Polybutadiene

Since butadiene monomer capacity is available in sizeable quantities and since, beyond that,
butadiene production techniques are constantly being improved (through oxidative
dehydrogenation, for example) , the desirability of butadiene as an economic and available
monomer is obvious. It is less expensive than isoprene and it is somewhat more attractive
operationally as a single monomer than is its utilization in a copolymer process. These factors,
coupled with the possibility that one may be able to produce a stereo rubber very similar to natural
rubber from butadiene rather than isoprene, have intensified research and development efforts on
polybutadiene rubbers.

It should be noted that it is possible to effect stereospecific polymerization in aqueous emulsions by

proper choice of catalysts even though stereo polymer production is usually thought of as being
restricted to solution polymerization in the presence of organometallic catalysts.

Thus, the use of rhodium chloride as a catalyst gives trans-polybutadiene as described by H.P. Smith
et al (to united states rubber co) in us3025286. The use of a cobaltous fluoride-alkali fluoride double
salt gives cis-polybutadiene as described by W.A. Hewett in US3174960.

Feed specifications

The monomer to be polymerize may in some cases be the crude feed obtained from the preparation
of butadiene, such feeds may contain as little as 10% by weight of butadiene while the remainder
comprises other C4 hydrocarbons as butane-1, cis and trans- butene-2, and the like. The amounts
of the carious C4 components will vary widely depending on the processes used to manufacture the
butadiene from other C4 fractions but it is immaterial how much butadiene or other C4
hydrocarbons are contained in the mixed feed. Such feed have boiling points that are below normal
temperatures and is order to carry out the polymerization most conveniently the feed is maintained
as a liquid during the polymerization. This may be done by lowering the temperature or by the use
of higher temperatures and elevated pressures. Either procedure is suitable as long as the feed is in
the liquid- phase according to E.A. Youngman (to shell oil co) in us3066128. This process is based on
the discovery that butenes will not copolymerize with butadiene in the presence of catalysts
containing nickel or cobalt chloride, bur that the butadiene is polymerized to a high cis-1, 4 content
polymers.

In addition to using as the monomer pure or rubber- grade butadiene, which contains about 99.6
weight percent of butadiene, the polymerization process using alfin catalysts can be applied to
impure or dilute butadiene, which contains about 12 to about 40 weight percent of butadiene. The
composition of the polymer prepared from a lean butadiene stream is the same as that prepared
from pure butadiene, that is about 30% of the 1,2 isomer and about 70% of the trans- 1 ,4 isomer
as described by H. Greenberg et al is US3067187.

Polymerization in the presence of TiCl4-LiBH4 catalysts as described by D.A.Fraser et al in

US2999088 can be brought about by mixing the various ingredients of the reaction mixture in any
order. Most suitably the components of the catalyst system are mixed before introducing the
conjugated alkene. Preferably, when carrying out this technique, the metal halide is added to the
lithium borohydride before the addition of the monomer or it can be added over a period of time in
successive portions. During the polymerization further quantities of conjugated alkene, catalyst
components and inert liquid vehicle can be added, if desired.

Treating the butadiene feed with a polyhydric alcohol prior to contact with the catalyst permits the
polymerization to be affected at relatively low catalyst levels to give from non-sticky rubbery
polymers according to J.N Short et al in US3095406.

Figure 49 shows a flow diagram of process embodying flash recovery of unreacted materials
showing a preferred control mechanism for controlling the rate of feed materials. This process has
been described by D.E.Smith et al in US3250757.

Referring now to figure 49 reactors 10,11,12 and 13 are shown connected in series for carrying out
the polymerization reaction. While four reactors are shown it should be understood that more or
fewer reactors can be employed, depending upon the design capacity of the reactors and the
desired residence time for the polymerization reaction. Monomer in conduit 14, solvent in conduit
16, and recycle material which is predominantly monomer and solvent in conduit 17 are combined
in conduit 18 and fed to rector 10, the first reactor in the series. Catalyst for the reaction is also
added via conduit 19 to this feed stream in conduit 18. The polymerization affluent from the last
reactor in the series, reactor 13, is removed through line 20 and passed to heat exchanger21.
Various additives can be injected into the polymerization effluent in conduit 20, for example, a
shortstop or catalyst inactivating agent to terminate the polymerization reaction, is injected into
conduit 20 by way of conduit 22. Also, an antioxidant is injected via conduit 23. The effluent stream
is then heated in heat exchanger 21 and passed to flash tank 24 where the pressure on the mixture
is reduced and reacted monomer together with some of the solvent is vaporized.

