Note: Descriptions are shown in the official language in which they were submitted.
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METHOD FOR PRODUCING POLYMERS FROM VINYLAROMATIC COMPOUNDS
BY DISPERSION POLYMERISATION WITH THE ADDITION OF
LUBRICATING AGENTS
The invention relates to a process for preparing polymers of
vinylaromatic compounds in dispersion in the presence of a
dispersing auxiliary and a catalyst, obtainable from A) a
transition metal complex of subgroups II to VIII, B) a
ration-forming agent and C), if desired, an aluminum compound.
The polymers thereby obtainable can be used to produce fibers,
films and moldings.
Polymerizing styrene in the presence of metallocene catalyst
systems leads to polymers of high stereoregularity and is
described at length, for example, in EP-A 0 210 615. Because of
its high crystallinity, syndiotactic polystyrene has a very high
melting point of about 270°C, high rigidity and tensile strength,
dimensional stability, a low dielectric constant and high
chemical stability. The profile of mechanical properties is
retained even above the glass transition temperature.
In the metallocene-catalyzed polymerization of styrene, there is
frequently crystallization of the resulting syndiotactic
polystyrene starting at a level of only about 10~ conversion.
This leads firstly to the formation of deposits on the walls and
secondly to an extreme viscosity rise during the polymerization,
which makes handling and dissipation of the heat of reaction more
difficult, especially on the industrial scale.
To solve this problem a variety of techniques using special
reactors or extruders have been tried out. EP-A-0 535 582
describes a process for preparing syndiotactic polystyrene in a
stirred bed of solids, which is able to reduce the wall deposits
but not prevent them. The reactor has to be equipped with a
special stirrer in order to produce a homogeneous fluidized bed.
Temperature control is by way of partial evaporation of styrene
by reduced pressure, using a complex vacuum control system.
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1a
EP-A 0 584 646 and EP-A 0 389 939 describe the preparation of
syndiotactic polystyrene in self-cleaning twin-screw extruders or
compounders with no dead spaces. In both processes, owing to the
sudden rise in frictional forces at higher levels of conversion,
and to the motor output required for continued operation,
polymerization is carried out not to complete conversion but only
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to a level where the polymer powder, soaked with monomers, no
longer agglomerates in the course of subsequent processing steps.
In the case of anionic initiation, the technique of dispersion
polymerization is known. It is employed specifically to prepare
small polystyrene particles, as described for example in Journal
of Polymer Science, Part A, Polymer Chemistry, Vol. 34 (1996),
pages 2633 - 2649. Of critical importance is the selection of the
dispersing auxiliary for stabilizing the dispersion.
DE-A 43 30 969 describes a process for preparing polystyrene
mixtures by polymerizing styrene in an organic liquid in the
presence of a styrene-butadiene block copolymer and of a
metallocene catalyst system. For the preferred embodiment,
however, pressures of from 5 to 20 bar are required; otherwise
the resulting polymers have a very low molecular weight of around
30,000 g/mol.
It is an object of the present invention to provide a process for
preparing syndiotactic vinylaromatic polymers using metallocene
catalysts, which does not have the above disadvantages, the
reaction mixture being of low viscosity and increasing the
productivity of the catalyst.
We have found that this object is achieved by a process for
preparing polymers of vinylaromatic compounds in dispersion in
the presence of a dispersing auxiliary and a catalyst, obtainable
from
A) a transition metal complex of subgroups II to VIII,
B) a cation-forming agent and
C), if desired, an aluminum compound, wherein lubricants are
added.
Particularly suitable vinylaromatic compounds are those of the
formula I
R1-C=CH2
R6 R2
(I).
RS ~ w R3
R4
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where
R1 is hydrogen or C1-C4-alkyl,
R2 to R6 independently are hydrogen, C1-C12-alkyl, C6-C18-aryl or
halogen, or two adjacent radicals together are cyclic
groups having 4 to 15 carbons, for example C4-C8-cyclo-
alkyl, or fused ring systems.
