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Патент USA US3095416

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United States Patent 0
3,095,406
Patented June 25, 1963
1
2
polymerization catalyst so as to thereby obtain rubbery
3,095,406
polymer products having desirable physical properties.
PREPARATION OF POLYMERS 0F
CONJUGATED DIENES
James N. Short and James E. Puckett, Bartlesville, Okla,
assignors to Phillips Petroleum Company, a corporation
Other and further objects and advantages of the in
vention will become apparent to those skilled in the art
No Drawing. Filed July 28, 1958, Ser. No. 751,187
15 Claims. (Cl. 260-943)
whereby conjugated dienes can be consistently polym
upon consideration of the ‘accompanying disclosure.
of Delaware
The instant invention is concerned with .a process
erized to rubbery polymers of a desired inherent vis
cosity. Broadly speaking, in a process in which a con
' This invention relates to the preparation of polymers 10 juga-ted diene is contacted with a polymerization cata
of conjugated dienes. In one ‘aspect, the invention re
lyst, the instant invention resides in the improvement
lates to a method for polymerizing conjugated dienes in
which comprises treating the conjugated diene with a
the presence iof a catalyst comprising an organomet-al
v polyhydric alcohol prior to its being contacted with the
or metal hydride. In another aspect, the invention relates
catalyst. It has been discovered that the polymerization
to ‘a polymerization process in which the conjugated 15 can be effected at relatively low catalyst levels to give
diene to be polymerized is pretreated prior to contact
?rm, non-sticky, rubbery polymers if the conjugated diene
with the polymerization catalyst.
is ?rst treated with a polyhydric alcohol. The poly
It has been previously disclosed that conjugated dienes
hydric alcohol treatment can be effected by ‘any suitable
can be polymerized in the presence of a catalyst com
method known in the art, for example, by liquid-liquid
However, 20 extraction with subsequent separation of the monomer
it has been found that when the polymerization is car
phase or by vapor-liquid extraction in a column.
.
'
ried out at low catalyst levels, for example, in the case
The monomeric material polymerized to produce rub
of butyllithinm at below 4 millimols per 100 grams of
bery polymers by the process of this invention comprises
monomer charged to the process, rather erratic results
conjugated dienes‘ containing from 4 to 10, inclusive,
‘are often obtained. In other words, the polymerization 25 carbon ‘atoms. Examples of conjugated dienes which
prising an organometal or a metal hydride.
reaction may or may not occur.
In many cases where
can be used include 1,3—butadiene, 2-methyl-l,3~buta
polymerization does take place, the product has a low
inherent viscosity (low molecular weight), and a poly
diene (isoprene), 2,3-dimethyl-l,3-butadiene, 1,3-penta
mer is often obtained which is soft and sticky or it may
in some instances resemble a wax instead of 1a rubber. 30
Although .the conjugated dienes are ordinarily used in
a high state of purity, it appears that they-still contain
diene, 2—methyl—1,3-pentadiene, 2,3-dimethyl-1,3-penta
diene, 3-methyl-1,3-pentadiene, 2-phenylbutadiene, vand
the like.
.
This invention is applicable to the polymerization of
the above-de?ned conjugated dienes either alone or in
small amounts of materials which have a deleterious
admixture with each other and/or with one or more
effect on the polymerization catalyst and which are be
‘other compounds containing an active CH2=C< group
35
lieved to be in some way responsible for the erratic
which are copolymerizable therewith. Included vamong
results obtained. Treatment of conjugated dienes, such
these latter compounds are aliphatic l-ole?ns having up
as butadiene or isoprene, with a drying agent, .e.g., cal
to and including 8 carbon atoms per molecule, such ‘as
cium sulfate, prior to polymerization has been tried in
ethylene, propylene, l-butene, l-hex-ene, and l-octen‘e.
order to remove traces of moisture which might account 40 Branched chain ole?ns, such as isobutylene, can be used
as well as 1,1-dialkyl-substituted and 1,2-di-alkyl-substi~
for the ‘unsatisfactory results. However, even when fol
lowing this procedure, polymerization may not occur
tuted ethylenes such as butene-Z, pentene-Z, hexene-Z,
heptene-Z, 2~rnethylbutene-1, 2-‘methylhexene-1, Z-ethyl
with any regularity unless comparatively large ‘amounts
heptene-l, and the like. Other ole?ns which can be
of catalyst ‘are utilized. Furthermore, in instances where
polymerization does occur, the conversion is frequently 45 used include di- ‘and polyole?ns, such as 1,5-hexadiene,
1,4-pentadiene and 1,4,7-octatriene, and cyclic ole?ns,
low and the polymer product may have ‘a low inherent
such as cyclohexene. Other examples of compounds
viscosity. While the use of higher catalyst levels might
containing an active CH2=C< group which ‘are co
polymerizable with one or more of .the conjugated dienes
appear to be feasible, increasing the amount of the cata
lyst often results in the production of polymers with de
are ‘styrene, acrylonitrile, methacrylonitrile, methyl acry
creasing inherent viscosity, and low molecular weight,
late, methyl methacrylate, vinyl acetate, vinyl chloride,
sticky ‘and non-rubbery products are often obtained.
It is an object of this invention, therefore, to provide
‘an improved process for polymerizing conjugated dienes
in the presence of a catalyst comprising an organometal
or a metal hydride.
