Note: Descriptions are shown in the official language in which they were submitted.
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BACKGROUND OF THE INVhrNTION
1. Field Of The Invention
This invention rel-ates to new types of ring-
opened, addition organic polymers such as polyoxyethylene_
polyoxypropylene polymers and methods for making them.
In particular, the present invention is concerned with
novel ring-opened, addition type polymers with controlled
monomer sequence distributions and processes for making
them.
2. Prior Art
A wide variety of polymers made from one or
more cyclic, organic monomers capable of ring-opening,
addition polymerization are in extensive use for a wide
range of applications. For example, copolymers of ethylene
oxide and propylene oxide represent a particularly fruitful
area in which to apply the present invention as a tool for
tailoring performance characteristics. This is so because
these two monomers form respective homopolymers which,
although generally similar in glass transition temperatures,
are basically dissimilar in solubility characteristics.
Poly(ethylene oxide) for example, is a water soluble poly-
mer which hydrogen bonds extensively in aqueous solution.
Poly(propylene oxide), on the other hand, is an oil soluble
polymer with greatly reduced tendencies toward hydrogen
bond formation. When these two monomers are copolymerized,
therefore, the products which result exhibit both hydro-
philic and hydrophobic character to an extent dependent
upon both the overall composition and the structure of the
copolymer in terms of monomer sequence distribution.
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Block copolymers of ethylene oxide and propylene
oxide have very distinct surface active characteristics.
They are efficient surface tension reducers in aqueous
solutions and function as surfactants, wetting agents, and
emulsifiers. The block copolymer structure thus maximizes
the performance characteristics of such copolymers in all
areas which depend upon well-defined hydrophile and hydro-
phobe structure. There is currently marketed a broad line
of such oxide copolymers, their product line being pre-
sented in the form of a grid whose axes are molecular
weight of the hydrophobe block (propylene oxide block) and
overall hydrophile content (weight percent ethylene oxide).
As a further consequence of the block structure, these commer-
cial copolymers have the ability to gel water solutions at
certain rather high fluid concentrations. This property
is utilized in the preparation of a broad line of clear
ringing gels for applications such as antiseptics, cosmetics,
sun-screening agents, hair bleaches and the like. Because
of their structural homogeneity within the hydrophile and
hydrophobe segments, block copolymers are often pastes or
solids at ambient temperatures.
Conventional random copolymers of ethylene oxide
and propylene oxide lack the pronounced surface active char-
acteristics of their blocked counterparts. Thus, they have
been much poorer reducers of surface tension in aqueous so-
lutions and are generally poorer wetting agents, surfactants
and emulsifiers. This behavior is a direct consequence of
the random structure, which does not permit the formation of
lengthy chains of either hydrophile or hydrophobe portions.
Because of their structural heterogeneity, random copoly-
mers are generally liquids at the same molecular weights and
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overall compositions where their blocked counterparts are
solids or pastes. A considerable number of random
ethylene oxide-propylene oxide copolymers are commercially
available but, unlike the block copolymers, the random
structures do not gel water. They find applications
which stress their utility as functional fluids such as
pump lubricants, quenching fluids in foundary operations,
brake fluids, "pusher" fluids in drilling operations and
the like. Inasmuch as these random structure fluids form
homogeneous aqueous solutions, they can be used
advantageously as base components for non-flammable
functional fluids.
Heretofore, the only types of oxide copolymers
known to the art have been the block and random types
which, as we have seen, are characterized by widely diver-
gent properties. The present invention is ideally suited
to the preparation of an infinite number of different
structural species intermediate between the block and random
extremes. In accomplishing these structural alterations by
this invention, it is observed that certain solution
properties of these copolymers change accordingly. The
present invention therefore represents a simple and
convenient means for tailoring the structure of such
copolymers so as to generate various desired solution pro-
perties of a type intermediate between those exhibited by
random and block copolymers. Exemplary of the solution
properties which can be altered by this technique are
aqueous and non-aqueous solution viscosity, wetting ability,
foam stability, cloud point, and surface tension. Addition-
ally, the present invention makes possible the preparation
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of liquid fluids with properties very similar to those of
block copolymers which are solids or pastes.
Certain process techniques disclosed in U.S.
Patent 3,804,881, and to some extent disclosed in U.S.
Patent 3,839,293, may be employed in the practice of this
invention. ~owever, the polymers of this invention are
not disclosed in either of these patents. The polymers
disclosed and claimed herein are new and possess unexpected
beneficial properties not heretofore attained for polymers
made from the same monomers. Attention is also drawn to
U.S. Patents 3,427,287; 3,448,173 and 3,562,235 and British
Patent 1,292,226. None of these latter patents disclose the
polymers of this invention or techniques for making them.
No other more pertinent prior art is known.
BROAD DESCRIPTION OF THE INVENTION
The present invention provides novel polymers of
at least two different cyclic organic monomers capable of
ring-opening, addition polymerization with themselves
and each other. The polymers of this invention comprise
polymer chains along which the proportion of mer units
provided by a first monomer in one or more given chain
lengths (also called "first chain lengths" herein) gradually
increases as the proportion of mer units provided by a
second monomer along the chain length gradually decreases.
