od for producing a heteropolymer of the iso
and 1 part of benzoyl peroxide was prepared in
ole?n with the ester by which a new and im
40 a glass container, under suil‘icient pressure .to
proved polymer is ,obtained. This new polymer
keep the isobutylene in the liquid state, and the .
is an lnterpolymer or heteropolymer of the ester
container was sealed to maintain the pressure.
‘ and iso-ol'e?n, characterized by greater toughness
and strength than the poly-ole?n, and much less
brittleness than the poly-ester. Furthermore,
_ The container with the included mixture was
then exposed to light rays from a mercury vapor
lamp for a period‘of approximately 50 hours.‘
At the close of this period, a substantial strati?
cation had occurred in the container, a portion
being a solid polymer, the remainder being liquid
cording to'the constituent substances. The proc
isobutylene. The container was then opened, the
' ess'of-the invention heteropolymerizes the un
saturated ester withpthe iso-ole?n by av treat-l v50 excess isobutylene removed, and the solid poly
' the product is a clear, transparent, ?exible, water
'white resin, having- more or less elasticity ac
mer separated; The solid polymer wasdissolved
In this instance also a tough, ?exible, strong,
in benzol and reprecipitated from the benzol
‘clear, white resin was obtained. A proximate
solution by the addition thereto or. a substantial
analysis of this resin indicated that the methyl
quantity of methyl alcohol. The precipitate was ‘ acrylate had interpolymerized' with the tryptene
then dried for a substantial number of hours at’ 5 , in the proportion of approximately 7.3 parts of
temperatures between 90 and ‘100° C. under a - methyl acrylate to 1 part oi’ tryptene (mole ra
vacuum or 2'! inches. A proximate analysis of a
tio 8.5;1).
- .
sample or the polymer showed the following com
_ Example IV
' Per cent
' Carbon'
.10 ‘.A similar reaction occurs with 2 methyl bu
_ tene-l, having the formula‘
>Oxygen (by di?erence) ___________ __,.-- 28.87
For isobutylene the corresponding values are:
.15 A mixture of approximately equal parts of methyl
acrylate and the 2 methyl butene-l was .pre
pared as in Example I and treated over a similar
Per cent
prolonged period with ultraviolet light. In this
also atough, ?exible, strong, clear resin
For this particular“ sample or methyl acrylate the 20.' instance
was obtained on whichv ' approximate analysis
corresponding values are:
showed the methyl acrylate to be present with
the 2 methyl butene-l in the proportion of 3parts
methyl acrylate to 1 part of the 2 methyl butene-i
Per cent
(or a mole ratio of 5:2). .
Oxygen (by diil'erence) ________________ __ 38.62 25
Based upon the relative hydrogen values, the co
polymer contains approximately 23.5% of iso
butylene, and based upon the relative carbon
between methyl acrylate and dimeth'allyl, having
values, the copolymer contains-25.5% isobutylene,
the formula
A similar heteropolymerization reaction occurs
the respective polymerizates then being present 80
in the heteropolymer in the ratio of approximately.
3 parts of methyl acrylate to 1 part of isobutylene.
The interpolymer as thus produced by the
A mixture of approximately equal parts. of methyl
'above polymerization procedure is a clear. ‘35 acrylate and dimethallyl were prepared'as in Ex
tough, strong resin, completely insoluble in
ample I and treatedunder ultraviolet light for ‘a
water or aqueous liquids, and strongly resist
. ant to acids and alkalies. It is soluble in benzcl
' similar time interval. A similar tough, ?exible,.
strong, clear, white resin was obtained which was
and aromatic hydrocarbon liquids generally but
found to be insoluble in any available solvent in
insoluble in oxygenated organic solvents such as - eluding alcohols, ethers, esters and hydrocarbons
the alcohols, ethers, aldehydes, and organic acids. 40 as well as chlorinated hydrocarbons.
‘ ' '
The invention is not limited to the heteropoly
Example VI
merization of methyl acrylate with isobutylene',
but may be applied to a considerable number 01' '
other acrylate type esters and iso-ole?ns.