It is preferred to employ vinylaromatic compounds of the formula
I in which
R1 is hydrogen.
Particularly suitable substituents Rz to R6 are hydrogen,
C1-C4-alkyl, chlorine or phenyl, biphenyl, naphthalene or
anthracene. Two adjacent radicals may also together be cyclic
groups having 4 to 12 carbons, so that compounds of the formula I
may also, for example, be naphthalene derivatives or anthracene
derivatives.
Examples of such preferred compounds are:
styrene, p-methylstyrene, p-chlorostyrene, 2,4-dimethylstyrene,
4-vinylbiphenyl, 2-vinylnaphthalene or 9-vinylanthracene.
It is also possible to employ mixtures of different vinylaromatic
compounds, in which case one component may also carry further
hydrocarbon radicals, such as vinyl, allyl, methallyl, butenyl or
pentenyl groups, preferably vinyl groups, on the phenyl ring. It
is preferred, however, to use only one vinylaromatic compound.
particularly preferred vinylaromatic compounds are styrene and
p-methylstyrene.
The preparation of vinylaromatic compounds of the formula I is
known per se and is described, for example, in Beilstein 5, 367,
474, 485.
Suitable dispersion auxiliaries are block copolymers having at
least one diene block B and at least one block S comprising a
copolymer of a vinylaromatic monomer of the formula (I) and
1,1-diphenylethylene or its aromatic ring-substituted
~~5~/49121 ~ 02334328 2000-12-05
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derivatives, including those substituted with alkyl of up to 22
carbons, as are described, for example, in DE-A 44 20 917.
Suitable examples are block copolymers with blocks S and B, of
the general structures (S-B)n, S-B-S, B-S-B, X[(S-B)n]m.
X[(B-S)n]m, X(S-B-S)m and X(B-S-B)m, where X is the radical of an
m-functional coupling agent or of an m-functional initiator, n is
an integer from 1 to 5 and m is an integer from 2 to 20.
All dienes are suitable in principle as the diene component for
the block B, although preference is given to those having
conjugated double bonds, such as butadiene, isoprene,
dimethylbutadiene and phenylbutadiene. The diene block may be
Partially or completely hydrogenated or unhydrogenated. The
molecular weights Mw of the blocks B are generally from 10,000 to
500,000, preferably from 50,000 to 350,000 and, with particular
preference, from 70,000 to 250,000, g/mol.
The blocks S consist of a copolymer of a vinylaromatic monomer of
the formula (I) and 1,1-diphenylethylene or its ring-substituted
derivatives, including those substituted with alkyl of up to 22
carbons, preferably of 1 to 4 carbons, such as methyl, ethyl,
isopropyl, n-propyl and n-, iso- or tert-butyl. Particular
Preference, however, is given to the use of unsubstituted
1,1-diphenylethylene itself. The proportion of diphenylethylene
in the block S is from 15 to 65~ by weight, preferably from 25 to
60% by weight. The molar ratio of the units derived from the
vinylaromatic monomer to units derived from 1,1-diphenylethylene
is generally in the range from 1 . 1 to 1 . 25, preferably from
1 . 1.05 to 1 . 15 and, with particular preference, in the range
from 1 . 1.1 to 1 . 10.
The copolymer block S is preferably random in composition and has
a molecular weight Mw of in general from 20,000 to 500,000,
preferably from 50,000 to 300,000. Particular preference is given
to a copolymer block S of styrene and 1,1-diphenylethylene.
The block ratio S to B is generally in the range from 90 . 10 to
20 . 80, particularly preferably from 90 . 15 to 65 . 35. The
block transitions can be either clean-cut or tapered. A tapered
transition is one where the adjacent blocks B and S may, in the
transition region, also contain monomers of the other block.