Unlike conventional polymers of monomers of this type,
the novel polymers have graded sections or chain lengths in
their molecules wherein the proportions of mers from the
respective monomers gradually shift from one type of
mer units to the other type or types of mer units. As
a consequence, the polymers of this invention exhibit
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performance characteristics not heretofore attainable
from polymers made from such monomers by conventional
procedures.
The monomers to which this invention applies are
typically oxirane or 1,2-epoxide monomers, i.e., monomers
having an oxirane oxygen bonded to vicinal carbon atoms,
such as ethylene oxide and propylene oxide but include other
classes of cyclic organic monomers which polymerize with
themselves and each other by ring-opening, addition reac-
tions. In addition to those mentioned above, further 1,2-
epoxide monomers which can be used in this invention include
butylene oxide, styrene oxide, cyclohexene oxide, 1,2-epoxy
butadiene, 3-phenoxy-1,2-propylene oxide, glycidyl acrylate,
1,2-epoxy-4,4,4-trichlorobutane, 1,2-epoxy-cyclohexene,
5,6-epoxy-2-norbornene, linseed oil epoxide, and glycidyl
methacrylate to mention but a few.
Additional types of cyclic organic monomers other
than the epoxides which can be used in the process of this
invention include cyclic amides (lactams), cyclic esters
(lactones), oxazolidine-2,5-diones, ketene dimers and lac-
tides. Specific examples of such ring systems are capro-
lactam, 2-pyrollidone and 2-azetidinone as cyclic amides,
~ -propiolactone, epsilon-caprolactone and valerolactone
as cyclic esters, glycine N-carboxyanhydride as an oxazo-
lidine 2,5-dione, the dimer of dimethylketene and lactide
itself.
It is recognized that some of these classes
of cyclic organic monomers are polymerized with catalyst
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systems other than the alkali metal hydroxides which are
used to catalyze the epoxide systems, such as organometal-
lic reagents, amines, alkali metal hydrides, Lewis acids,
metal oxides, and the like. The fact that types of cataly-
sis other than that used herein for the epoxides may be
required or preferred for certain classes of monomers is
not intended to represent a limitation of this invention.
Rather it is to be understood that the present invention
is applicable to the preparation both of copolymers
derived from monomers of the same basic type or class and
to copolymers derived from monomers representing different
classes of cyclic organic monomers. For purposes of
example, the Lewis acid ~e.g., boron trifluoride) catalyzed
copolymerization of ethylene oxide with ~-caprolactone to
afford a polyether-polyester copolymer is cited as a mixed
system to which the power feed process can be applied. It
will be obvious to those skilled in the art that the sole
limitations on the types of copolymers which may be
prepared are that the catalyst system used in mixed class
copolymerizations must be one which is active for all
types of monomers involved and that the reaction conditions
employed must be otherwise compatible with the chemistries
of the respective monomers employed.
The process for producing the novel polymers of
this invention includes at least one stage which comprises
the steps of introducing at least one primary polymerizable
feed composition comprising at least one of the cyclic
organic monomers capable of ring-opening, addition
polymerization from at least one primary feed source to a
polymerization zone, the primary polymerizable feed
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composition continually varying in compositional content
of the polymerizable monomers therein during the continuous
introduction; simultaneously adding to the primary feed
source at least one different secondary polymerizable
feed composition comprising at least one different cyclic
organic monomer capable of ring-opening, addition polymer-
ization with itself and the first mentioned monomer, from
at least one secondary feed source so as to continually
change the compositional content of the polymerizable
monomers in the primary polymerizable feed composition in
the primary feed source; and continuously polymerizing
the primary polymerizable feed composition introduced to
the polymerization zone until the desired polymerization
has been achieved. In those instances where the respec-
tive monomers are of substantially different reactivities
or reaction rates it is essential to maintain conditions in
the polymerization zone approaching monomer starvation so
that the monomer mixture reaching the polymerization zone
polymerizes almost instantaneously to provide a composition
for the polymer portions which closely resemble the compo-
sition of the monomer mixture as fed to the polymerization
zone.
It can be readily appreciated that the present
invention permits the skilled worker to prepare at will
a large number of polymers having different patterns of
compositional content along the chains of the polymer
molecules. If desired, more than two cyclic organic
monomers can be used. In addition, if desired, sections
of the novel polymer chains can also include conventional
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blocks of mers of one or the other of the monomers (e.g.,
as in conventional block copolymers) by employing known
techniques for forming such blocks. Furthermore, the
skilled worker has the further option of including sections
of random polymerized monomers (e.g., as in conventional
random copolymers) by employing known techniques for forming
random copolymers.
The terminal portions of the polymer chains of
this invention can comprise up to 100% of mer units pro-
vided by one of the monomers at both ends or at one end
with up to 100% of mer units provided by the other monomer
at the other end. The terminal portions at both ends
can comprise mixtures of mer units derived from two or
more different monomers or the terminal portion at one end
can comprise a mixture of mer units of different monomers
and at the other end they can comprise up to 100% of mer
units provided by one of the monomers. As pointed out
above, the novel polymers can also comprise one or more
blocks (also called "second chain lengths" herein) of mer
units derived from one monomer. These blocks or second
chain lengths can be positioned at the terminal positions
of the polymer chains or at intermediate portions thereof.