The unvolatilized residue together with polymer is passed from flask tank 24 via conduit 26 and heat
exchanger 27 to flask tank 28. This material is repressurized in conduit 26 by a pump, not shown,
and the pressure is again reduced in flask tank 28 so that the heat added in heat exchanger 27 causes
a portion of the solvent to vaporize together with more of the unreacted monomer . this operation
is repeated with the in volatilized material being removed through conduit 29 and passing through
heat exchanger 30to the final flash step in tank 31. More solvent is vaporized together with any
remaining in reacted monomer and the vapors pass overhead from flash tanks 24,28 and 31 through
conduits 32,33 and 34 respectively. These vapors are combined in header 36 and passed to
condenser 37 where they are condenser the condensate passes through conduit 38 to accumulator
39. The un vaporized solvent together with the polymer is removed from flash tank 31 through
conduit40 and passed to further polymer recovery steps which are not shown in this drawing since
they are not essential to an understanding of this invention. A constant inventory is maintained in
vessels 24, 28 and 31 by liquids level controllers, not shown.

Condensate from accumulator 39 is withdrawn via conduit 41. a portion of this condensate is purged
from the polymerization system by passing it to a solvent purification step via conduit 42. Liquid
level controller 43 on accumulator 39 is operably connected to motor valve 44 in conduit 42 so that
the flow of condensate through line 42 can be regulated in order to maintain a substantially constant
liquid level in the accumulator vessel. Flow through line 42 is sensed by flow sensing element 46 and
the associated transducer 47 produces a signal which is transmitted to flow recorder 48. The
remainder of the condensate in line 41 is recycled to the reaction by way of conduit 17 as previously
described.

The flow in conduit 17 is sensed by flow sensing element 49 which transmits a signal to flow recorder
50 operably connected to motor valve 51 in conduit 17 so that the flow of recycle materials in
conduit 17 is thereby maintained substantially constant. In one embodiment of this invention a
predetermined set point is established manually for flow controller 50. Flow sensing element 52 in
conduit 14 transmits a signal as function of the flow through this conduit to flow recorder controller
53 which is operably connected to motor valve 54 in conduit 14. The flow of make-up monomer
through conduit 14 is thereby maintained at a substantially constant predetermined value
established by the set point of flow recorder controller 53. The flow sensing elements ca be of any
conventional variety but turbine type flowmeters are preferred. These flowmeters can be calibrated
to produce outputs proportional to the mass (gravimetric) rate of flow of the measured stream.

A sample of the feed stream in conduit 18 is passed by way of sample line 56 to analyzer recorder
57 which is an instrument capable of measuring the concentration of monomer in the feed stream,
for example, the concentration of butadiene in a stream of toluene. A number of well known
analyzers such as infrared analyzers, ultraviolet analyzers, differential refractometers, or mass
spectrometers can be used for this service although a gas phase chromatographic analyzer, such as
described in US patent 2943702 to Hudson et al, is preferred.

Analyzer 57 produces a signal which as a function of the concentration of monomer in the feed
stream in conduit 18. This signal is transmitted to recorder controller 53. The set point of analysis
recorder controller 58 is the desired monomer concentration in the feed stream tends to decrease,
this change is sensed by analyzer 57 and a signal is transmitted to controller 58 which senses the
deviation of the monomer content from the desired value established as its set point. This deviation
causes a manipulation of the set point of controller 53 so that a higher feed rate of make- up
monomer is required by this controller and thereby the concentration of the monomer in the feed
stream is returned to its desired value.

The flow of make-up diluent in conduit 16 is sensed by flow sensing element 59 which transmits a
signal as a function of this rate of flow to flow recorder 60 and to adding relay 61. Adding relay 61
also receives a signal from flow sensing element 49. This signal is a function of the flow of recycle
material through conduit 17. Relay 61 also receives a signal from flow sensing element 52. This signal
is a function of make-up monomer flow through conduit 14. Adding relay 61 produces a signal which
is a function of the sum of the signals received from flow sensing elements 48, 52 and 59. This
summation signal is transmitted to recorder controller 62 which has as its setpoint the desired total
flow of these three feed steams. Recorder controller 62 is operably connected to motor valve 63 in
conduit 16. Thus, the flow rate of the make-up stream substantially constant. As in the situation
discussed above, where an increase in the monomer make-up flow rate is required in order to offset
a decrease in the monomer concentration of the total feed stream, a corresponding decrease in the
solvent flow rate is automatically made in order to maintain the total flow rate of the feed stream
in conduit 18 at a substantially constant value.

