Note: Descriptions are shown in the official language in which they were submitted.
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The present invention relates to a method for polymer-
izing difficultly polymerizable olefins or mixtures thereof to
obtain polymers in good yields. Still more particularly, it is
concerned with a method for polymerizing olefins, such as ~-
pinene, isoprene, isobutylene, terpenes or mixtures of same,
utilising a catalyst system comprising an aluminum halide an
alkyl germanium or an aryl germanium halide or alkoxide and
optionally a (lower) alkyl, alkenyl or aralkyl halide to obtain
polymers having softening points of at least 100C and possess-
. 10 ing relatively high molecular weights.
, Alpha-pinene has been subjected to isomerization and
polymerization utilising catalyst systems, such as aluminum
chloride alone or in conjunction with either a trialkyl silicon
halide or a dialkyl tin dichloride, attention being directed to
' United States Patent Nos. 3,354,132 and 3,478,007. However,
~! none of the prior methods is entirely satisfactory. The yields
obtained are poor and softening points low. Moreover, even to
obtain such unsatisfactory yields, such prior procedures require
rigorous drying of the olefin monomer and solvent prior to
polymerization. If a simple process could be provided to insure
' high yields hitherto unobtainable, and without scrupulously dry-
!, ing of the materials present, such a process would fulfill a
need long recognized in the art.
Thus, according to the present invention there is pro-
vided a catalyst system for the polymerization of an olefin
i monomer which comprises: a minor amount of an admixture of an
alkyl germanium halide or an aryl germanium halide and an alkyl,
alkenyl or aralkyl halide and (2) a major amount of aluminum
chloride or aluminum bromide or mixtures thereof.
The present invention also provides a process for
~ polymerizing olefin monomers which comprise the steps of:
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establishing a catalyst system comprising (a) a minor amount
; of a mixture of (a) an alkyl germanium halide, alkyl germanium
.;~ alkoxide or an aryl germanium halide (b) and from 0 to about
; 1% based on the weight of the monomer of an alkyl halide,
,
alkenyl or aralkyl halide, (2) a major amount of aluminum
chloride or aluminum bromide or mixtures of the latter in an
inert solvent, adding at a temperature between about minus
30 C and about plus 30 C the olefin incrementally with agitation
adjusting and maintaining the temperature of the mixture at
about minus 30C to about plus 30C for from about one to about
four hours, quenching the latter mixture with an aqueous sol- :
.': ution, separating the phases, and recovering a solid polymer .
:- from the hydrocarbon phase.
Particularly the present invention provides the above
process wherein the olefin monomer is a alpha-pinene.
. In a preferred embodiment of the aforesaid catalyst
~,
system the alkyl germanium halide is trimethyl germanium ;
chloride ranging from about 0.08% to 0.1% and the alkyl halide
. is t-butyl-chloride ranging from 0.4% to 1.0%.
The aforementioned catalyst system is first prepared :: .
in an inert solvent and the undried or dried olefin is then
added incrementally with vigorous stirring while
.
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1 maintaining the reaction mixture at from about minus (-) 30C.
to about plus (+) 30C. and, preferably, between about -20C.
to +20C., to insure maximum yield of resin of high softening
point. After the olefln has been added, stirring and cooling
S are continued for at least fifteen minutes or until the amount
i - of unreacted monomer is substantially reduced. Thereafter,
j the reaction temperature is permitted to rise slowly to a
temperature of about 20C. over a period of one to four hours.
The reaction mixture is then quenched with water or dilute
hydrochloric acid with the production of an organic phase
and an aqueous phase. Resultant polymer is then recovered
as a residue from the organic phase after removal of the sol-
` vent, as by steam distillation.
., .
Illustrative of the olefins which can be employed
herein are: linear aliphatic mono- or di-olefins, such as
isobutylene, isoprene, or piperylene, and terpenic olefins,
such as ~-pinenee, B-pinene, camphene, dipentenè, limonene,
and mixtures of the same, such as ~-pinene and isoprene or
a-pinene and limonene, so as to obtain either homopolymers
j 20 or copolymers.
Exemplary solvents or diluents include: aromatic
hydrocarbons such ao toluene, mixed xylenes, mesitylene, and
diethyl benzenes. Other solvents that can be employed here-
.
in are halogenated hydrocarbons, such as methylene chloride,
25 ethyl chloride or chlorobenzene. ~- -
Advantageously, the ratio of the organo germanium
halide to aluminum chloride or bromide in the catalyst ~ystem
may vary within wide limits. The amount of aluminum chloride
or bromide may vary from 2-10% and the alkyl germanium halide
~30 from 0.1 to 1.5%, both based on the weight of monomer. ~t
has been found that particularly satisfactory results are
attained with catalyst systems comprising 3 to 5 weight per-
'
cent of aluminum chloride and 0.6 weight percent of a trialkyl
' . .