The novel polymers can also contain in their
polymer chains a single given or first chain length as
described above, alone or connected to one or more second
chain lengths as described above. Alternatively, the
polymer chains can contain, connected to the first chain
length or second chain length, if any, another chain length
(also called "third chain length" hereinafter) which is
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similar to or the same as the first chain length. That
is, in the third chain length the proportion of mer units
provided by a first monomer gradually increases as the
proportion of mer units provided by a second monomer de-
creases, or the proportion of mer units provided by the
first monomer gradually decreases as the proportion of mer
units provided by the second monomer increases. The pro-
portion of mer units provided by the first monomer in the
third chain length can gradually increase at the same or
different rate as that in the first chain length. The third
chain length when the same as, or similar to but different
from, the first chain length can be connected to the second
chain length. When similar to but different from the first
chain length, the third chain length can be connected
directly to the first chain length.
The process of this invention enables the polymer-
ization scientist to control the polymerization process
in such manner that he can produce polymers having the de-
sired chemical structures and utilities. The polymers are
produced by a process in which the concentrations of the
polymerizable cyclic organic monomers in the primary poly-
merizable feed composition are continually changing during
the introduction of the primary polymerizable feed mixture
to the polymerization zone by the simultaneous addition of
a different secondary polymerizable cyclic organic monomer
feed mixture to the primary polymerizable feed mixture.
The distinguishing feature of this process is the introduc-
tion of primary polymerizable cyclic organic monomer feed
mixture to the polymerization zone from a primary feed
source while simultaneously introducing at least one
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different secondary polymerizable cyclic organic monomer
feed composition from a secondary feed source to the primary
polymerizable feed composition in the primary feed source.
The polymerization zone is any reactor, properly
equipped, that can be used for the production of polymers.
The different types of reactors and their suitability for
a particular polymerization reaction are well known to
those skilled in the art and do not require elaboration
herein. Connecting to the polymerization reactor is at
least one primary feed source. The term "primary feed
source" defines one or more tanks or source of polymerizable
reactants feeding directly into the polymerization zone or
reactor, for example, it can be an in-line mixer or a tank.
The primary feed source is equipped with efficient mixing
means to assure adequate mixing of the contents thereof.
Connecting, in turn, to any of the primary feed sources is
at least one secondary feed source. The term "secondary
feed source" defines one or more tanks or sources of
polymerizable cyclic organic monomers feeding to any of
the primary feed sources. There can be one or more second-
ary feed sources with all of the secondary feed sources
feeding directly into the primary feed source, or one or
more of the secondary feed sources can feed in series to
another secondary feed source and thoroughly mixed therein
with finally an ultimate secondary feed source feeding
directly into one or more of the primary feed sources.
The rate of feed from any one feed source to any other
feed source or tank, whether primary or secondary, can be
varied at the will of the skilled scientist to meet his
desires and objectives. The configurations that can be
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engineered are many; however, in all instances there must
be a polymerization zone or reactor connected to at least
one primary feed source or tank equipped with mixing means
which in turn is connected to at least one secondary feed
source or tank which secondary feed sources (when more than
one thereof is used) can all or in part feed directly into
one or more of the primary feed source or tank or can feed
in series into one another and ultimately feed into the
primary feed source or tank.
The primary polymerizable feed composition is the
mixture of reactants present at any particular time in
the primary feed source or tank. This mixture can contain
the polymerizable reactants alone or it can include any
additive which will not have a deleterious effect on the
polymerizable reactants, for example, diluents or solvents,
colorants, dispersion or emulsion agents, antioxidants,
stabilizers, chain transfer agents, crosslinkers, initia-
tors, one of the components of a redox catalyst system,
and the like. The compositional content of the primary
polymerizable feed composition is continually changing as
secondary polymerizable feed composition is fed into and
mixed with it. By the term compositional content is
meant the content or concentration in the polymerizable
feed composition of each reactant therein. As becomes
apparent from this teaching and description the simultaneous
feeding of primary polymerizable feed composition from the
primary feed source to the polymerization zone and feeding
of a different secondary polymerizable feed composition
from the secondary feed source to the primary feed source
will result in a continual change of the content or
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concentration of each reactant present in the primary
polymerizable feed composition or in the compositional
content of the primary polymerizable feed composition.
This continual change in compositional content can also
occur in the secondary polymerizable feed compositions when
more than one thereof is being used and they are feeding
in series into each other before ultimately feeding into
the primary polymerizable feed composition.
The secondary polymerizable feed composition is
the mixture of reactants present at any particular time in
any one or more of the secondary feed sources or tanks and
can contain the same types of additives that were previously
indicated could be present in the primary polymerizable
feed composition. It should be remembered, however,
that if one of the polymerizable feed mixtures contains
one of the components of a catalyst system that the other
such mixture cannot contain the other component thereof,
otherwise polymerization will occur in the feed tanks
before the polymerizable reactants are introduced into
the polymerization zone.