According to another aspect of the invention, analyzer 57 analyses not only for the monomer
content in feed stream 18 but also for the content of inert materials, for example, low boiling
hydrocarbons which are vaporized in the flash vessels and returned with the recycle stream but
which do not enter into the reaction under the conditions maintained. In this embodiment analyzer
57 transmits a second signal to analysis controller 64 as a function of the concentration of the inert
components in the feed stream 18. Controller 64 is connected to manipulate the set point of flow
recorder 500 which in turn regulates the flow of recycle materials through conduit 17. According to
this arrangement the maximum allowable.

Referring now to figure 49, reactors 10,11,12 and 13 are shown connected in series for carrying out
the polymerization reaction. While four reactors are shown it should be understood that more or
fewer reactors can be employed, depending upon the design capacity of the reactors and the
desired residence time for the polymerization reaction. Monomer in conduit 14, solvent in conduit
16, and recycle material which is predominantly monomer and solvent in conduit 17 are combined
in conduit 18 and fed to reactor 10, the first reactor in the series. Catalyst for the reaction is also
added via conduit 19 to this feed stream in conduit 18. The polymerization effluent from the last
reactor in the series, reactor 13, is removed through line 20 and passed to heat exchanger 21.
Various additives can be injected into the polymerization effluent in conduit 23. The effluent stream
is then heated in heat exchanger 21 and passed to flash tank 24 where the pressure on the mixture
is reduced and reacted monomer together with some of solvent is vaporized.

The unvolatilized residue together with polymer is passed from flask tank 24 via conduit 26 and heat
exchanger 27 to flask tank 28. This material is repressurized in conduit 26 by a pump, not shown,
and the pressure is again reduced in flask tank 228 so that the heat added in heat exchanger 27
causes a portion of the solvent to vaporized together with more of the unreacted monomer. This
operation is repeated with the unvolatilized material being removed through conduit 29 and passing
through heat exchanger 30 to the final flash step in the tank 31. More solvent is vaporized together
with any remaining unreacted monomer and the vapors pass overhead from flash tank 24,28 and
31 through conduits 32,33 and 34 respectively. These vapors are combined in g=header 36 and
passed to condenser 37 where they are condenser and the condensate passes through conduit 38
to accumulator 39. The unvaporized solvent together with the polymer is removed from flash tank
31 through conduit 40 and passed to further polymer recovery steps which are not shown in this
drawing since they are not essential to an understanding of this invention. A constant inventory is
maintained in vessels 24,28, and 31 by liquid level controllers, not shown.

Condensate from accumulator 36 is withdrawn via conduit 41. A portion of this condensate is purged
from the polymerization system by passing it to a solvent purification step via conduit 42. liquid level
controller 43 on accumulator 39 is operably connected to motor valve 44 in conduit 42 so that the
flow of condensate through line 42 can be regulated in order to maintain a substantially constant
liquid level in the accumulator vessel. Flow through line 42 is sensed by flow sensing element and
the associated transducer 47 produces a signal which is transmitted to flow recorder 48. The
remainder of the condensate in line 41 is recycled to the reaction by way of conduit 17 as previously
described.

The flow in conduit 17 is sensed by flow sensing element 49 which transmits a signal to flow recorder
50 operably connected to motor valve 51 in conduit 17 so that the flow of recycle materials in
conduit 17 is thereby maintained substantially constant. In one embodiment of this invention a
predetermined set point is established manually for flow controller 50. Flow sensing element 52 in
conduit 14 transmits a signal as a function of the flow through this conduit to flow recorder
controller 53 which is operably connected to motor valve 54 in conduit 14. The flow of make-up
monomer through conduit 14 is thereby maintained at a substantially constant predetermined value
established by the set point of flow recorder.

Controller 53. The flow sensing elements can be of any conventional variety but turbine type
flowmeters are preferred. These flowmeters can be calibrated to produce outputs proportional to
the mass (gravimetric) rate of flow of the measured stream.