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-' 10774~j~
germanium halide or a triaryl geDanium halide,
The organo germanium halide or alkoxide utilized in the process of
this invention can be represented by the formula:
RnGeXy
where R is lower alkyl or aryl, X is halogen or lower alkoxide, y is an
integer from l to 3 and n is 4-y. Illustrative of the organo germanium
halide or alkoxide co-catalyst component employed are: trimethyl germanium
chloride, trimethyl ge Danium methoxide, triethyl germanium chloride, tri- ~-
butyl germanium chloride, iodide, tri-t-butyl ge Danium chloride, dimethyl
ge Danium dichloride, diethyl germanium dibromide, monoethyl germanium
trichloride, monopropyl germanium trifluoride, diphenyl geDanium dibromide,
triphenyl germanium chloride and tri-n-propyl ge Danium chloride.
Due to the present high cost of organo geDanium halide the process
can be appropriately modified whereby the cost is substantially reduced -~
without dramatically decreasing yield of resin. This modification employs a -
co-catalyst.
Exemplary co-catalysts are: lower alkyl halides such as t-butyl
chloride, allyl chloride, benzyl chloride, benzyl bromide, sec-butyl bromide,
isopropyl chloride, n-propyl bromide and equivalents thereof.
The ratio of mixture of the alkyl, alkenyl or aralkyl halide and
the organo germanium synergist to aluminum chloride or bromide may vary
within wide limits. A ratio of 0.08 to 1.5%, and preferably 0.2 to 0.8% -
geDanium compound; 2 to 10% and preferably 3 to 5% aluminum chloride or
bromide; and 0.4 to 1.0% of an alkyl, alkenyl or aralkyl halide co-catalyst
all based on the weight of the monomer used. It has been found that
satisfactory results are particularly attained with a catalyst system com-
prising 5 weight percent of aluminum chloride and 0.6 weight percent of a
triaryl ger-
E - 3 _
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1(~774~4
1 manium halide synergist plus .8 weight percent of an alkyl,
alkenyl, aralkyl halide.
Advantageously, in the production of the high
yields of high softening point resin which characterizes the
S present invention, both the terpenic olefin reactant and the
inert solvent can be utilized without the removal of water
therefrom. For instance, it is known that a solvent can con-
tain as much as 400 ppm. water and the monomer as much as
200 ppm. water under ambient conditions. Greater amounts
of water, however, cannot be tolerated without concomitant
reductions in yields of polymer. Alternatively, the solvent
and monomer can be dried prior to reaction.
In a preferred practice of the invention, monomeric
olefin such as, for instance, ~-pinene, and solvent are each
employed undried, i.e. with respectively 100 and 300 ppm.
; ; detectable water. The overall system is flushed with an in-
ert gas, suitably nitrogen. ~he solvent and catalyst system
are introduced into the vessel and the monomeric olefin is
then added incrementally and progressively, while vigorously
stirring the reaction medium. As soon as the monomeric ole-
fin addition begins, an exotherm occurs and cooling is ap-
plied to maintain the reaction medium at -15C. to -20C.
Stirring and temperature control at this level are continued
for a period of time, generally 30 minutes, after all o} the
olefin has been added. Thereafter, the temperature is al-
lowed to gradually rise over a period of one to two hours
to +20C. to +25C,, where it is maintained for two to four
hours. Normally, reaction is continued until essentially
all monomer is converted.
me reaction mixture is then quenched to inactivate
the catalyst, as by adding a volume of water equal to the
volume of a-pinene used. Alternatively, a dilute solution
of an acid or base may be used. In all cases two layers are
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107746~
1 formed, one of which constitutes a hydrocarbon phase and the
other an aqueous phase. After separation, the hydrocarbon ~-
phase is washed repeatedly with equal amounts of water until
neutral.
- 5 The polymerization reaction may be carried out con-
tinuously by utilizing two reactors, the first held at -15
to -20C. and the second at +20C. The overflow from the
second reactor is continuously quenched and the polymer iso-
lated by a suitable technique. For instance, a-pinene of -
95 percent purity is commercially available and will give
excellent results
The following examples illustrate the invention.
Unless otherwise noted, the parts and percentages are by
weight.
-~ 15 Example 1
To a suitable three-neck flask are introduced 210
parts of xylene and there are next added 9 parts of aluminum
chloride and 1.8 parts of triethyl germanium chloride,
(C2H5)3GeCl, providing a weight ratio of 5:1. The resultant
mixture is vigorously stirred. 300 Parts of a-pinene are
then introduced over a period of 30 minutes. The reaction
mixture is held at minus 15C. to minus 20C. by a cooling
bath. Thereafter, the contents of the flas~ are maintained
in an inert nitrogen atmosphere at this temperature for one-
half hour. Thereafter, the temperature is allowed to risegradually with controlled cooling while finally reaching +20C.
to +25C. after two and one-half hours. There is next add-
ed water equal in volume to the ~-pinene, to inact1vate the
catalyst system, and to cause separation of the aqueous and
organic phases. The phases are separated, and the organic
one is washed three times with equal amounts of water. It
is then charged to a flask provided with a heater, thermom-
eter and nitrogen atmosphere, and the temperature raised to
- 5 -
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; 1 210C., thereby removing the solvent and recovering a sub-
stantial amount of the volatile germanium constituent in the
distillate. The introduction of~nitrogen is discontinued
and in its place steam is passed in and the temperature in-
creased to 230C. Steaming is continued until the resin soft-
ening point reaches the desired limit. Application of vac-
`j uum removes any trace of moisture and the molten resin is
obtained in 96.7% yield and having:
Softening point 120C., ring and ball
.