The block copolymers can be prepared by customary methods of
anionic polymerization, as described for example in M. Morton,
Anionic Polymerisation, Principles and Practice, Academic Press,
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New York 1983. The anionic polymerization is initiated by means
of organometallic compounds. Preference is given to compounds of
the alkali metals, especially of lithium. Examples of initiators
are lithium alkyls such as methyllithium, ethyllithium,
5 isopropyllithium, n-, sec- or tert-butyllithium. It is
particularly preferred to employ n- or s-butyllithium. Suitable
solvents are those which are inert toward the organometallic
initiator. Aliphatic or aromatic hydrocarbons are judiciously
used. Examples of suitable solvents are cyclohexane,
methylcyclohexane, benzene, toluene, ethylbenzene and xylene.
To influence the polymerization parameters, small amounts of
polar aprotic substances may be added to the solvent. Suitable
examples are ethers, such as diethyl ether, diisopropyl ether,
diethylene glycol dimethyl ether, diethylene glycol dibutyl ether
or, in particular, tetrahydrofuran, and also tertiary amines,
such as tetramethylethylenediamine or pyridine. The polar
cosolvent is added to the apolar solvent in a small amount of
from about 0.01 to 5% by volume. Particular preference is given
to tetrahydrofuran in an amount of from about 0.1 to 0.3% by
volume.
In a preferred embodiment of the novel process, at least one
branching monomer can be employed.
As branching monomers it is possible to use compounds of the
formula II
RbC= CHZ
IR,a-1p-M- (cH2)m--~~~ (II)
n
Rc
where
Ra is hydrogen, halogen or an inert organic radical of up to 20
carbons, where if p ; 2 each Ra can be identical or different
and two radicals Ra can form a 3- to 8-membered ring together
with the metal atom attached to them, and Ra can also be a
customary complex ligand if M is a transition metal,
Rb is hydrogen, C1-C4-alkyl or phenyl;
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R~ is hydrogen, C1-C4-alkyl, phenyl, chlorine or an unsaturated
hydrocarbon radical of 2 to 6 carbons;
M is C, Si, Ge, Sn, 8, Al, Ga, N, P, Sb, Ti, Zr, Hf, V, Nb, Ta,
Cr Mo W Mn Fe Ru Os Co Rh Ir Ni Pd Pt Cu Zn or
~ . . . . . . ~
Cd,
n is 2-6;
m is 0-20;
p is 0-4;
with the proviso that the sum of n + p corresponds to the valency
of M.
These monomers can be obtained, for example, by way of the
Grignard compounds of the chloro(alkyl)styrenes with the
corresponding carbon, metal or transition metal compounds, for
example the halogen compounds. Where M is silicon, germanium or
tin, for example, such reactions are described in K. Nakanishi,
J. Chem. Soc. Perkin Trans I, 1990, page 3362.
30
Particularly preferred branching monomer units are those of the
formula II in which M is carbon, silicon, germanium, tin or
titanium, because they are easy to obtain. The index m is
preferably from 0 to 8, particularly preferably from 0 to 4.
For example, the titanium-containing monomers of the formula IIa
RbC= CH2
[Ra-~p Ti--(CHZ)m (IIa)
n
Rc
and the titanium compound IIb
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RbC- CHZ
Ti (CHy)m (IIb)
4
Rc
where Ra, Rb, Rc, m, n and p are as defined above, can be employed
as branching monomers.
The inert organic radical or radicals Ra are not of great
importance to the process. Rather, they serve merely to satisfy
the free valencies of M and can be selected for ease of
availability. Examples of suitable radicals are aliphatic and
cycloaliphatic radicals, aryls, hetaryls and aralkyls. Aliphatic
radicals include alkyls, alkoxys, alkenyls or alkynyls having,
for example, from 1 to 2 or 20 carbons. Cycloaliphatic radicals
include cycloalkyls or cycloalkane radicals of 3 to 8 carbons.