A sample of the feed stream in conduit 18 is passed by way of sample line 56 to analyzer recorder
57 which is an instrument capable of measuring the concentration of monomer in the feed stream,
for example, the concentration of butadiene in a stream of toluene. A number of well-known
analyzers such as infrared analyzers, ultraviolet analyzers, differential refractometers, or mass
spectrometers can be used for this service although a gas phase chromatographic analyzer, such as
described un US2943702 to Hudson et al, is preferred.

Analyzer 57 produces a signal which is a function of the concentration of monomer in the feed
stream in conduit 18. This signal is transmitted to recorder controller 58 which in turn is connected
to manipulate the set point of flow recorder controller 53. The set point of analysis recorder
controller 58 is the desired monomer concentration in the feed stream. It can be seen, therefore,
that if the monomer concentration in the feed stream tends to decrease, this change is sensed by
analyzer 57 and a signal is transmitted to controller 58 which senses the deviation of the monomer
content from the desired value established as its set point. This deviation causes a manipulation of
the set point of controller 53 so that a higher feed rate of make-up monomer is requires by this
controller and thereby the concentration of the monomer in the feed stream is returned to its
desired value.

The flow of make-up diluent in conduit 16 is sensed element 59 which transmits a signal as a function
if this rate of flow to flow recorder 60 and to adding relay 61. Adding relay 61 also receives a signal
from flow sensing element 49. This signal is a function of the flow of recycle material through
conduit 17 relay 61 also receives a signal from flow sensing element 52. This signal is a function of
make-up monomer flow through conduit 14. Adding relay 61 produces a signal which is a function
of the sum of the signals received from flow sensing elements 49, 52 and 59. This summation signal
is transmitted to recorder controller 62 which has as its set point the desired total flow of these
three feed streams. Recorder controller 62 is operably connected to motor valve 63 in conduit 16.
Thus, the flow rate of the make-up diluent is regulated in order to maintain the total flow of the
recycle and make-up substantially constant. As in the situation discussed above, where an increase
in the monomer make-up flow rate is required in order to offset a decrease in the monomer
concentration of the total feed stream, a corresponding decrease in the solvent flow rate is
automatically made in order to maintain the total flow rate of the feed stream in conduit 18 at a
substantially constant value.

According to another aspect of the invention, analyzer 57 analyses not only for the monomer
content in feed stream 18 but also for the content of inert materials, for example, ow boiling
hydrocarbons which are vaporized in the flash vessels and returner with the recycle stream but
which do not enter into the reaction under the conditions maintained. In this embodiment analyzer
57 transmits a second signal to analysis controller 64 as a function of the concentration of the inert
components in the feed stream 18. Controller 64 is connected to manipulate the set point of flow
recorder 50 which in turn regulates the flow of recycle materials through conduit 17. According to
this arrangement the maximum allowable. Referring now to figure 49 reactors 10, 11, 12 and 13 are
shown connected in series for carrying out the polymerization reaction. While four reactors are
shown it should be understood that more or fewer reactors can be employed, depending upon the
design capacity of the reactors and the desired residence time for the polymerization reaction.
Monomer in conduit 14, solvent in conduit 16, and recycle material which is predominantly
monomer and solvent in conduit 17 are combined in conduit 18 and fed and fed to reactor 10, the
fist reactor in the series. Catalyst for the reaction is also added via conduit 19 to this feed stream in
conduit 18. The polymerization effluent from the last reactor in the series, reactor 13, is removed
through line 20 and passed to heat exchanger 21. Various additives can be injected into the
polymerization effluent in conduit 20, for example, a shortstop or catalyst inactivating agent to
terminate the polymerization reaction, is injected into conduit 20 by way of conduit 22. Also, an
antioxidant is injected via conduit 23. The effluent stream is then heated in heat exchanger 21 and
passed to flash tank 24 where the pressure on the mixture is reduced and reacted monomer
together with some of the solvent is vaporized.

The unvolatilized residue together with polymer is passed from flash tank 24 via conduit 26 and heat
exchanger 27 to flash tank 28. This material is repressurized in conduit 26 by a pump, not shown,
and the pressure is again reduced in flask tank 28 so that the heat added in heat exchanger 27 causes
a portion of the solvent to vaporize together with more of the unreacted monomer. This operation
is repeated with the unvolatilized material being removed through conduit 29 and passing through
heat exchanger 30 to the final flash step in tank 31. More solvent is vaporized together with any
remaining unreacted monomer and the vapors pass overhead from flash tank 24, 28 and 31 through
conduits 32, 33 and 34 respectively. These vapors are combined in header 36 and passed to
condenser 37 where they are condensed and the condensate passes through conduit 38 to
accumulator 39. The unvaporized solvent together with the polymer is removed from flash tank 31
through conduit 40 and passed to further polymer recovery steps which are not shown in this
drawing since they are not essential to an understanding of this invention. A constant inventory is
maintained in vessels 24, 28 and 31 by liquid level controllers, not shown.