Another object of the invention is to provide a process
for polymerizing conjugated dienes in which the polym
erization is carried out at catalyst levels lower than those
vinyl-idene bromide, Z-methyl-S-vinylpyridine, 2-vinylpy
ridine, 3-vinylpyridine, 3-viny-1tol-uene, l-vinylnap-htha
lene, Z-Vinylnaphthalene, 4-v-inyltoluene.
55
As previously mentioned prior to contact with the
polymerization catalyst, the conjugated dienes to be
polymerized are treated with a po'lyhydric alcohol. The
polyhydric alcohol is liquid under the treating condi
tions and preferably contains not more than 10, more
usually employed while obtaining a product having good 60 desirably not more than .5, carbon atoms per molecule.
physical properties.
The term “polyhydric alcohol” as used herein is intended
A further object of the invention is to provide a proc
to designate an alcohol containing two or three hydroxy
1 ess for polymerizing conjugated dienes in which the con
groups. As the treating agent, it is preferred to use the
j jugated dienes are pretreated prior to contact with the
glycols', particularly ethylene glycol. Examples of poly
3,095,406
3
hydric alcohols which can be employed include glycols,
such as ethylene glycol, propylene glycol, ‘diethylene
glycol, trimethylene glycol, triethylene glycol, tetrameth
ylene glycol, diethylene glycol, triethylene glycol, butyl
ene glycol, amylene glycol, 1,6-hexamethylene glycol
(1,6-hexanediol), 2,4-hexanediol, 1,8-octanediol, 4,5
octanediol, 1,10-decanedio-l, and 1,2-decanediol, glycerol,
1,2,3-butanetriol, 1,3,5-pent-anetriol, and 2,3,4-hexane
tr-iol. With the lower viscosity treating agents, such as
ethylene glycol, the treatment can be effected at room
temperature, e.g., at about 25° C. However, with ma
terials which are very viscous or solid at room tempera—
4
cyclohexane, 1,2,3,5-tetralithio-4-hexylanthracene, and
the like.
When employing a two component catalyst system to
polymerize conjugated dienes according to this invention,
one component is an organometal or a metal hydride and
the second component is 1a Group IV to V1 and VIII
(Mendeleef’s Periodic System) metal compound, e.g., a
salt or alcoholate. The organometal compounds referred
to include, without limitation, alkyl, cycloalkyl, aryl,
alkaryl, aralkyl, alkylcycloaryl, or cycloalkylaryl com
pounds of di-, tri-, or tetravalent metals, particularly
Group I, II, III or IVB metals such as sodium, potassium,
lithium, rubidium, cesium, magnesium, cadmium, mer
ture, such as glycerol or 1,8-octanediol, higher tempera
cury, zinc, barium, lead, tin, aluminum, boron, gallium,
tures, e.g., up to about 80° C., are advantageously uti
lized in order to facilitate contact of the conjugated diene 15 indium and beryllium, or such organometal compounds
in which one or more of the organo groups is replaced
with the treating agent in liquid form.
by a hydrogen atom and/ or a halogen atom. The organo
After treatment of the conjugated dienes with the poly
groups can be quite large, compounds being applicable
hydric alcohol treating agent, the polymerization is
which have 15 or more carbon atoms in each group and
effected by contacting the conjugated dienes with the
polymerization catalyst. Because of this treatment of 20 40 or more carbon atoms in the molecule. Speci?c ex
amples of such organometal compounds include triethyl
the monomeric materials, it has been found that the
polymerization can be carried out at much lower catalyst
levels than those ordinarily employed. Thus, it has been
found that polymerization can be e?ected using catalyst
levels as low as 1.5 millimoles per 100 grams of mono
mers. On the other hand, when untreated monomers are
used, about 3 millimoles are required. Furthermore,
when operating at a catalyst level of 1.5 to 3 millimoles,
high conversions are consistently obtained while produc
aluminum, triisobutylaluminum, a mixture of diethyl
aluminum chloride and ethylaluminum dichloride, some
times referred to as ethylaluminum sesquichloride, di
ethylaluminum hydride, ethylaluminum dichloride or di
ethylaluminum chloride, taken alone, trioctylaluminum,
tridodecylaluminum, triphenylaluminum, triphenylgal
lium, ‘diphenylberyllium, dicyclohexylberyllium, diethyl
zinc, cyclohexylzinc chloride, tetraphenyllead, tetracthyl
adversely affect the polymerization catalyst. Since treat
til'l, land CHgAlClz, (C4H9)2AIBI‘, CQHHAIIQ,
(031402631:
(C6H11)2GaCl (cyclohexane derivative), C5H5GaBrZ,
Cz0H4iGaBr2, (c14H29)2GaF, (ceHshlncl, caHnlnFz,
CGHHInBrZ (cyclohexane derivative), C17H35BGI, and the
corresponding to the general formula R(Li)x, ‘wherein
halogen, and R is an organic radical, usually having 20
ing rubbery polymers having desirable physical character
istics. The reason for such improvement in the polymer
ization is not completely understood. However, it ap
pears that the treatment with the polyhydric alcohols
results in the removal of materials which when present
like.
ment with a conventional drying agent does not result in
The metal hydrides which can be employed include
the unexpected improvement, it appears that the poly
hydrides of Groups I, II and III metals. Speci?c ex
hydric alcohol treatment of the conjugated dienes has an
effect other than the mere removal of moisture from the 40 amples of suitable hydrides are aluminum hydride, lithium
aluminum hydride, barium hydride, gallium hydride, in
monomeric materials.