Instead of a methylene in the alkyl or cycloalkyl it is also
possible for there to be an oxygen in ether function. Examples of
aryls are phenyls or naphthyls, it also being possible for two
phenyls to be connected by an oxygen. Examples of aralkyls are
those of 7 to 20 carbons that result from combination of a phenyl
with an alkyl. Examples of hetaryls are pyridyl, pyrimidyl and
furyl. These radicals can also be substituted further, for
example by alkyl, alkoxy, halogen, such as fluorine, chlorine or
bromine, cyano, nitro, epoxy, carbonyl, ester groups, amides, and
so on. Two of the radicals Ra can also form a 3- to 6-membered
ring with the atom M, for example where two radicals Ra form an
alkylene chain in which one or more CH2 groups may also have been
replaced by O in ether function.
If M is a transition metal, Ra can also be a customary a- or
-bonded complex ligand, such as ethylene, allyl, butadiene or
cyclopentadiene, mono- or polysubstituted cyclopentadienes, such
as methylcyclopentadiene or pentamethylcyclopentadiene, benzene,
cyclohexadiene, cycloheptatriene, cycloheptadiene,
cyclooctatetraene, cyclococtatriene, cyclooctadiene, carbonyl,
oxalato, cyano, isonitrile, fulminato-C, fulminato-O, cyanato,
dinitrogen, ethylenediamine, diethylenetriamine,
triethylenetetramine, ethylenediaminetetraacetate, nitrosyl,
nitro, isocyano, pyridine, a,a-bipyridyl, trifluorophosphane,
phosphane, diphosphane, arsane, acetylacetonato.
~
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Rb is with particular preference hydrogen or methyl. R~ is
hydrogen, C1-C4-alkyl such as methyl, ethyl, propyl, isopropyl,
n-butyl and the isomeric butyls, phenyl, chlorine or an
unsaturated hydrocarbon radical of 2 to 6 carbons such as vinyl,
allyl, methallyl, butenyl or pentenyl.
The branching monomer unit is judiciously employed in a molar
ratio of vinylaromatic monomer to branching unit of from
10,000,000 . 1 to 10 . 1.
Transition metal complexes of subgroups II to VIII, preferably
III to VIII, are used as catalyst component A). Very particular
preference is given to complexes of the transition metals of
subgroup IV, i.e. of titanium, zirconium or hafnium.
If the branching monomer unit of the formula II already has a
transition metal M, especially titanium, then depending on the
concentration used it can also simultaneously be employed as
catalyst component A in addition to its function as a branching
unit.
Particularly preferred catalyst components A) are metallocene
complexes, especially those of the formula III
Ril R7
Rl~~ \R$ (III).
R9
M(Z1) (ZZ) (Z3) (Z4) (Z5)
21 Z2 23 Z4 25
where
R~ to R11 are hydrogen, C1-Clo-alkyl, 5- to 7-membered cycloalkyl
which in turn can carry C1-C6-alkyls as substituents,
C6-C15-aryl or arylalkyl, and where two adjacent rad-
icals may if desired together be cyclic groups of 4 to
15 carbons, for example fused ring systems of 4 to 12
carbons, or are Si(R12)3,
where Rlz is C1-Clo-alkyl, C6-C15-aryl or C3-Clo-cycloalkyl,
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M is a metal from subgroups III to VI of the Periodic
Table of the Elements or is a metal of the lanthanide
series,
Z1 to Z5 are hydrogen, halogen, C1-Clo-alkyl, C6-C15-aryl,
C1-Clo-alkoxy or C1-C15-aryloxy
and
zi to z5 are 0, 1, 2, 3, 4 or 5, the sum zl+z2+z3+z4+z5 corre-
sponding to the valency of M minus 1.
Particularly preferred metallocene complexes of the formula III
are those in which
M is a metal from subgroup IV of the Periodic Table of
the Elements, i.e. titanium, zirconium or hafnium, es-
pecially titanium,
and
Z1 to Z5 are C1-Clo-alkyl, C1-Clo-alkoxy or halogen.
Examples of such preferred metallocene complexes are:
pentamethylcyclopentadienyltitanium trichloride,
pentamethylcyclopentadienyltitanium trimethyl and
pentamethylcyclopentadienyltitanium trimethylate.