Color Gardner 2
; No. average molecular 820
weight
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Example 2
i ~ Repeating Example l in every detail except that
trimethyl germanium chloride, trimethyI germanium bromide
or triphenyl germanium chloride is substituted for triethyl
¦ germanium chloride, there i 8 obtained a-pinene polymer in
oxcellent yields.
Example 3
The procedure of Example 1 is repeated in every de-
tail except that trimethyl germanium bromide in lieu of tri-~
ethyl germanium chloride is dissolved directly in the monomer
~ feed rather than in the solvent. There resules a yield of
i 95% a-pinene resin having a softening point of 113C.
~ 25 Ex~e~c_4
f: The procedure of Example 1 is followed in every
,; detail except that the monomeric a-pinene reactant and the
~ solvent are carefully dried. There is obtained a resin yield
,~ . . .
(polymer) of 91.0%, based on the weight of the monomer, and
a softening point of 125C.
Examples 5 - 27
The procedure of Example 1 is followed in every re-
spect except that the specific solvent, temperature, catalyst
.
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`-' 1077464
1 system and polymeric product are set and summarized in
Table I below.
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~1 Examples 29 - 38
The following examples all illustrate the
AlC13/RnGeXy catalyst system, where R, X, n and y are defined
above, as useful for the preparation of homopolymers and co- --
5 polymers derived from a variety of monomers by utilizing the -:~
procedure of Example 1. The modifications and results are :-
summarized in Table II below.
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1 ~ Example 39
` ~ a-Pinene and a-pinene-limonene resins, as prepared
in accordance with Examples 1 and 33, respectively, are ex-
tremely light in color and show exceptionally wide compat- -
ibility with commonly used polymers and film formers. They
have -the ability to tackify other materials with which they
are compatible, such as styrene-butadiene rubber, natural
rubber, ethylene-propylene elastomers chlorobutyl and butyl
rubbers.
The following table lists results of test evalua-
tions of pressure-sensitive adhesives employing a-pinene resin
and a 1:1 a-pinene-limonene copolymer as tackifier with pale
crepe natural rubber and styrene-butadiene-styrene block co-
~`~ polymer, respectively.
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; 1 The tackifiers listed above are employed in the
following formulation:
100 parts elastomer
75 parts tackifying resin
1 part antioxidant
Polyisoprene natural rubber is milled to a Mooney viscosity
of 50 prior to use. Kraton 1102~ a linear block styrene- -
-butadiene-styrene, is used as received.
Example 40
a-pinene-isobutylene copolymer as prepared in ac-
cordance with Example 34, is a resin having a softening point
of 35C. In addition to its use in pressure-sensitive tapes
as shown in Example 39, the low molecular weight polymer ha~
a large variety of applications, such as an oil additive,
viscosity index improver, sealant, caulking agent, special
lubricant, soundproofing compound, ink, or as a waterproofing,
leather impregnating, and paper coating agent.
Example 41
The procedure of Example 17 is repeated in every
detail except that trimethyl germanium bromide in lieu of
triethyl germanium chloride is dissolved directly in the mo~-
,
omer feed rather than in the solvent. There results an 84.0%
yield of a-pinene resin having a softening point of 113C.
Example 42
The procedure of Example 17 is followed in every
dètail except that the a-pinene monomer and the solvent are
carefuily dried. There is obtained a resin yield (polymer)
of 83%, based on the weight of the monomer, and a softening
point of 115C.
a-Pinene polymers prepared as in Examples 1 to 10,
and 12-28, have molecular weights of from about 700 to 900
by vapor pressure osmometry, and a softening point of at least
about 110C. These polymers are soluble in solvents, such
- 14 -
.
,
\ ` lo7746~ :
1 as hexane, benzene, heptane, toluene, xylene and mineral spir-
its. However, the latter differ from other related polymers,
namely the ~-pinene polymers, in exhibiting solubility in
methyl ethyl ketonef dioxane, ethyl acetate and cyclohexanol.
Example 43
~-Pinene resin as prepared in accordance with Ex- -
ample 17 is extremely light in coior and shows exceptionally
; wide compatability with commonly used polymers and film form-
- ers. It has the ability to tackify other materials with which
it is compatible, such as styrene-butadiene rubber, natural
- rubber, ethylene-propylene elastomers chlorobutyl and butyl
rubber by method5 well known in the art. -
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