dium hydride, sodium aluminum hydride, and potassium
The catalysts used in the practice of the process of this
beryllium hydride, and the like.
invention are, in general, those which are effective for
The compounds of a metal of Groups IV to VI and
polymerizing conjugated ‘dienes to solid polymers. It is
VIII of the Periodic System include the oxides, hydrides,
usually preferred to employ a catalyst comprising a
member selected from the group consisting of organo 45 halides, oxyhalides, and salts of organic acids, usually
having 20 or less carbon atoms, such as formic acid. Ex
metals and metal hydrides. The organometals and the
amples of these metals are titanium, zirconium, thorium,
metal hydrides are often used in admixture with certain
hafnium, vanadium, chromium, molybdenum and iridium.
metal compounds as will become apparent hereinafter
The 'alcoholates of a metal of Group IV of the Periodic
from the description of catalyst systems containing two
System which can be employed with an organometal or
components.
metal hydride conform to the formula XnM(OR)m,
One particularly effective catalyst for use in the process
where
m-l-n equals the valence of the metal M, X is a
of this invention comprises an organolithium compound
R is a hydrocarbon radical selected from the group con
or less carbon atoms and preferably being an alkyl, cyclo
sisting of aliphatic, cycloaliphatic and aromatic radicals 55 alkyl or aryl group. Speci?c examples of such alcohol
ates rare titanium butoxide (tetra-n-butyl titanate), tetra
sec-butyl titanate, tetraisopropyl titanate, tetra-Z-ethyl
from 1 to 4, inclusive. The R group has a valence equal
butyl titanate, tetrastearyl titanate, tetracthyl titanate,
to the integer x and preferably contains from 1 to 20,
tetra(choroethyl)titanate, tetra-m-tolyl titanate, tetraallyl
inclusive, carbon atoms, although it is within the scope of
the invention to use higher molecular weight compounds. 60 titanate, tetracyclohexenyl titanate, tetracyclopentyl
titanate, tetracthyl zirconate, tetramethyl zirconate, tetra
Examples of org-anolithium compounds which can be
and combinations of these radicals and x is an integer
used include methyllithium, isopropyllithium, n-butyl
lithium, tert-octyllithium, n-‘decyllithium, phenyllithium,
naphthyllithium, 4-butylphenyllithium, p-tolyllithium, 4
phenylbutyllithium, cyclohexyllithium, 4-butylcyclohexyl
lithium, 4-cyclohexylbutyllithium, dilithiomethane, 1,4
dilithiobutane, 1,10-dilithiodecane, 1,20-di1ithioeicosane,
1,4-dilithiocyclohexane, 1,4-dilithiobutene-2, 1,8-dilithio
3-decene, 1,4-dilithiobenzene, 1,5-dilithionaphthalene, 1,2
dilithio-1,2-diphenylethane, 1,5-dilithioanthracene, 1,2-‘di
lithio-1,8-diphenyloctane, 1,3,5-trilithiopentane, 1,5,15
trilithioeicosane, 1,3,S-trilithiocyclohexane, 1,2,5-tri1ithio
naphthalene, 1,3,S-trilithioanthracene, 1,3,5,8-tetralithio
decane, 1,5,l0,20-tetralithioeicosane, 1,2,4,6-tetralithio
isopropyl zirconate, tetraamyl zirconate, dichlorodiethyl
titanate (Cl2Ti(OC2H5)2), monochlorotriethyl titanate
(ClTi(OC2H5)3), and ‘dichlorodiethyl zirconate
(C12ZT(OC2H5)2)
Also included are such compounds as Hf(OCH3)4,
Tl(OC3H7)4, Th(OC6H5)4, Cl3Ti(OC6H4OH3),
ZF(OC4H7)4,
C12Hf(OC10H21)2, Th(OCsHia)4, and ZT(OC12H25)4
-A particularly useful catalyst system for employment
in the process of this invention comprises (1) a compound
corresponding to the formula M'R’X, where M’ is one
of the metals aluminum, gallium, indium, thallium, beryl
3,095,406
5
6
lium, mercury, lead, zinc or mercury, R’ is hydrogen, an
lithium compound as the catalyst, it has been found that
the use of polar compounds in admixture with the hydro
carbon diluent increases the reaction rate of the polym
erization process of this invention. Examples of polar
compounds which do not inactivate the organolithium
alkyl, cycloalkyl, aryl, alkaryl, :aralkyl, alkylcycloalkyl,
or cycloalkylalkyl radical and x is equal to the valence
of the metal M, and (2) a halide of a Group IV, V or VI
metal, such as titanium, vanadium or molybdenum. Ex
amples of the M’R'x compounds have been given herein
catalyst and which may, therefore, be utilized with the
before. The M'R'x compounds can also be used in the
hydrocarbon diluents are ethers, thioethers (sul?des),
form of their known and stable organic complexes, such
and tertiary amines. Speci?c examples of such polar
as complexes with ethers, thioethers, amines, alkali metal
materials include dimethyl ether, diethyl ether, ethyl
hydrides, alkali metal alkyls or alkali metal ,aryls. Ex 10 methyl ether, ethyl propyl ether, di-nspropyl ether, di-n
amples or such complex compounds which can be em
octyl ether, tetramethylene oxide (tetrahydrofuran), di
ployed include LiAlH4, NaAl(CH3)4, NaBe(C6H5)3,
NaBe(C2H5)3, and the like.