As indicated, in the process of this invention
there are used primary polymerizable feed compositions and
secondary polymerizable feed compositions. The primary
polymerizable feed composition can initially contain a
single polymerizable reactant or it can initially contain
a plurality of polymerizable reactants; the same is true
for the initial content of the secondary polymerizable
feed composition. However, when the primary polymerizable
feed composition is a single reactant the secondary poly-
merizable feed composition cannot be solely that same
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single reactant, it can be a different single reactant or
a mixture of a plurality of reactants that can include
that same reactant in the mixture. Likewise, when the
primary polymerizable feed composition is a mixture of a
plurality of reactants the secondary polymerizable feed
composition cannot be that same mixture having the same
concentrations for each reactant, it can be a single
reactant or it can be a different mixture of reactants or
it can be a mixture of the same reactants but at different
initial concentrations of the reactants. The important
and ever present factor is that the initial compositional
contents of the primary polymerizable feed composition and
of the secondary polymerizable feed composition are always
different, they are not initially identical in make-up
of polymerizable reactants.
As a result of the initial differences in the
compositional contents of the primary and secondary poly-
merizable feed compositions and of the simultaneous addition
of secondary polymerizable feed composition to primary
polymerizable feed composition while the primary polymeriz-
able feed composition is introduced into the polymerization
zone there is a continual variation in the compositional
content of the primary polymerizable feed composition.
Hence, any portion of the primary polymerizable feed
composition entering the polymerization zone is at all
times different than the portion that preceded it and the
portion that succeeds it. Consequently, the composition of
the polymer produced in the reactor during the addition
is likewise continuously changing and reflects the compo-
sition of the primary polymerizable feed composition
l~lS9~ 9454
entering the polymerization zone. In a rapid polymeriza-
tion reaction, one wherein there is essentially instanta-
neous reaction of the monomers when they are introduced to
the polymerization zone, one has what is known as a monomer
starved system. In other reactions one may have a so-
called monomer rich system, i.e., a system in which there
is some time delay between introduction of the reactants
to the polymerization zone and essentially complete poly-
merization of the reactants. Thus, in a monomer starved
system the polymer produced at any one period of time
differs in constitutional content from the polymer produced
prior to that period of time or subsequent to that period
of time. However, in a monomer rich system the composition
of the polymer formed at any instant is dependent upon the
concentration of each monomer in the polymerization zone
and the respective reactivity of each monomer present
therein in relation to the other monomers. There are
thus produced certain novel non-uniform polymer compositions
of polymer molecules having infinite variation in molecular
structures. The instant invention provides a novel process
for the production of polymers and certain novel non-uniform
polymers themselves. By the term infinite variation in
molecular structures is meant the mixture of the infinite
number of different polymers that is produced in the poly-
merization zone by our process. 8y the term non-uniform
is meant that polymer molecules formed at any one time
during the polymerization reaction are not the same as
polymer molecules formed at any other time.
The process of the invention can be described in
its simplest manner by a reaction involving a single
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primary feed source initially containing a single polymer-
izable reactant and a single secondary feed source initially
containing a single different polymerizable reactant. The
contents in the primary feed source or tank at any time
during the process are known as the primary polymerizable
feed composition and the contents of the secondary feed
source or tank are known as the secondary polymerizable
feed composition. Secondary feed source feeds into primary
feed source by suitable lines and pumps; primary feed
source is equipped with an efficient stirrer or mixer and
feeds into the polymerization zone. At the start of the
polymerization reaction the flow of primary polymerizable
feed composition from primary feed source to the polymeriza-
tion zone is commenced at a predetermined rate, simultaneous-
ly the flow of secondary polymerizable feed composition
from secondary feed source to the primary feed source is
initiated and this rate of flow can be the same as or
different from the rate of flow from the primary feed
source to the polymerization zone. As the secondary
polymerizable feed composition enters the primary feed
source it is thoroughly mixed with the contents thereof
resulting in a continual change in the compositional
content of the primary polymerizable feed composition.
~his continually changing primary polymerizable feed
composition is simultaneously and continuously entering the
polymerization zone and the polymer produced therein is
varied in accord with the compositional content of the
reactants mixture in the polymerization zone. As is
apparent from the prior description either or both of the
primary or secondary feed source can contain more than one
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polymerizable reactant.
The variations in the engineering arrangements of
the primary and secondary feed sources are innumerable
and no attempt will be made to set forth each specific
tank configuration or arrangement possible; these can
readily be devised by skilled individuals at will for the
purpose of obtaining maximum operational efficiency or
for the purpose of obtaining products having certain desired
properties. In the preceding paragraph there has been
outlined a simple arrangement employing a single primary
feed source and a single secondary feed source. Slightly
more complex arrangements would be those wherein there was
a single primary feed source and a plurality of secondary
feed sources; in these instances all of the secondary feed
sources could be feeding in parallel directly into the
primary feed source or some of the secondary feed sources
could be feeding in series to other secondary feed sources
with at least one secondary feed source, whether in series
or not, ultimately feeding directly into the primary feed
source. Other arrangements would be those wherein there
were a plurality of primary feed sources; in these instances
there could be a single secondary feed source feeding into
one or more of the plurality of the primary feed sources,
or there could be a plurality of secondary feed sources
all feeding in parallel directly into only one of the
primary feed sources, or a plurality of secondary feed
sources directly feeding into more than one primary feed
source or all of the plurality of secondary feed sources
could be feeding in series into only one of the primary
feed sources, or the plurality of secondary feed sources can
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be feeding in series into more than one of the primary
feed sources. When a plurality of secondary feed sources
is used they can be used in any combination desired, all
can be used in series, some can be used in series while
others are not, or none need be used in series with all of
them being added directly to the primary feed source.