Condensate from accumulator 39 is withdrawn via conduit 41. A portion of this condensate is purged
from the polymerization system by passing it to a solvent purification step via conduit 42. Liquid
level controller 43 on accumulator 39 is operably connected to motor valve 44 in conduit 42 so that
the flow of condensate through line 42 can be regulated in order to maintain a substantially constant
liquid level in the accumulator vessel. Flow through line 42 in sensed by flow sensing element 46
and the associated transducer 47 produces a signal which is transmitted to flow recorder 48. The
remainder of the condensate in line 41 is recycle to the reaction by way of conduit 17 as previously
described.

The flow in conduit 17 is sensed by flow sensing element 49 which transmits a signal to flow recorder
50 operably connected to motor valve 51 in conduit 17 so that the flow of recycle materials in
conduit 17 is thereby maintained substantially constant. In one embodiment of this invention a
predetermined set point is established manually for flow controller 50. Flow sensing element 52 in
conduit 14 transmits a signal as a function of the flow through this conduit to flow recorder
controller 53 which is operably connected to motor valve 54 in conduit 14. The flow of make-up
monomer through conduit 14 is thereby maintained at a substantially constant predetermined value
established by the set point of flow recorder controller 53. The flow sensing elements can be of any
conventional variety but turbine type flowmeters are preferred. These flowmeters can be calibrated
to produce outputs proportional to the mass (gravimetric) rate of flow of the measured stream.

A sample of the feed stream in conduit 18 is passed by way of sample line 56 to analyzer recorder
57 which is an instrument capable of measuring the concentration of monomer in the feed stream,
for example, the concentration of butadiene in a stream of toluene. A number of well know
analyzers such as infrared analyzers, ultraviolet analyzers, differential refractometers, or mass
spectrometers can be used for this service although a gas phase chromatographic analyzer, such as
described in U.S. Patent 2,943,702 to Hudson et al, is preferred.

Analyzer 57 produces a signal which is a function of the concentration of monomer in the feed
stream in conduit 18. This signal is transmitted to recorder controller 58 which in turn is connected
to manipulate the set point of flow recorder controller 53. The set point of analysis recorder
controller 58 is the desired monomer concentration in the feed stream. If can be seen, therefore,
that if the monomer concentration in the feed stream tends to decrease, this change is sensed by
analyzer 57 and a signal is transmitted to controller 58 which senses the deviation of the monomer
content from the desired value established as its set point. This deviation causes a manipulation of
the set point of controller 53 so that a higher feed rate of make-up monomer is required by this
controller and thereby the concentration of the monomer in the feed stream is returned to its
desired value.

The flow of make-up diluent in conduit 16 is sensed by flow sensing element 59 which transmits a
signal as a function of this rate of flow to flow recorder 60 and to adding relay 61. Adding relay 61
also receives a signal from flow sensing element 49. This signal is a function of the flow of recycle
material through conduit 17. Relay 61 also receives a signal from flow sensing element 52. This signal
is a function of make-up monomer flow through conduit 14. Adding relay 61 produces a signal which
is a function of the sum of the signals received from flow sensing elements 49, 52, and 59. This
summation signal is transmitted to recorder controller 62 which has as its set point the desired total
flow of these three feed streams. Recorder controller 62 is operably connected to motor valve 63 in
conduit 16. Thus, the flow rate of the make-up diluent is regulated in order to maintain the total
flow of the recycle and make-up stream substantially constant. As in the situation above, where an
increase in the monomer make-up flow rate is required in order to offset a decrease in the monomer
concentration of the total feed stream, a corresponding decrease in the solvent flow rate is
automatically made in order to maintain the total flow rate of the feed stream in conduit 18 at a
substantially constant value.