‘Examples of suitable catalyst systems in accordance
with the foregoing disclosure are as iollows:
(a) Aluminum trialkyls, e.g., triethylaluminum or tri
isobutylaluminum, and the tetravalent metal halides of
the type represented ‘by titanium tetrachloride or titanium
15
oxane, paraldehyde, anisole, 1,2-dimethoxyethane, di
benzyl ether, diphenyl ether, dimethyl sul?de, diethyl
sul?de, di-n-propyl sul?de, di-n-butyl sul?de, methyl ethyl
sul?de, dimethylethylamine, tri-n-propylamine, tri-n-tbut
ylamine, trimethylamine, triethylamine, N,N-dimethyl
amine, pyridine, quinoline, N-ethylpiperidine, 'N-methyl
N-ethyl aniline, N-methylmorpholine, ‘and the like. It is
tetraiodide;
to be understood also that mixtures of these polar com
(b) Molybdenum pentachloride and an organometal 20 pounds can be employed in the practice of the instant
compound exempli?ed by diethylzinc or diisobutylmer
invention. When a polar compound is used in admixture
CUTS’;
with the hydrocarbon diluent, the polar compound is
(c) A complex metal hydride, such as lithium alumi
num hydride, and a Group IV metal halide, such as titani
_ um tetraiodide or titanium tetrachloride;
usually present in an amount in the range of 0.005 to 50
percent by weight of the total solvent mixture.
25
'(d) A complex metal halide, exempli?ed by potassium
iluotitanate, and an organometal compound, exempli?ed
by triethylaluminum;
I
(e) A derivative of a Group VIII metal selected from
the group consisting of halides, oxides and complex com
The polymerization process of this invention can be
carried out at any temperature within the range of about
—80 to 150° C., but it is preferred to operate in the
range of —Z0 to 80° C. The polymerizatoin reaction
can be carried out under autogen-ous pressures. It is
usually desirable to operate at pressures suf?cient to
pounds of iridium, platinum and osmium, said complex
compounds corresponding to the formula M",,M"’Xb,
maintain the monomeric material substantially in the
liquid phase. The pressure will thus depend upon the
where M” is an alkali metal or an ammonium radical,
particular material :being polymerized, the diluent being
M'” is irridium, platinum or osmium, X is a halogen,
employed, and the temperature at which polymerization is
and b is at least 1 and the sum of a and b is equal 35 conducted. However, higher pressures can be employed
to the valence of M'” and an organometal compound
exempli?ed by triethylaluminum, for example, iridium
chloride and triethylaluminum or ethylaluminum sesqui
if desired, these pressures being obtained ‘by some such
suitable method as the pressurization of a reactor with a
gas which is inert with respect to the polymerization
reaction. The polymerization according to this invention
(f) At least one derivative selected from the group 40 is generally carried out in the liquid phase. However,
consisting of oxides, halides, and oxyhalides of vanadium
depending upon the diluent and polymerization tempera
and complex salts of said halides with a member selected
ture selected, the polymerization can be conducted in the
from the group consisting of ammonium halide and an
solid phase.
7
alkali metal halide and an organometal compound, for
As previously indicated, the process of this invention is
example, vanadium oxide and triethylaluminum;
45 concerned with the production of rubbery polymers of
(g) A derivative of a Group VI metal selected from
conjugated dienes. The term “rubbery polymer” in—
chloride;
the group consisting of halides, oxyhalides, hydroxy
halides, oxyhydroxyhalides of a metal selected from the
cludes elastomeric, vulcanizable, polymeric material
which after vulcanization, i.e., crosslinking, possesses the
group consisting of molybdenum, tungsten, uranium,
properties normally associated with vulcanized rubber
selenium, tellurium- and polonium, and complex salts of 50 including materials which when compounded and cured
said halides and said oxyhalides with a member selected
from the group consisting of halides of sodium, potassium,
lithium, rubidium, cesium and ammonia and an organo
metal compound, for example, molybdenum pentachlo
ride and ethylaluminum dichloride;
(h) A chromyl halide and an org-anometal compound,
exhibit reversible extensibility at 801° F. of over 100 per
cent of a specimen’s original length with a retraction of
at least ‘90 percent within one minute a?ter release of
the stress necessary to- elongate to 100 percent. The rub
bery polymers produced in accordance with this inven
tion are linear polymers. With regard to the solubility
such as chromyl chloride and triisobutylaluminum; and
(i) At least one halide of titanium, zirconium or hafni
um and at least one hydride of lithium, sodium, potassium,
of the rubbery polymers of this invention, it is preferred
derstood that mixtures of these materials can also be used.
is not intended to limit the invention to a speci?c charging
that they contain less than 50% gel as determined by
the standard gel determination test. Actually, it has been
rubidium, cesium, magnesium, calcium, strontium, bari 60 found that the polymers produced in accordance with the
um, lanthanium or thorium, for example, zirconium tetra
instant process generally contain not gel or substantially
chloride and calcium hydride.
no ‘gel.