In all instances the primary feed sources feed the primary
polymerizable feed composition to the polymerization zone;
the secondary feed sources feed the secondary polymerizable
feed composition directly to the primary feed source or
in series to another secondary feed source with the reactants
therein ultimately terminating in the primary feed source
before entering the polymerization zone. During these
movements of reactants from one feed source to another
there is a resultant continual change in the compositional
content of the contents of the tank to which polymerizable
reactant is added and the contents of the tanks are agitated
to obtain efficient mixing of the contents therein. One
can also vary the process by having periods of time at
the start, during or near the end of the reaction wherein
there is feeding of primary polymerizable feed composition
from the primary feed source into the polymerization
reactor without any simultaneous feeding of secondary
polymerization feed composition into the primary feed
source or tank for a selected period of time. In addition,
the flow rates between feed tanks or polymerization zone
can be varied at will at any time during the polymerization
reaction. One can also, with suitable known means, using
variable feed valves, feed polymerizable reactants from a
plurality of secondary feed sources through an in-line
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9454
mixer which serves as the primary feed source wherein
the primary polymerizable feed composition is produced.
The in-line mixer then feeds the primary polymerizable
feed composition directly into the polymerization zone.
In the process of this invention non-uniform
polymers are produced in a controlled manner. By the
term non-uniform polymer is meant a polymer composition
produced by the reaction of a polymerizable reactants
mixture which during a portion of the polymerization
period is continually changing in compositional content.
The polymers produced by this process can have unexpected
properties and/or performance characteristics compared to
similar polymers produced by the conventional processes
used in the past. In addition, it was found that one can
design polymers having the desired properties and per-
formance characteristics. It was further found that
polymers having satisfactory and desirable properties
can be produced from mixtures of polymerizable reactants
that in the past could not be used to obtain satisfactory
polymers. The process also enables one to unite bas~ally
incompatible monomers for the production of useable
polymers by virtue of the continuous change in composition
of the polymer being produced during the polymerization
reaction.
The incorporation of functional groups on the
surface of the polymer particles, for example for external
cross-linking or adhesion promotion, can also be controlled
by gradually and continually increasing the concentration
of reactants containing such groups in the primary
polymerizable feed composition towards the end of the
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polymerization reaction.
The processes of this invention can be used to
polymerize any mixture of polymerizable cyclic organic
monomers or reactants that will co-react or copolymerize
with each other at a rate such that there is no
substantial build-up of any one monomer or reactant or
group of monomers or reactants while the other monomers
or reactants are reacting and forming polymer. The
invention is not restricted to any limited group or class
of polymerizable cyclic organic monomers or reactants,
the process is broad in its application and use.
The concentrations of a particular polymerizable
reactant initially present in the primary polymerizable
feed composition or initially present in the secondary
polymerizable feed composition can vary from 0.01
weight percent to 100 weight percent based on the total
weight of polymerizable reactants initially present
in the particular feed stream. These concentrations
can be varied at the will of the skilled individual,
as is recognized in the art, to obtain the particular
final concentrations of each reactant in the polymer or
to obtain a particular property or characteristic in the
polymer. The rate of flow from secondary feed sources
and from primary feed sources can also be varied at the
will of the skilled individual and do not require
elaborate discussion herein. The process employs the
temperature and pressure conditions known suitable for
the reactants employed. As a consequence of the control
over monomer sequence distribution provided by this
invention, the resulting polymers exhibit performance
lili~9~
9454
characteristics not heretofore attainable from the same
monomers.
BRIEF DESCRIPTION OF THE D~A~INGS
Fig. 1 is a schematic diagram illustrating apparatus
that can be used to carry out this invention;
Fig. 2 is a graph plotting viscosities in
centipoises at 25C. of aqueous solutions of the
copolymers produced in Examples 1, 2, 3, A and B described
hereinafter versus the copolymer concentrations in weight
percent.
Fig. 3 is a graph plotting viscosities in
centipoises at 25C. of aqueous solutions of the copolymers
of Examples 5, 6, 7, 8 A and B described hereinafter versus
the copolymer concentrations in weight percent.
DESCRIPTION OF PREFERRED EMBODIMENTS
Among the preferred polymers, of this invention,
are the polyoxyethylene-polyoxypropylene copolymers
prepared according to this invention. That is, the
preferred polymers comprise polymer chains along which
the porportion of oxypropylene units in a given chain
length gradually increases (or decreases) as the
proportion of oxyethylene units gradually decreases
(or increases).
A preferred process for preparing ethylene oxide-
propylene oxide copolymers of the present invention differs
from processes employing conventional block or random free
techniques, primarily in the manner in which the
comonomer feed stocks are introduced into the
polymerization zone. This difference, of course,
represents the essence of the process of the present
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llil~94
9454
invention. Another important difference, which often
arises as a requirement of the process of this invention
lies in operating under conditions approaching monomer
starvation in the reaction system. The latter difference
is an important one in ethylene oxide - propylene oxide
copolymerizations because these two monomers are quite
different in terms of their quite different reactivities.