According to another aspect of the invention, analyzer 57 analyses not only for the monomer
content in feed stream 18 but also for the content of inert materials, for example, low boiling
hydrocarbons which are vaporized in the flash vessels and returned with the recycle stream but
which do not enter into the reaction under the conditions maintained. In this embodiment analyzer
57 transmits a second signal to analysis controller 64 as a function of the concentration of the inert
components in the feed stream 18. Controller 64 in connected to manipulate the set point of flow
recorder 50 which in turn regulates the flow of recycle materials through conduit 17. According to
this arrangement the maximum allowable concentration of inert components in the feed stream ca
be established as the set point for controller 64. The recycle flow, therefore, is always at the
maximum value permissible for this maximum concentration of inert components in the feed
materials to the reactor. Since low boiling inert components are introduced with the make-up
monomer stream and are removed only through the purge stream in conduit 42, it can be seen that
these inert components are passed to the reaction zone primarily by way of the recycle stream.
According to this embodiment, as the concentration of inert components tends to become too high
in the feed stream, the amount of recycle material is correspondingly reduced which in turn passes
more of the return condensate from accumulator 39 to solvent purification steps. This reduction in
recycle flow likewise calls for an increase in the flow rate of make-up diluent which will ordinarily
result in a reduced analysis of monomer content in the feed stream, thereby demanding a higher
flow rate of make-up monomer.

A balance is ultimately achieved in which the net result is that the recycle stream is reduced and the
flow rates of both the make-up monomer and make-up diluent streams are increased. Should the
concentration of these inert components become lower than can be tolerated, the flow rate of the
recycle stream is increased with a corresponding decrease and less load is passes on to the solvent
purification steps. Also since the recycle materials have been through the reaction they are
essentially free of catalyst poisons: therefore, reuse of this material enables maximum utilization of
the catalyst.

Temperature: the reaction temperature can vary somewhat, although for higher cis-1, 4 polymers
the lower temperature are preferred. Temperatures of up to 50° C can be employed. The lower limit
on temperatures sated more by the freeze-point of the reaction medium than by catalyst activity.
Temperatures seems to be dictated more by the freeze-pint of the reaction medium than by catalyst
activity. Temperatures as low as -35° C have been employed. However, nearly as good results are
obtained in the range from about -10- C to about 30° C according to H. Tucker US3094514.

Catalyst systems containing TiCl4 and LiBH4 as described by D. A. Fraser et al in US2999088, are
generally sufficiently active for polymerization to be initiated at normal ambient temperatures or
below. The rate of polymerization is generally increased by raising the temperature of the reaction
mixture, but normally it is undesirable to employ temperatures far in excess of 150° C. it is preferred
to carry out the reaction in the temperature range 15-90° C. It has further been found that the
activity of such polymerization initiator systems re in some cases increased by heating the
components of the system before the polymerization reaction. It is preferred to heat them at a
temperature above 50° C, for instance in the range 60° to 100° C, for a sufficient time to cause an
increase in their catalytic activity.

Pressure: the pressure in the reaction vessel in which the polymerization is carried out is not critical
and may be varied at will. It is advantageous when dealing with normally gaseous materials, to carry
out the polymerization process under slightly elevated pressures because in this way the handling
of the materials is facilitated.

The pressures of the reaction are sufficient to maintain the diluent employed substantially in the
liquid-phase. Although pressures ranging from atmospheric up to 30000 pounds per square inch
gauge or higher can be employed, depending upon the diluent and monomer system, a pressure In
the range of from atmospheric to 1000 pounds per square inch gauge is usually preferred as noted
by J. N. Short et al in US2999089.

In actual practice as pointed out by L.M.Porter et al in US3066125, all that is normally required is
that the polymerization reactor be sealed so as to exclude the atmosphere from the reactor. This is
desirable because oxygen and moisture are harmful to the polymerization. Accordingly, in the
preferred because oxygen and moisture are harmful to the polymerization. Accordingly, in the
preferred embodiment it will be found that atmospheric pressures are suitable when the
polymerization is conducted at higher temperatures then higher pressures will be created within
the reactor but in almost all instances it is unnecessary to increase the pressures from external
sources. The preferred pressures are suitably defined as autogenic pressures which refers to the
pressures created by the system under the conditions of reaction. Such pressures will vary vary
depending upon the temperature, the nature and quantity of the diluent, and the like.