The polymerization process of this invention is usually
The process of this invention can be carried out as a
carried out in the presence of a hydrocarbon diluent
batch process by charging the monomeric material after
which is liquid and inert under the conditions of the 65 treatment with the polyhydric alcohol treating agent into
process. Examples of suitable diluents include aromatic,
a reactor containing the polymerization catalyst and
para?inic and cycloparaf?nic hydrocarbons, it being un
the hydrocarbon diluent. It is to be understood that it
Speci?c examples of suitable hydrocarbon diluents include
procedure since the catalyst diluent and monomer can be
propane, isobutane, n-pentane, iso-octane, n-dodecane, 70 added in any desired order. The process can also be
cyclopentane, cyclohexane, methylcyclohex-ane, benzene,
carried out continuously by maintaining the above-men
toluene, xylene, and the like. It is also within the scope
of the invention to employ in admixture with the hydro
carbon diluent polar compounds which do not inactivate
the organolithium catalyst. When employing an organo 75
tioned concentration of reactants in the reactor for a suit
able residence time. The residence time in a continuous
process will, of course, vary within rather wide limits de
pending on such variables as the reaction'temperature
3,095,406
7
and pressure, the amount of catalyst used, and the mono
meric material which is being polymerized. In a con
8
A. Butadiene was passed upward through a 2" x 24"
column packed with calcium hydride, through a 3” X 30"
tinuous process, the residence time generally falls within
column packed with Drierite (calcium sulfate), through a
and moisture from the reaction vessel in which the polym
The bottle was swept with prepuri?ed nitrogen prior to
transfer of the butadiene.
Vigreux column with Dry Ice re?ux to remove any
the range of 1 second to 1 hour when conditions within
dimer that was present, and then into a receiver pro
the speci?ed ranges are employed. When a batch process
tected with a calcium sulfate drying tube. The liquid
is being utilized, the time for the reaction can be as
butadiene was allowed to stand for approximately 45
high as 24 hours or more, although it is generally less
minutes at ~80° C. in a Dry Ice-acetone bath to freeze
than 24 hours.
out any water which might still be present. It was then
It is preferred that the diluent used in the process be
substantially free of impurities such as water, oxygen and 10 transferred to a bottle containing calcium sulfate, using
100 grams of calcium sulfate per 300 grams of butadiene.
the like. In this connection, it is desirable to remove air
erization is carried out.
B. Butadiene was passed through a knock out column
At the conclusion of the polymerization reaction, when
a batch process is used, the total reaction mixture is then 15 (Vigreux column with Dry Ice re?ux) to remove any
treated by any suitable method to inactivate the catalyst
and recover the polymer. In one suitable method, a
catalyst inactivating material, such as water or an alco
dimer that was present, through ethylene glycol which
had been dried by heating it to 200° C. and cooling it
in an atmosphere of nitrogen, then through a 1" x 13”
tube packed with glass helices to remove ethylene glycol,
hol, e.g. isopropyl alcohol, is added in amount which is
su?icient to deactivate the catalyst without causing pre 20 and then into a receiver protected with a calcium sul
fate drying tube. It was transferred immediately from
cipitation of the desired polymer. It has also been found
to be advantageous to add an antioxidant, such as phenyl
beta-naphthylamine, to the polymer solution prior to
precipitation of the polymer. After addition of the cata
the receiver to a 24-ounce beverage bottle which had
been swept with prepuri?ed nitrogen.
present in ‘the solution can then be precipitated by the
C. But-adiene was passed through a knock out column
as in 13 above, and then over the surface of water. The
bu-tadiene was thereafter passed as in B above through
addition of an excess of a material such as water, ethyl
alcohol or isopropyl alcohol. It is to be understood that
to remove ethylene glycol, and ?nally into a receiver. It
lyst inactivating agent and the anti-oxidant, the polymer
ethylene glycol, through a tube packed with glass helices
was transferred immediately from the receiver to a 24
mer can be accomplished in a single step. The precipi 30 ounce beverage bottle which has been swept with pre
deactivation of the catalyst and precipitation of the poly
puri?ed nitrogen.
tated polymer can then be recovered by ?ltration, decan
D. Butadiene was passed through a knock out column
tation, or the like.
as in B and then through water. Treatment of the buta
The rubbery polymers which result when a monomeric
diene was then continued by passing same through ethyl~
material comprising a conjugated ‘diene is polymerized
ene glycol, etc., as described in B and C hereinabove.
by the method of this invention can be compounded by
E. Butadiene was distilled, shaken with ethylene glycol
any of the known methods such as have been used in the
using 10 parts by weight of the glycol per 100 parts
past for compounding natural rubber. Vulcanization ac
butadiene, passed through a l” x 18” tube packed with
celerators, reenforcing agent, and ?llers such as have
glass helices to remove the ethylene glycol, and then
been employed in natural rubber can likewise be used in
40 passed into a receiver protected with a calcium sulfate
the compounds of this invention.
drying tube. It was transferred immediately from the
A more comprehensive understanding of the invention
receiver to a 24-ounce beverage bottle which had been
can ‘be obtained by referring to the following illustrated
swept with prepuri?ed nitrogen.
examples which are not intended, however, to be unduly
Butadiene, treated according to the above-described
limitative of the invention.
methods, was polymerized in accordance with the fol
EXAMPLE I
lowing recipe:
Grams
Butadiene, treated in various Ways with ethylene rglycol
Butadiene _________________________________ __ 100
and also without the glycol treatment, was polymerized
in a series of runs using n-butyllithium as the catalyst.