Ethylene oxide reacts faster than propylene oxide under the
conditions of a base-catalyzed alkoxylation. Additionally,
the ethylene oxide addition generates a primary hydroxyl
group on the polymer chain as opposed to predominantly a
secondary hydroxyl group with 1,2-propylene oxide
addition. Since the primary hydroxyls are more reactive
than the secondaries, there is an inherent tendency for
lengthy sequences of ethyleneoxy units to form in such
copolymerizations. However, by operating at atmospheric
pressure to ensure a low concentration of unreacted
oxides in the liquid phase and feeding monomers at a rate
such that they are consumed as rapidly as they are fed,
the problem of unequal reactivities of the two oxides
can be largely overcome. In conducting the copolymeriza-
tions given in the Examples hereinafter presented,
conditions approaching monomer starvation were established
and maintained by ensuring that the visually monitored
reflux rate of unreacted oxide monomers did not exceed one
drop per every 15 drops of monomer feedstock introduced.
Otherwise, the process of this invention for making
the novel copolymers is no different from conventional
processes using random or sequential feeds. For example,
a preferred process for ma~ing polyoxyethylene-polyoxypro-
pylene copolymers comprises feeding the appropriate
9454
quantities of the monomers to a kettle charge containing
a starter and some base catalyst, usually the potassium
alcoholate derivative of the starter. The starters are
known to those skilled in the art and can be monofunctional
or polyfunctional. Since these compounds are well illustra-
ted in the prior art, they require no further elaboration
to enable one skilled in the art to comprehend which
compounds are intended. Any of the known starters can be
used. They include alcohols, polyols, primary or secondary
amines, hydroxyl amines and carboxylic acid compounds; water
can also be used as a starter. The amount of starter charge
is dictated by the molecular weight desired and the quantity
of monomer to be fed; for example, a charge of one mole
of a starter of molecular weight x with 2000 grams of the
oxide monomers should give a theoretical number average mole-
cular weight of 2000 + x. As a general rule the actual
molecular weight achieved is somewhat below theory
because side reactions, traces of moisture in the feed,
and/or other factors tend to depress the molecular
weight. A typical catalyst charge is 0.1 - 0.5% by weight
(such as potassium hydroxide) based upon the final weight
of product expected. The catalyst solution can be
prepared from the starter alcohol either by direct
reaction with metallic potassium or potassium hydroxide,
or by an exchange reaction with some other potassium
alcoholate. If KOH is used, the water generated in the
catalyst preparation should be removed by some means such
as azeotropic distillation, for example, prior to the
addition of any oxide monomer feeds. In the case of
starter prepara'ion by an alcoholate exchange reaction,
the lower boiling alcohol released from the added
alcoholate by exchange should be removed, by distillation,
_~A _
1111~94
9454
for example, prior to the addition of oxide monomer feeds.
Other alkali metals or their derivatives such as sodium,
sodium hydroxide or a sodium alcoholate can be employed
as polymerization catalysts also, but the potassium
species are preferred.
The usual polymerization temperature for ethylene
oxide - propylene oxide copolymerizations of this type is
about 100-125C. with the preferred range being about 100-
110C. In general, the temperature used should be the
minimum temperature consistent with an acceptable reaction
rate because higher temperatures promote side reactions or
isomerizations which generate unsaturated species. The
polymerization should be conducted in the presence of
nitrogen or some other inert gas to repress oxidation
reactions leading to poor color. Atmospheric or super-
atmospheric pressures may be employed, but for purposes
of the present invention pressures nearer atmospheric are
preferred in order to prevent an appreciable build-up of
unreacted oxide monomers in the liquid phase. Upon
completion of the oxide monomer addition, standard
procedure is used to cook out the charge for a short period
of time prior to neutralization, filtration and stripping.
The neutralization can be conducted with various mineral
or organic acids, or alternatively with certain diatomaceous
earths, such as the commercial "Magnesol" product. Other
procedures such as ion-exchanging are also acceptable.
Following neutralization, which is preferably carried out
at 100-110C., the charge is filtered to remove salts of
neutralication and held for a short period of time under
reduced pressure so as to free it of any residual monomers
or other volatiles.
Sg4
9454
It must be emphasized that this invention is not
limited to any particular techniques of operation or
workup. Each manufacturer has certain procedures and/or
techniques which he prefers and which may be unique
to his situation. The process described hereinabove is
for purposes of illustration; the utility of the process
of this invention is not limited in scope to any specific
set of conditions or procedures.
Suitable apparatus for carrying out the present
invention is shown in Fig. 1. Other apparatus can be
used. The apparatus shown in Fig. 1 was used in carrying
out the examples presented hereinafter.
The apparatus of Fig. 1 includes a polymerization
vessel or reactor 1 equipped with a stirrer 2 driven by a
motor 3 and a thermocouple 4 for monitoring the temperature
of polymerization. The polymerization vessel 1 is closed
and is fitted with a vent 5 connected to a dry ice
condenser 6 which is connected to cold traps (not shown).
The polymerization vessel 1 is also fitted with an inlet 7
connected to a primary feed source 8 also called feed tank
I hereinafter. Feed tank I or primary feed source 8 is
equipped with a stirrer 9, a motor 10 and brine cooling
means 11. A valve 12 is located in the line 13 leading
from the primary feed source 8 to the polymerization
vessel 1 for controlling the rate of flow of primary
polymerizable feed composition from source 8 to vessel 1.