Reaction time: the residence time in a continuous process will, of course, vary within rather wide
limits depending upon such variables as temperatures, pressure, the catalyst system being
employed, and the material which is being polymerized. In a continuous process, the residence time
will generally fall within the range of one second to one hour when conditions within the specified
ranges are employed. When a batch process is being employed, the time for the reaction can be as
high as 24 hours or more. While the reaction times given necessarily cover a rather broad range, it
should be understood that for any desired conversion level the reaction period can be considerably
shortened by using promoters for the basic catalyst composition such as polycyclic aromatic
hydrocarbons as described by J. N. short et al in US2999089. This effect is especially pronounced
when the reaction temperatures are quite low and the solubility of the promoter is low.

Reaction medium: the butadiene polymerization reaction may be carried out in a hydrocarbon
which is a solvent or least for the monomer including saturated aliphatic hydrocarbons from
propane through pentane, hexane, heptane and higher boiling petroleum fraction such as debase
(a hydrogenated kerosene fraction) : aromatic hydrocarbons such as benzene, xylene, toluene, and
other +s: and cycloaliphatics such as cyclohexane. It is preferers, however, to employ a solvent
medium which includes at least about 15% by weight of an aromatic hydrocarbon such as benzene
or xylene. The presence of the aromatic hydrocarbon produces somewhat faster reactions and a
more easily processed polymer. Mixed butane or pentane/benzene solvents can be employed to
advantage because of higher solids possible with the slurry-like products produced. Commercial
supplies of the aromatic hydrocarbons may be highly impure and should be treated with sulfuric
acid and then distilled and dried before use.

The proportion or concentration of monomeric material in the reaction mixture can vary somewhat
depending on the particular solvent or diluent medium employed. In most solvents in which both
monomer and polymer are completely soluble, up to about 10% by weigh of monomer, based on
the total liquid mixture, can be present with the production of flowable, cement-like products. In
the order solvents in which the polymer mixture is obtained, a monomer concentration of up to
about 20% can be employed according to H. Turcher in US3094514.

According to F. E. Naylor in US3202646, it is desirable to initiate the polymerization in the presence

of a minor amount of an aromatic diluent and thereafter introducing an aliphatic hydrocarbon
diluent, either in increments or continuously as the polymerization proceeds. At the conclusion of
the polymerization, the aliphatic hydrocarbon diluent present is a major amount of the total diluent
added. It has been discovered that if the polymerization is initiated in the presence of a small
amount of an aromatic hydrocarbon and an aliphatic hydrocarbon is added in increments or
continuously as the polymerization progresses, there is a marked reduction in viscosity of the
reaction mixture with no substantial effect on the cis-content of the product. Also, when operating
in this manner, a much smaller amount of total diluent than is generally required when an aromatic
hydrocarbon is used as the sole diluent can be used to maintain the mixture in a fluid state. This is,
of course, a very important economic advantage. Other advantages of the present process are that
aliphatic hydrocarbons are easier to remove at the conclusion of the reaction and they are less
expensive than aromatic hydrocarbons.

It is possible to conduct the reaction in the presence of an extender oil as the reaction medium (the
oil remaining in the product polymer) if the polymerization is carried out in a worm extruder
according to F. Engel et al (to chemisch werke huls) in US3183204)

During the polymerization operation where in the 1, 3-butadiene is polymerized to a rubbery

polymer employing a catalyst system containing TiL4 and R3Al and a diluent such as toluene, there
accumulates in the diluent or solvent material poisonous to the catalyst system. This material
includes water and other impurities which are effective to reduce the activity of the catalyst.
Accordingly, it is necessary to purify the solvent if it is to be reused. Thus in the production of a
product containing a rubbery polymer of 1, 3-butadiene characterized by at least 85% of cis 1, 4-
addition using, say, toluene as a solvent it is necessary to treat the recycle toluene solvent by
fractionation and alumina adsorption to remove water poisons to the polymerization catalyst
system before this toluene can be fed to the reactor.

A process for such purification has been described by D.M.Haskell et al in US3244686.

According to the invention, a solvent or diluent used in the catalytic polymerization of a hydrocarbon
is purified of materials tending to poison the catalyst employed by passing the same to a
fractionation zone at an intermediate point thereof, removing water as a low boiling vaporous
product from the fractionation zone, removing a major portion of solvent from the fractionation
zone as a high boiling product and removing, and if desired purifying a minor stream of solvent from
a point intermediate the points at which the low boiling vaporous product is removed from the
fractionation zone and at which solvent is removed therefrom. When treated, the minor stream is
then recombined with the high boiling or bottoms product for further use.