Cyclohexane _______________________________ __ 390
The n-butyllithium catalyst was prepared and used in 50 Butyllithium (0.244 M solution) ____________ __ Variable
Temperature, ‘’ C ___________________________ __
50
n-pentane solution. A 1000 milliliter three-necked ?ask,
?tted with a re?ux condenser, a dropping funnel with a
Time, hours _________________________________ _.
17
gas outlet sidearm, and a high speed stirrer, was swept
The polymerization runs were conducted in 7-ounce
with prepuri?ed nitrogen and charged With 300 milliliters
of dry, ole?n-free n-pentane and 5.9 grams of lithium 55 beverage bottles which were ?rst charged with dry cyclo
hexane. Prior to charging, prepuri?ed nitrogen was
wire which was cut into lengths of about 0.5 centimeter.
bubbled through the cyclohexane for 30 minutes at the
The dropping funnel was then attached, and a solution
of 38.9‘ grams of l-chlorobutane in 100 milliliters of n
pentane was charged to it. The stirrer was started and
brought to high speed, and the chlorobutane solution was
added without cooling at a rate so as to maintain gentle
re?ux. After the addition was completed, stirring was
continued for three hours. The mixture was allowed to
stand overnight in a nitrogen atmosphere and was then
transferred to a 7-ounce beverage bottle and centrifuged.
The supernatant n-butyllithium solution was pressured
into a dry, nitrogen-?lled bottle. Analysis showed the
solution to be 0.610 M n-butyllithium. This solution
was diluted with n-pentane to a concentration of 0.244
rate of 3 liters per minute. After the diluent was charged,
prepuri?ed nitrogen was dispersed through a fritted glass
tube and bubbled through it at the rate of 3 liters per
minute for 5 minutes. The bottles were capped with
rubber gaskets and perforated metal caps, and the mono
mer and n-butyllithium were introduced in that order
by syringe. The bottles were then agitated in a constant
temperature bath (50° C.) for 17 hours.
The polymer in each run was precipitated by the addi~
tion of isopropanol, separated, and then dried in a
vacuum oven.
Five series of runs were made in which the butadiene
M when used in the polymerization runs hereinafter de 70
was treated in each series by one of the treating pro
scribed.
cedures described above. The catalyst levels and results
There is set forth hereinbelow a description of the
are set forth below in Table I, and the letters A, B, C,
procedures (designated as A, B, C, D and E) used in
D and E are used in the table to designate the particular
treating the butadiene prior to its being contacted with n
75 procedure used in treating the butadiene.
butyllithium.
3,095,406
10
Table I
Millimols
Run
N0.
Bntadiene
Treatment
Catalyst/-
100 Grams
70° C. Toluene which had been dried ‘by a nitrogen
purge was added to the bottles. After addition to the
bottles, the toluene was purged with nitrogen for an addi
tional minute at 3 liters per minute for each 50 m1. of
‘
Conversion, percent
Inherent
viscosity
Monomer
toluene. The catalyst was prepared by adding triiso
butyl aluminum and titanium tetrachloride to toluene.
A (control)_.
Aliquots of this toluene suspension were then added to
the bottles by means of a syringe. Thereafter, the buta
A (control)..
A (control __
A (control)_.
A (c0ntrol)__
diene was added to the bottles. In run 31, as shown in
Table II, the butadiene prior to use was passed Ifrom a
% (e0ntrol)__
storage cylinder through a column to knock out dimer
and then collected in a Dry Ice-cooled container. In
run 32, as shown in Table II, the butadiene was passed
through a tower which was ?lled to a depth of 8 inches
with ethylene glycol and then collected in a Dry Ice—
cooled container. Both samples of butadiene until used
were then stored in quart bottles over Drierite (calcium
sulfate) at —20° C.
The polymerization recipe used in these runs was as
follows:
Parts by weight
Butadiene
Toluene
100
._____
440
Triisobutylaluminum '(TBA) _____________ __ Variable
Titanium tetrachloride (TIC) ____________ __ Variable
Temperature,
° C ______ __‘_________________ __
30
Time, hours
16-17
Polymerization was obtained in control run 3 but the
The results of these runs are shown hereinbelow in
product had a much higher inherent viscosity than that
in runs 9, 15, 21, and 27. The catalyst level was the 30 Table II.
Table 11
same in all runs. The data show that with the glycol
treated butadiene, polymerization can be effected‘ at rela
tively low catalyst levels to give consistently good con
versions whereas with the untreated butadiene, erratic
results were obtained with only one run of the ?rst four 35
Run No.
TBA,
MHM 1
T'I‘C,
Conver
MHM 1
sion,
percent
-
yielding any polymer.
1. 0
1. 0
EXAMPLE RII
Polymerization grade isoprene was distilled, and the 40
center cut was used in :a series of polymerization runs
O, 83
0. 83
10
18
1 Millimoles per 100 parts of monomer.
9 Not treated with ethylene glycol.
3 Treated with ethylene glycol.
in which n-lbutyllithium was employed as the catalyst.