The primary feed source 8 is also provided with an inlet
14 which is connected to a secondary feed source 15, also
called feed tank II hereinafter, which contains brine
cooling means 16 and a nitrogen inlet 17. A valve 18 is
- 26 -
:~lllS9~
9454
located in line lg leading from secondary feed source
15 to primary feed source 8 for controlling the rate of
flow of secondary polymerizable feed composition from
secondary feed source 15 to primary feed source 8.
The arrangement depicted in Fig.l-isoneof the
simpler arrangements out of the many possible multiple
feed tank possibilities inherent in the present
invention. One feature which is preferably common to all
configurations is that of a mix~ng capability in the
primary feed tank 8 which ultimately feeds directly the
polymerization reactor 1.
The process of this invention can be regarded as a
multi-stage process having an infinite number of stages.
Implicit in its use in the production of polymers from
monomers having divergent rates of polymerization (e.g.
ethylene oxide and propylene oxide) is the fulfillment
of the requirement that the polymerization be conducted
under conditions approaching monomer starvation, i.e.,
conditions which ensure that conversion of monomer feed to
polymer proceeds at a rate equal to or exceeding the rate
at which the monomers are introduced into the reaction zone
1. Thus, the composition of the copolymer formed at any
given instant must ~hen necessarily differ slightly from
that formed just prior to or just subse~uent to it in
points of time.
An infinite variety of monomer feed profiles are
possible through application of this invention to a given
copolymer system. Providing that conditions approaching
monomer starvation prevail in the reaction system in the
usual case, each combination of conditions will generate
- 2~ -
1~ 11594
9454
a copolymer whose structure will be unique to the
particular feed profile employed. If the specific
monomers comprising the copolymer are ones whose
respective homopolymers are basically dissimilar in
properties, copolymers generated by different feed
profiles can be expected to exhibit differences in their
performance characteristics.
~xAMæLEs
The following examples are presented. Unless
otherwise stated, all parts and percentages are on a
weight basis and all temperatures are on the Centigrade
scale. ~xamples A, B and C given below do not illustrate
the present invention but are presented for comparison
purposes.
The evaluation tests performed in providing the
data in the following examples to characterize the
products of this invention analytically and functionally
are summarized below:
A. Analytical Cha_acterization
1. Molecular Weights - Number average molecular weights
are obtained by a wet chemical method wherein the
hydroxyl content is determined through reaction
wit~ phthalic anhydride in pyridine solution
followed by titration of the excess anhydride with
a standard solution of sodium hydroxide.
2. Gross Compositions - The overall compositions were
obtained by nuclear magnetic resonance spectroscopy
in deuterochloroform solvent. The area of the
9~
9454
propylene oxide methyl group protons at
1.15 ppm is subtracted from the total area of all
methylene and methine protons in the region of
3.2 ~ 3.9 ppm. The difference represents the
contribution due to ethylene oxide.
3. Glass Transition Temperatures - The glass
transition temperatures ~Tg) were determined by
plotting torsion pendulum-generated loss modulus
data against temperature.
4. Monomer Sequence Average Lengths - These were
obtained by nuclear magnetic resonance spectroscopy
in carbon disulfide solvent using tris(divaloyl-
methanato) europium as the shift reagent. Sequence
lengths were calculated ~rom knowledge of triad
distribution and gross composition data.
B. Bulk Fluid Properties
1. Viscosity/temperature Relationships - These data
were obtained by Ubbelohde viscometric
measurements at temperatures of 70, 100, 130 and
210F.
2. Specific Gravity/Temperature Relationships - These
data were obtained by pyknometer measurements at
70, 130 and 210F.
3. Surface Tensio s - These values were obtained by
the De Nouy Ring Tensiometer method with the
measured 70F specific gravity being used for the
calculation correction along with the ring
calibration value (0.896) supplied by the
instrument manufacturer.
~q _
9~
94S4
C. Solution Pro erties
p
1. A ueous Solution Viscosities - These data were
q
obtained by incrementally adding water to 100 g
of the fluid, stirring with a Mag-mix for 5
minutes, and measuring the viscosity with a
Brookfield Synchro-Lectric Viscometer, Model RVF.
2. Heptane Solution Viscosities - Same procedure as
C.1. above using heptane in place of water.
3. Foaming and Foam Stabilities - These data were
obtained by agitating a 0.1% by weight aqueous
solution of the fluid for 30 seconds in a
calibrated Waring Blender, recording the initial
foam height, and then recording the times at which
the liquid level generated by drainage of the
foam reached the 100, 125, 150, 175, 200 and
225 ml. markings on the calibrated Blender.
4. Wetting characteristics - Wetting characteristics
were determined by the Draves Method (see American
Dyestuff Reporter 20, 201 (1931). In this method
the time required for a standard cotton ~kein~tta~h~d
to a standard lead weight by a standard copper
hook to sink in a 500 ml. graduate containing
a 0.1% aqueous solution of the fluid is measured;
the value reported in all Tables is the average
of 3 determinations.
5. Surface Tensions at Critical Micelle Concentrations -
These values were obtained by the graphic
intercept method off a semi-log plot of De Nouy Ring
Tensiometer values as a function of solution
concentration over the range from 0.1 to 0.0003125%.