It is also possible to employ those metallocene complexes
described in EP-A 584 646.
Mixtures of different metallocene complexes can also be used.
Complex compounds of this kind can be synthesized by methods
known per se, preference being given to reacting the
correspondingly substituted, cyclic hydrogen anions with halides
of titanium, zirconium, hafnium, vanadium, niobium or tantalum.
Examples of appropriate preparation techniques are described,
inter alia, in Journal of Organometallic Chemistry, 369 (1989),
359-370.
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As compound 8 which forms cations, especially metallocenium ions,
the catalyst systems can comprise open-chain or cyclic alumoxane
compounds.
5 Suitable examples are open-chain or cyclic alumoxane compounds of
the formula IV or V
R13\
Al-f-O-Al-jk R13 (IV)
10 R13~
R13
or
o-Al-~ (V).
R13
where R13 is C1-C4-alkyl, preferably methyl or ethyl, and k is an
integer from 5 to 30, preferably from 10 to 25.
25
The preparation of these oligomeric alumoxane compounds is
usually carried out by reacting a solution of a trialkylaluminum
with water and is described, inter alia, in EP-A 284 708 and US-A
4,794,096.
In general, the oligomeric alumoxane compounds obtained are in
the form of mixtures of both linear and cyclic chain molecules of
different lengths, so that k is to be regarded as an average
value. The alumoxanes may also be present in a mixture with other
metal alkyls, preferably with aluminum alkyls.
It has been found advantageous to use the metallocene complexes
and the oligomeric alumoxane compound in amounts such that the
atomic ratio between aluminum from the oligomeric alumoxane and
the transition metal from the metallocene complexes is in the
range from 10:1 to 106:1, in particular from 10:1 to 104:1.
As compound B) forming metallocenium ions it is also possible to
employ coordination complex compounds selected from the group
consisting of strong, neutral Lewis acids, ionic compounds having
Lewis-acid cations and ionic compounds having Bronsted acids as
cations.
preferred strong neutral Lewis acids are compounds of the formula
VI
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MiX1X2X3 (VI)
where
M1 is an element from main group III of the Periodic
Table, especially B, A1 or Ga, preferably B,
Xl,Xz and X3 are hydrogen, C1-Cio-alkyl, C6-C15-aryl, alkylaryl,
arylalkyl, haloalkyl or haloaryl each of 1 to 10 car-
bons in the alkyl and 6 to 20 carbons in the aryl, or
are fluorine, chlorine, bromine or iodine, especially
haloaryls, preferably pentafluorophenyl.
Particular preference is given to compounds of the formula VI in
which X1, XZ and X3 are identical; preferably
tris(pentafluorophenyl)borane. These compounds and processes for
their preparation are known per se and are described, for
example, in WO 93/3067.
Suitable ionic compounds having Lewis-acid cations are compounds
of the formula VII
((Ya+)Q1Q2~..Qz)d+ (VII)
where
Y is an element from main groups I to VI or subgroups I
to VIII of the Periodic Table,
Q1 to Qz are radicals with a single negative charge, such as
C1-C28-alkyl, C6-C15-aryl, alkylaryl, arylalkyl, ha-
loalkyl or haloaryl each having 6 to 20 carbons in
the aryl and 1 to 28 carbons in the alkyl,
C1-Cla-cycloalkyl, which can be unsubstituted or sub-
stituted by C1-Cio-alkyls, or are halogen, C1-Cze-al-
koxy, C6-C15-aryloxy, silyl or mercaptyl, such as
trimethylsilyl,
a is an integer from 1 to 6,
z is an integer from 0 to 5, and
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0050/49121
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d corresponds to the difference a - z, but is greater
than or equal to 1.
Particular suitability is possessed by carbonium cations, oxonium
cations and sulfonium cations, and also cationic transition metal
complexes. Particular mention may be made of the triphenylmethyl,
silver and 1,1'-dimethylferrocenyl cations.