Example [I
A similar mixture 01' methyl acrylate was pre
pared with chloro
ethyl vinyl ether‘, having the‘
Methyl acrylate and- dimethallyl I ether react
45 similarly to the reaction‘ in Example I and Exams
ple V. A mixture or approximately equal parts
_‘ or methyl acrylate with dimethallyl ether, hav
ing the formula
was prepared as in Example I and treated for a‘
. similar length of time with ultraviolet light. In
this instance also a tough, elastic, strong, clear
in approximately equal parts and treated ‘with 55 ‘resin was obtainedv which also was found to be
insoluble in any of the ordinary solvents. ultra-violet light for a similar period or time.
This mixture likewise was found to interpolymer
Example VII
ize to yield a clear resin, and a similar‘ proximate
analysis showed that-the methyl acrylate and the
A similar reaction occurs-between methyl acry
ether interpolymerized in the ratio of approxi 60 late and methallyl alcohol, having the formula
mately 3 ‘molecules or methyl acrylate to 1 or the
chloro ethyl vinyl ether. This product likewise
is a tough, strong, ?exible, clear, white resin.
A mixture of methyl acrylate and methallyl al
Example III
‘35 cohol ‘in approximately equal proportions was
The reaction similarly proceeds with methyl
prepared as in Example I and subiectedto ultra
acrylate and tryptene, having the formula
6H; /CH!
A similar mixture of methyl acrylate and tryp
violet light for a prolonged time interval as in
Example I to produce a similar tough, elastic,
strong, clear, white resin in which a similar prox
70 imate analysis showed that the methyl acrylate
was present in the proportion of 2 parts to 1 part
of the methallyl alcohol (or mole ratio of about‘
3:2). This copolymer is readily soluble in the
tene was prepared as in Example I and treated
alcohols thus distinguishing it"from the
m a similar time interval with ultraviolet light. 75 lower
pure polyester of methyl acrylate.
the 3 to 2 ratio for methyl acrylate and methallyl
Example VIII ,
alcohol under ultraviolet light.
A similar reaction occurs between methyl acry
Example X
late and methallyl acetal, having the formula
Similarly methyl methacrylate and chloro ethyl
vinyl ether react under ultraviolet light to form
C a
CH: _
a copolymer similar to that obtained in Example
II containing approximately 3 percent of chlo
rine, in which there, appear to be approximately
As in previous examples, a mixture of approxi l0 11 molecular parts of the ester with 1 molecular
part of the ether. Other tests show. that the
mately equal parts of methyl acrylate and the sec
methyl methacrylate reacts in generally the same
ond constituent, in this instance methallyl acetal,
manner to produce similar heteropolymers as in, '
was prepared in approximately equal parts and
the case of the simple methyl acrylate. However,
treated with ultra-violet light as before. The
the reaction under the in?uence of ultraviolet
reaction yielded a similar strong, ?exible, clear, ‘ light
is noticeably slower, but it is generally more
white resin which, however, was found to be in
in the presence of peroxide cata
soluble in any of the usual solvents.
lysts, at elevated temperatures.
A similar experiment utilizing a mixture of
These resins, being thermo-plastic, are par
methyl acrylate in approximately equal parts with
ticularly well adapted for the preparation of
3 methyl butene-l, having the formula
molding compositions by themselves or in com
bination with a wide range of fillers, such as the '
inert pigments including ferric oxide, carbon
black, chrome green. zinc oxide, lithopone,
did not yield a polymerizate, indicating that the
absence of the iso-oleiinic structure prevented the
‘barytes and the like, as well as the various or-.
occurrence of this reaction. Similarly as the size
of the molecule ‘increases, the ratio of interpoly
merization decreases. This is well shown in the
cellulose ?bers generally and the like, either’v
ganic ?llers including paper, cloth, wood ?our,
with or without the various dyes which may be
applied to the various pigments. vor with the var
ious oil soluble dyes which are soluble in the
case of tryptene as above indicated, in which the
high molecular weight of the tryptene resulted in
‘a much lower proportion of hydrocarbon to
30 present resins. Similarly, being clear, white
resins, these materials are useful for transparent
molding compositions including lenses, various
Similar experiments were conducted with di
items of tableware and decorative articles either“:
pentene and producedonlynegligible quantities
of polymers, possibly because of the high molecu 35 in the clear, white of the pure resin or the clear 1
colors. produced'by dyes or the opaque colors
lar weight of the dipen'tene. Similar experiments
produced by ?llers with or without pigments,
were conducted with safrole, having the formula
methyl acrylate in the heteropolymer.