1111594
9454
6. Cloud Points - The cloud point values were
obtained by heating 40 ml. of a 1% aqueous
solution of fluid contained in a large test tube
in a water bath. The solution was stirred
manually with a thermometer and the cloud point
was taken at the temperature at which the bulb
of the thermometer was essentially invisible
due to clouding.
EXAMPLES 1-4, A and B
Examples 1-4 describe a group of butanol-started
fluids prepared under various single-stage, simple feed
conditions as given in Table 1. These copolymers are all
of 50/50W~ ~ nominal composition. For comparative
purposes, Examples A and B illustrate control fluids
made under conventional block and random feed conditions.
Table 1 summarizes the reactor charges, feed tank charges
and feed rates used to prepare these fluids; Table 1
contains evaluation data and Figure 2 shows a plot of
aqueous solution viscosity characteristics.
The results summarized in Table 2 reveal the
similarity of these fluids in terms of most bul~
properties, but not in solution properties. Their
aqueous and organic solution viscosity behavior, their
aqueous solution foaming, wetting and surface tension
characteristics, and their cloud point temperatures all
indicate that these fluids are structurally different
from one another despite their comparable overall
compositions. The NMR monomer sequence length data,
where determined, confirms these structural differences.
- 31 -
94
9454
A comparison of the bulk appearances and
performance characteristics of Example 1 with the block
and random feed controls Examples A and B points up one
obvious advantage of power feed. The product of Example
1, although generally similar to the block feed control
(Example B) in solution properties, is a liquid at room
temperature whereas the block feed control product
(Example B) is a solid. The random feed control product
(Example A) while also a liquid, does not have the
surface activity chaxacteristics of the product of
Examples 1-4. This clearly demonstrates that the
present invention generates copolymers structurally
of a type intermediate between random and block products,
combining certain desirable features of both.
- 32 -
l~ liS94
9454
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1111~94
9454
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111~
9454
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--36--
llllS94
9454
EXAMPLES 5-8
These examples describe a group of butanol-started
fluids prepared under two-stage power feed conditions.
These copolymers are all of 50/50 w/w % nominal composition.
Table 3 gives pertinent data on reactor charges, feed tank
charges and feed rates while Table 4 covers evaluation
results and Figure 2 shows a plot of aqueous solution vis-
cosity characteristics. For purposes of comparison, the
group again includes control samples Examples A and B
representing conventional block and random feed preparations.
The results in Table 4 demonstrate clearly that
the performance characteristics of polyether copolymers
can be tailored conveniently by the present invention.
The aqueous solution viscosity behavior, for example, can
be altered all the way from a water-gelling liquid to one
which decreases continually in viscosity upon dilution.
In between these extremes lie fluids whose viscosity pro-
files upon water dilution are rather flat or even proceed
through maxima without reaching a gel condition. These
fluids can be readily made by the power feed process. Ac-
companying these changes are the indicated changes in other
; solution properties such as wetting, foaming, surface
tension and tolerance for organic liquids such as hydro-
carbons.
'
-37-
lillS94 9454
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llllS9~ 9454
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--39--
l~llS94
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1~11594
9454
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-- 42 --
1111594 9454
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-- 43 --
~llS94 9454
EXAMPLES 9 AND 10
The examples cover butanol-started fluids prepared
by two-stage feed processes wherein a uniform feed stage
precedes the gradient feed stage. These ethylene oxide-
propylene oxide copolymers are nominally of 50/50% w/w
composition. Reactor and feed tank charges and rates
are summarized in Table 5 and evaluation data are given
in Table 6.
The data in Table 6 reveal strikingly the influence
of this invention on fluid solution properties. Example 9
is highly efficient water-gelling fluid, a good solvent
for heptane, and an effective foam stabilizer, wetter, and
reducer of surface tension. Example 10, on the other
hand, is a water non-gelle~ a poor solvent for heptane,
and a totally ineffective foam stabilizer and wetter.
These remarkable property differences occur despite
the fact that these two fluids have, within limits of
experimental error, the same overall composition.
- ~4 -
1111~94 9454
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1111~;~ 9454
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1~11594 9~54
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-- 47 --
l~iS94 9454
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-- 49 --
llllS94 9454
EXAMPLES 11 AND 12
These examples cover allyl alcohol-started fluids
prepared under single-stage gradient feed conditions. For
comparative purposes, a sample of similar composition
prepared under random feed conditions is included. The
nominal overall compositions of these copolymers is 42%
ethylene oxide and 58% propylene oxide. The starter
solutions for these polymerizations were prepared by
treating allyl alcohol with potassium hydroxide and
azeotropically removing the water of neutralization with
benzene. Following completion of the drying, the benzene
was removed from the starter solution by distillation.
Table 7 summarizes the various charges and feed rates;
Table 8 contains evaluation data. Allyl alcohol-started
copolymers of this type find utility as starting
materials for the manufacture of siliconesurfactants for
flexible urethane foams.
The data in Table 8 demonstrates basic differences
between the random feed sample and the two gradient feed
samples of comparable composition. The two gradient feed
samples, while generally similar in properties due to
similarities in the feed profiles used in their preparation,
nevertheless do exhibit differences in their solution
property characteristics.
- 50 -
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