They preferably have noncoordinating counterions, especially
boron compounds, as also mentioned in WO 91/09882, preferably
tetrakis(pentafluorophenyl) borate.
Ionic compounds with Bronsted acids as cations and preferably
also with likewise noncoordinated counterions are specified in WO
93/3067; a preferred cation is N,N-dimethylanilinium.
It has been found to be particularly appropriate if the molar
ratio of boron from the compound that forms metallocenium ions to
transition metal from the metal complex is in the range from
0.1:1 to 10:1, in particular from 1:1 to 5:1.
The catalyst system employed in the novel process may include as
component C) an aluminum compound, for example of the formula
VIII
A1R14R15R16 ( VIII ) ,
where
R14 to R16 are hydrogen, fluorine, chlorine, bromine, iodine or
C1-C12-alkyl, preferably C1-C$-alkyl.
Preferably, R14 to R15 are identical and are C1-C6-alkyl, such as
methyl, ethyl, isobutyl or n-hexyl, and R16 is hydrogen.
The content of component C) in the catalyst system is preferably
from 1 . 2000 to 1 : 1, in particular from 1 . 800 to 1 . 10
(molar ratio of transition metal from III to A1 from VIII).
As solvents for the metallocene complexes it is common to employ
aromatic hydrocarbons, preferably those having 6 to 20 carbons,
and especially xylenes, toluene and ethylbenzene and mixtures
thereof.
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The metallocene complexes can be employed with or without a
support.
Examples of suitable support materials are silica gels,
preferably those of the formula Si02 ~ bA1203, where b is a number
from 0 to 2, preferably from 0 to 0.5; i.e. essentially
alumosilicates or silicon dioxide. The supports preferably have a
particle diameter of from 1 to 200 ~.m, in particular from 30 to
80 Eun. Such products are obtainable commercially, for example as
silica gel 332 from Grace.
Further supports include finely divided polyolefins, for example
finely divided polypropylene or polyethylene, and also
p°lyethylene glycol, polybutylene terephthalate, polyethylene
terephthalate, polyvinyl alcohol, polystyrene, syndiotactic
polystyrene, polybutadiene, polycarbonates and copolymers
thereof .
The molar ratio of transition metal catalyst A) to vinylaromatic
monomer is generally from 1 . 1000 to 1 . 10,000,000, but
preferably from 1 . 2000 to 1 . 1,000,000.
The process according to the invention is conducted as a
dispersion polymerization. The dispersing medium employed may
judiciously comprise aliphatic hydrocarbons, especially those of
4 to 10 carbon atoms, or hydrocarbon mixtures. Examples are
butane, pentane, hexane and heptane. The concentration of the
monomers that are to be polymerized in the dispersion medium is
in general from 5 to 65 percent by volume, preferably from 10 to
50 % by volume.
The dispersing auxiliary is preferably used in an amount of from
0.1 to 10% by weight, particularly preferably from 1 to 8% by
weight, based on the vinylaromatic compound employed. It is
judiciously dissolved in the vinylaromatic monomer that is to be
polymerized.
Suitable lubricants are organic and inorganic compounds. Examples
of organic lubricants are lubricating oils such as mineral oils,
i.e. liquid products obtained from petroleum, hard-coal tar or
lignite tar, such as benzines, white oils, petroleum or gas oils,
and also polyether oils, ester oils and silicone oils, or else
lubricant greases. Examples of inorganic lubricants are
molybdenum(IV) sulfide or titanium(IV) sulfide. Further suitable
lubricants are glyceryl esters or fatty acids. Preference is
given to hydrocarbons such as liquid paraffins, other paraffins,
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polar and nonpolar polyethylene waxes, alcohols such as cetyl
alcohol or stearyl alcohol, carboxylic acids such as lauric acid,
palmitic acid or stearic acid, metal salts of carboxylic acids,
such as Ca stearate, 2n stearate, carboxamides and carboxylic
esters such as ethyl stearate, n-butyl stearate or distearyl
phthalate. Further lubricants are described, for example, in the
Taschenbuch der Kunststoff-Additive, edited by Gachter and Miiller
for the Carl Hanser Verlag, 2nd Edition, page 309 to 327.