A portion of the center cut from the distillation of iso
From a consideration of the data in Table II, it is seen
that a higher conversion of the 1,3-butadiene to polymer
prene was contacted in vapor phase with ethylene gly
col which had ‘been dried by heating to 200° C. and 4:5 is obtained when the monomer is treated with ethylene
glycol prior to use in the polymerization. It is noted
then cooling in an atmosphere of nitrogen. The iso
that
these runs were carried out ‘at very low catalyst
prene vapor was dispersed into the ‘glycol through a
levels, indicating that the treatment of the monomer
fritted glass v‘disk. It was then passed through a tube
with a polyhydric alcohol makes it feasible to employ
packed with glass helices to remove the ethylene glycol,
lower
catalyst levels in the polymerization than is pos
50
through a Vigreux column, and then into a receiver pro
sible with the untreated monomer.
vided with a calcium sulfate drying tube. Nitrogen
was passed slowly through the system to maintain a
EXAMPLE IV
positive nitrogen pressure during this operation.
A solution of n-butyllithium in n-pentane was pre
pared in the manner ‘described in Example I. The con
55
centration of the solution employed in the polymeriza
tion of isoprene was 0.330 M.
Samples of the distilled isoprene and samples of dis
tilled isoprene which had been treated with ethylene gly
A series of runs was carried out in which 1,3-butadi
one was polymerized in the presence of a catalyst con
sisting of diethylzinc and molybdenum pentachloride.
In runs 33 and 35, as shown in Table III, the butadiene
was not treated with ethylene glycol while in runs 34
and 36 the butadiene was treated with ethylene glycol
col were employed in two series of polymerization runs 60 as described in Example III. Essentially the same pro
using 2.5, 3.0, and 3.5 millimols of n-butyllithium per
cedure as described in Example III was followed in con
100 grams of monomer. Cyclohexane (390 grams) was
ducting these runs.
‘
employed as the diluent. Polymerization was effected
The polymerization recipe used in these runs was as
in the manner described in Example I using a tempera 65 follows:
ture of 50° C. and a reaction time of four hours. Po
Parts by weight
Butadiene
100
lymerization occurred in all cases.
Toluene
EXAMPLE 1r
But-adiene, treated with ethylene glycol and also with 70
out the glycol treatment, was polymerized in runs using
a catalyst consisting of triisobutyla-luminum and titani
um tetrachloride.
The runs were carried out in 7-ounce
beverage bottles which had been ‘dried in an air oven at 75
_
_.__._.. 880
Diethylzinc _
Variable
Molybdenum pentachloride ______________ __ Variable
Temperature,
Time,
° C ___________________________ ..
50
hours _______________________________ ....
72
The results of these runs are shown hereinbelow in
Table III.
‘
3,095,406
Table V
Table III
Run No.
TBA
Diethylzinc,
M0015
Con
MHM 1
MHM 1
version,
3. 6
3. 6
3.0
3. 0
percent
3. O
3.0
2. 5
2. 5
T'I‘I
Run No.
Conversion,
percent
Parts MHM1 Parts MHM1
15
35
0
15
411 ____________________ __
423 ____________________ __
10
1 Millimoles per 100 parts of monomer.
2 Not treated with ethylene glycol.
B Treated with ethylene glycol.
0.397
0.397
2.00
2.00
0.222
0.222
0.400
0.400
0
05
1 Millimoles per 100 parts of monomer.
1 Not treated with ethylene glycol.
3 Treated with ethylene glycol.
From an examination of the data in Tables IV and V,
it is seen that higher conversions are obtained when the
a polyhydric alcohol prior to use in the polymerization. 15 monomer is treated with a polyhydric alcohol prior to the
It is apparent from the data in Table III that a higher
conversion is obtained when the monomer is treated with
polymerization.
The rubbery polymers produced in accordance with this
invention have utility in applications where natural and
EXAMPLE V
A series of runs were carried out in which 1,3-buta
diene was polymerized in the presence of a catalyst con
synthetic rubbers are used.
sisting of lithium aluminum hydride and titanium tetra
other rubber articles.
As will be evident to those skilled in the art, many
variations and modi?cations can be practiced upon con
iodide. In runs 37 and 39, as shown in Table IV, the
butadiene was not treated with ethylene glycol while in
runs 38 and 40 the butadiene Was treated with ethylene
glycol as described in Example III. Essentially the same
procedure as described in Example 111 was followed in
conducting these runs.
sideration of the foregoing disclosure. Such variations
and modi?cations are believed to be within the spirit and
scope of the invention.
We claim:
1. In a process for preparing rubbery polymers com
The following polymerization recipe was employed in
these runs:
For example, they can be
20 used in the manufacture of automobile tires, gaskets, and
prising contacting a conjugated diene suitable for polym
erization and containing from 4 to 10, inclusive, carbon
Parts by weight
_____________________________ __
100
atoms per molecule with a catalyst selected from the
Cyclohexane ___________________________ __
780
group consisting of (1) a compound corresponding to the
Bu-tadiene
Lithium aluminum hydride (LAH) _______ __ Variable
formula RLiX, wherein R is a hydrocarbon radical se
Titanium tetraiodide (TTI) _______________ __ Variable
M01 ratio, LAH/TTI ____________________ __
1.20/1
lected from the group consisting of aliphatic, cycloali
Temperature, ° C _______________________ __
50
Time, hours _________________________ _t____
17.5
The results of these runs are shown hereinbelow in
Table IV.