The_ resins are good bases for '7
paints, enamelsyvarnishes, _etc.; are good elec
trical insulators and are useful for molded in
lakes or dyes.
40 sulators either with or without insulating ma
terial fillers. and are particularly useful as re
placement material for uses where physical
properties of the type processed by-leather are
desired, since they are sumciently ?exible and
45 'elastic'to serve as leather substitutes, and in
and with citronellal, having the formula
some instances as replacement for rubber where
less elasticity‘ than is characteristic of rubber,
even when rubber is heavily loaded with pigment
but in these instances also little or no‘interpoly
fillers, is desirable.
mer was obtained, apparently because of the high
By the process of the invention there are thus
molecular‘ weight of the substances or possibhr
obtained a series of new and useful hetero
because they do not contain the
polymers in the form of resins of high strength,
high toughness, ?exibility, low brittleness, low
.solubility in solvents generally and a clear, trans
parent character which are particularly useful
for lacquers, adhesives, molded articles and the
‘ When dimethallyl is one of the. reacting com
ponents, both of the double bonds therein appear
to react giving cross-linkages between chains and
While there are above disclosed but a limited
resulting. in insolubility of the heteropolymer.
number of'embodiments of the invention, it is
Similar copolymerizations may be effected with
methyl methacrylate but‘ the reaction is gener 60 possible to produce still other embodiments
ally slower than that with the methyl acrylate, ' without departing from the inventive concept
herein disclosed, and it is therefore desired that
in spite of the supposed greater activity of the
only such limitations be embodied upon the ap
methacrylate. However, in this instance the
polymerization by 'the ‘use of a peroxide‘ catalyst 1
isgenerally satisfactory.
pended claims as are stated therein or required ‘I
05 by the prior: art.
Example IX
A ‘mixture of approximately equal parts of
methyl methacrylate andmethallyl alcohol was
4 prepared with‘ a‘ small quantity of benzoyl per
oxide and heatedlto a temperature of 85° C. for
This reaction was found to yield
‘ several hours.
aheteropolymer in which the methallyl alcohol 1
and methyl methacrylate were present in an ap
The invention claimed is:
- 1. The polymerization process comprising the
steps in combination of mixing a methylacrylate
and an alpha ole?n in liquid form at room tem- -
perature and interpolymerizing the mixture by
the application thereto of ultra violet light to
yield a high molecular weight, solid interpolymer
of a methyl acrylate and an alpha ole?n.
2. The polymerization process comprising the
proximately 1 to 1 'mole ratio as compared with 76 steps in combination of mixing a methylacrylate,
' 9,411,599
an alpha.- ole?n, and an organic peroxide in liquid .
iorm'at room temperature and interpolymerizing
the mixture by the application thereto of ultra
violet light to- yield ahigh molecular weight. solid
irlig?nerpolymer of a. methyl acrylate and an alpha.
"3. The polymerization process comprising the
-steps of mixing methylacrylate and isobutylene
phenyl ether in liquid i'orm under pressure at’ Y
room temperature and polymerizing the mixture
by the application thereto of ultra violet'light
to yield a high molecular weight, solid inter
polymer of a methacrylate and a chlor ethyl
phenyi ether.
5. The polymerization process comprising the
steps of mixing methylacrylate and dimethallyl
in liquid form under pressure at room tempera
‘ in liquid form under pressure at room tempera
ture and polymerizing the mixture by the ap-‘ m ture and polymerizing the mixture by the appli
plication thereto 0! ultra violet ‘light to yield a
cation thereto of ultra‘ violet light to yield a
high molecular weight, solid interpolymer 01' a
high molecular weight, solid oopolymer 01' a
methacrylate and isobutylene.
' 4. The polymerization process comprising the
steps of mixing methylacrylate and chlorethyl 1'5
methaorylate and 'dimethallyl.
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