Further lubricants which can be employed are polymers such as
polystyrene, preferably low molecular mass polystyrene having
molecular weights MW of from 2000 to 40,000, polyethylene,
polypropylene, or else copolymers of ethylene with other
1-alkenes.
Particular preference is given to distearyl phthalate and mineral
oil hydrocarbons such as white oils. Mixtures of different
lubricants can also be employed.
25
The amount of lubricants can vary within wide ranges, with
preference being given to from 0.01 to 50% by weight, in
particular from 0.1 to 40% by weight and, with particular
preference, from 0.2 to 10% by weight based on monomer employed.
The lubricants are preferably added, prior to the addition of the
transition metal complex, to the vinylaromatic compound, the
dispersant, the dispersing medium, the cation-forming agent and,
if appropriate, the aluminum compound.
The polymerization conditions are not critical. Polymerization is
preferably conducted at from 50 to 100°C under a pressure of from
0.05 to 30 bar, preferably from 0.1 to 20 bar. The polymerization
is generally at an end after from 0.5 to 10 hours. It can be
terminated by adding protic compounds, for example methanol, and
the dispersion medium can be removed by filtration or evaporation
and recycled to the process.
The novel process is technically simple and permits the
preparation of vinylaromatic polymers having a high syndiotactic
content with low viscosities of less than 5 mPas with high
catalyst productivity. Furthermore, the polymers are obtained in
particulate form. The resultant polymers are suitable for
producing fibers, films and moldings.
0050/49121 ~ 02334328 2000-12-05
Examples
Purifying 1,1-diphenylethylene (DPE)
5 Crude DPE (Aldrich or prepared by reacting phenylmagnesium
bromide with acetophenone, acetylating with acetic anhydride and
thermally eliminating the acetic acid) is distilled to 99.8%
purity on a column having at least 50 theoretical plates
10 (spinning band column; for larger quantities, a column with
Sulzer packing). The distillate, which is usually pale yellow, is
filtered through a 20 cm alox column (Woelm alumina for
chromatography, anhydrous), titrated with 1.5 N sec-butyllithium
until there is a strong red coloration, and distilled over under
15 reduced pressure (1 mbar). The resulting product is completely
colorless and can be employed directly in the anionic
polymerization.
Purifying the monomers and solvent
The cyclohexane (H) employed as solvent was dried over anhydrous
alumina and titrated with the adduct of sec-butyllithium and
1,1-diphenylethylene until a yellow coloration was obtained. The
butadiene (Bu) was distilled off from triisobutyaluminum, the
1,1-diphenylethylene (DPE) from sec-butyllithium (s-BuLi). A 0.5
molar solution of s-BuLi in cyclohexane was used as initiator.
Styrene (S) was dried over alumina directly before use.
All polymerizations were conducted under purified nitrogen with
rigorous exclusion of air and moisture. The reactors were
pretreated for a number of hours with a solution of
1,1-diphenylethylene and sec-butyllithium in cyclohexane under
reflux before being filled.
In the Examples below, Bu is 1,3-butadiene, S is styrene and DPE
is 1,1-diphenylethylene. Also, the proportions are by weight.
Preparing a Bu-S/DPE block copolymer
Dispersant D1
7.1 1 of cyclohexane and a few drops (about 2 ml) of DPE were
charged to a 10 1 stirred reactor and titrated with a 0.278 molar
sec-butyllithium solution until the mixture began to take on a
red coloration. Following the addition of 15.1 ml (4.2 mmol) of
the 0.278 molar sec-butyllithium solution, 1.6 1 (19.4 mol)) of
0050/49121 ~ 02334328 2000-12-05
16
1,3-butadiene were added in portions (100 ml) over the course of
one hour at 70°C and the mixture was polymerized at 70°C for a
further hour. The molecular weights of the resulting
polybutadiene block were determined on a sample by means of gel
permeation chromatography (GPC) with polybutadiene calibration: Mw
- 248,000 g/mol, Mw/Mn = 1.28, M (peak maximum) = 226,000 g/mol.