Table IV
LAH
35 phatic and aromatic radicals and x is an integer from
1 to 4, inclusive, and (2) mixtures obtained by mixing
at least two essential components, one of said components
eing selected from the group consisting of hydrides of
metals of Groups I, II and III and organo compounds of
40 Groups I, II, III and IV-B metals and the other of said
components being a metal compound selected from the
group consisting of Group IV—A, Group V, Group VI
TTI
Run No.
and Group VIII metal compounds, said contacting occur
ring in the presence of a hydrocarbon diluent, the im
Conversion,
percent
Parts MHM! Parts MHMl
45
1.50
l. 50
1.25
1. 25
0. 695
0. 695
0.578
0. 578
1. 25
1.25
1.04
1. 04
85
95
0
95
50
1 Millimoles per 100 parts of monomer.
1 Not treated with ethylene glycol.
3 Treated with ethylene glycol.
provement which comprises mixing said conjugated diene
with a polyhydric alcohol, thereby forming a conjugated
diene phase and an alcohol phase, said polyhydric alcohol
being liquid under the mixing conditions and being sc
leoted from the group consisting of dihydric and tri
hydric alcohols having from 2 to 10 carbon atoms per
molecule; separating said conjugated diene phase from
said alcohol phase; and contacting said catalyst with said
conjugated diene phase.
EXAMPLE VI
as described in Example III was followed in conducting
2. The process according to claim 1 in which said poly
hydric alcohol is a glycol.
3. The process according to claim 2 in which said gly
col is ethylene glycol.
4. The process according to claim 1 in which said poly
hydric alcohol is glycerol.
5. A process for preparing rubbery polymers of con
jugated dienes which comprises passing a conjugated diene
suitable for polymerization and containing from 4 to 10,
[these runs.
inclusive, carbon atoms per molecule into a treating zone;
Butadiene, treated with ethylene glycol and also with
out glycol treatment, was polymerized in runs using a
catalyst consisting of triisobutylaluminum and titanium
tetraiodide. In run 41, as shown in Table V, the buta
diene was not treated with ethylene glycol while in run
42 the butadiene was treated with ethylene glycol as de
scribed in Example III. Essentially the same procedure
The polymerization recipe used in these runs Was as
follows:
Butadiene
Parts by weight
_____________________________ __
100
Toluene _______________________________ __
866
Triisobutylaluminum (TBA) ______________ __ Variable
Titanium tetraiodide (TTI) _______________ __ Variable
Mol ratio, TBA/TTI _____________________ __
5.00/1
Temperature, ° C _______________________ __
50
Time, hours ____________________________ __
3
The results of these runs are shown hereinbelow in
Table V.
mixing said conjugated diene with a substantially anhy
drous polyhydric alcohol having from 2 to 10 carbon
atoms per molecule in said treating zone, thereby form
ing a conjugated diene phase and an alcohol phase, said
polyhydric alcohol being liquid under the mixing condi
tions and being selected from the group consisting of
dihydric and trihydric alcohols; recovering said conju
gated diene phase from said treating zone; contacting
said conjugated diene phase with a catalyst selected from
the group consisting of (l) a compound corresponding
to the formula RLix, wherein R is a hydrocarbon radical
selected from the group consisting of aliphatic, cyclo
3,095,406
13
1.4
aliphatic and aromatic radicals and x is an integer from
12. The process according to claim 5 in which said
1 t0 4, inclusive, and (2) mixtures obtained by mixing
catalyst consists essentially of triisobutylaluminum and
at least two essential components, one of said compo—
titanium tetrachloride.
13. The process according to claim 5 in which said
nents being selected from the group consisting of hy
drides of Groups I, l1 and Ill metals and organo com
catalyst consists essentially of diethylzinc and molyb
denum pentachlori-de.
pounds of Groups I, II, III and IV~B metals and the
other of said components being Ia metal compound se
14. The process according to claim 5 in which said
catalyst consists essentially of lithium aluminum hydride
lected from the group consisting of Group ‘IV-A, Group
V, Group VI and Group VIII metal compounds, said con
‘and titanium tetraiodide.
15. The process according to claim 5 in which said
tasting occurring at a temperature in the range of —20
to 150° C. and in the presence of a hydrocarbon diluent,
inert and liquid under conditions of the process; and
catalyst consists essentially of triisobutylaluminum and
titanium tetraiodide.
recovering a rubbery polymer of said conjugated diene.
6. The process according to claim 5 in which said con
jugated diene is 1,3-butadiene.
7. The process according to claim 5 in which said con
15
jugated diene is isoprene.
jugated diene is 1,3-pentadiene.
9. The process according to claim 5 in which said poly 20
hydric alcohol is a glycol.
10. The process according to claim 9 in which said
glycol is ethylene glycol.
’
11. The process according to claim 5 in which said
catalyst consists essentially of n-butyllithium.
References Cited in the ?le of this patent
UNITED STATES PATENTS
2,552,198
2,832,759
8. The process according to claim 5 in which said con
25
'
2,913,444
2,925,452
2,953,556
2,979,488
Mayland et a1 __________ __ May 8,
Nowlin et al. _________ __ Apr. 29,
Diem _______________ __ Nov. 17,
Broughton ___________ __ Feb. 16,
Wolfe _______________ __ Sept. 20,
Carpenter ___________ __ Apr. 11,
1951
1958
1959
1960
1960
1961
OTHER REFERENCES
Moor et al.: Chem. Abstracts, vol. 29, 6034 (1935).
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