To the resulting polybutadiene block there were added, in
succession at an interval of 15 minutes, 98.3 ml (0.56 mol) of
1,1-diphenylethylene and 259 ml (2.25 mol) of styrene, and
polymerization was continued at 70°C for 5 hours more. After the
reaction had subsided, the reaction mixture was titrated with
ethanol until it became colorless and was acidified with
C02/water. The colorless solution was freed from solvent under
reduced pressure in a devolatilizing extruder, and the product
was granulated.
GPC {polybutadiene calibration): two peaks: 1st peak (20%) M
(peak maximum) = 32,000 g/mol; 2nd peak (80%): peak maximum at
260,000 g/mol.
Examples 1 to 4
532 ml of pentane and a mixture of 2.61 g of dispersant D1 in
104.2 g (1 mol) of styrene were introduced with stirring into an
autoclave which had been rendered intert [sic] with argon.
8.16 ml of a 1.53 molar solution of methylaluminoxane (MAO) in
toluene (obtained from Witco) and 2.08 ml of a 1.0 molar solution
of diisobutylaluminum hydride (DIBAH) in cyclohexane (obtained
from Aldrich) were added. Prior to the addition of the transition
metal complex, a defined amount of lubricant was then added to
this mixture. Subsequently, 1.5 1 of hydrogen were injected at
room temperature and the reaction solution was heated to 80~C.
Then 1.14 mg (0.05 mmol) of pentamethylcyclopentadienyltitanium
trimethyl Cp*TiMe3 were added, and an internal pressure of 7.5 bar
developed. After 2 hours, the polymerization was terminated by
adding 10 ml of methanol. After cooling to room temperature, a
homogeneous, readily flowing suspension was obtained. The
resultant polymer was washed with methanol and dried under
reduced pressure at 50~C.
The molecular weights Mw and Mn were determined by means of
high-temperature gel permetion [sic] chromatography GPC (135~C,
1,2,4-trichlorobenzene, polystyrene standard). The syndiotactic
content was determined by means of 13C-NMR spectroscopy. The
particle sizes lay within the range from 2 to 10 dun and were
determined on a sample, slurried in immersion oil, between two
0050/49121 ~ 02334328 2000-12-05
17
planar glass plates under the transition microscope (Axiophot
from Carl Zeiss).
The conversion is based on the amount of styrene employed.
Comparative Experiment C1
Polymerization was carried out as in Examples 1 to 4 but without
the addition of a lubricant.
Ex. Lubricant Mw Vis- Con- Productivity
[g/mol] Mi,,/Mncosity ver- [kg s-Ps/gTi)
[mPas] sion
(%]
1 0.5% by 422,800 1.9 2.99 67 69.2
wt.
Winog 60
2 5% by wt. 278,500 2.0 4.81 73 82.1
Winog 60
3 1% by wt. 296,700 2.0 2.43 69 49.7
distearyl
phthalate
4 8% by wt. 301,400 2.2 4.01 71 66.5
Winog 70
C1 - 321,500 2.1 2.35 34 15.4
The syndiotacticity of the polymers was >_ 95%.
The percentages by weight for the lubricants are based on styrene
monomer employed.
WinogOO60 and Winog070 are white oils (mineral oil hydrocarbons)
to DAB [German Pharmacopeia] 9 from Wintershall Mineralol GmbH.
Winog 70 has a dynamic viscosity (to DIN 51562] of 136 mPas, a
molecular weight in the range from 400 to 550, and a density of
0.865 g/cm3.
Winog 60 has a dynamic viscosity (to DIN 51562] of 180 mPas and a
density of 0.863 g/cm3.
45
