U.S. patent application number 14/368645 was filed with the patent office on 2014-12-04 for propylene random copolymer.
The applicant listed for this patent is BOREALIS AG. Invention is credited to Torvald Vestberg, Ville Virkkunen.
Application Number | 20140357816 14/368645 |
Document ID | / |
Family ID | 47471822 |
Filed Date | 2014-12-04 |
United States Patent
Application |
20140357816 |
Kind Code |
A1 |
Virkkunen; Ville ; et
al. |
December 4, 2014 |
PROPYLENE RANDOM COPOLYMER
Abstract
Propylene random copolymers with low randomness and being free
of from catalyst originating phthalates.
Inventors: |
Virkkunen; Ville; (Helsinki,
FI) ; Vestberg; Torvald; (Porvoo, FI) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
BOREALIS AG |
Vienna |
|
AT |
|
|
Family ID: |
47471822 |
Appl. No.: |
14/368645 |
Filed: |
December 19, 2012 |
PCT Filed: |
December 19, 2012 |
PCT NO: |
PCT/EP2012/076118 |
371 Date: |
June 25, 2014 |
Current U.S.
Class: |
526/123.1 |
Current CPC
Class: |
C08F 4/50 20130101; C08F
210/06 20130101; C08F 210/06 20130101; C08F 210/06 20130101; C08F
210/06 20130101; C08F 210/06 20130101; C08F 4/16 20130101; C08F
4/651 20130101; C08F 210/16 20130101; C08F 4/6548 20130101; C08F
4/6555 20130101; C08F 2500/12 20130101 |
Class at
Publication: |
526/123.1 |
International
Class: |
C08F 4/50 20060101
C08F004/50; C08F 4/16 20060101 C08F004/16 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 30, 2011 |
EP |
11196169.4 |
Claims
1. Propylene random copolymers comprising, a) a comonomer selected
from ethylene, C.sub.4-C.sub.20-alpha olefin, and any combination
thereof b) a comonomer content in the range of 1.5 to at most 5.0
wt % c) a randomness in the range of 60% to at most 80% d) a xylene
soluble (XS) content of 2 to <12 wt %, the propylene random
copolymers being free of from catalyst originating phthalates.
2. Propylene random copolymers according to claim 1, wherein a) the
comonomer is ethylene b) the comonomer content is in the range of
2.0 to 4.9 wt % c) the randomness is in the range of 65% to 80% d)
a xylene soluble (XS) content of 3.0 to <11.5 wt %, the
propylene random copolymers being free of from catalyst originating
phthalates.
3. Process for preparing propylene random copolymers according to
claim 1, said propylene random copolymers being produced by
copolymerising propylene with a comonomer selected from ethylene,
C.sub.4-C.sub.20-alpha olefin, and any combination thereof using a
catalyst system comprising a co-catalyst and optionally an external
electron donor and an olefin polymerisation catalyst component in
the form of solid particles being produced by a) preparing a
solution of at least one alkoxy compound (Ax) being the reaction
product of at least one compound of a Group 2 metal with at least a
monohydric alcohol (A) in an organic liquid reaction medium, b)
adding said solution to at least one compound of a transition metal
and c) preparing the solid catalyst component particles, wherein an
internal electron donor selected from benzoates, alkylene glycol
dibenzoates, maleates, 1-cyclohexene-1,2-dicarboxylic dialkylester,
and 1,3-ethers, or a mixture of any selected donors, or a
corresponding precursor is added at any step prior to step c).
4. Process according to claim 3, wherein the internal donors are
selected from a) benzoates of the formula (I) ##STR00006## with R
being a linear or branched C.sub.1-C.sub.12-alkyl group, preferably
a linear or branched C.sub.2-C.sub.10-alkyl group, more preferably
a linear or branched C.sub.4-C.sub.9-alkyl group and most
preferably a branched C.sub.6-C.sub.8-alkyl group and R' being H or
a linear or branched C.sub.1-C.sub.12-alkyl group, preferably a
linear or branched C.sub.2-C.sub.10-alkyl group more preferably a
linear or branched C.sub.4-C.sub.8-alkyl group, whereby the alkyl
group can contain one or more heteroatoms selected from O, N or S,
preferably O or N, more preferably O, in the alkyl chain, or can be
substituted by one or more substituents selected from .dbd.O,
halogen, like chlorine, fluorine or bromine, or optionally
substituted C.sub.6-C.sub.14-aryl, b) alkylene glycol dibenzoates
of the formula (II) ##STR00007## with n being 1 or 2, if n=1 then
R.dbd.CH.sub.3 and if n=2 then R.dbd.H, c) maleates of formula
(III) ##STR00008## with R.sub.1 and R.sub.2 being the same or
different and being a linear or branched C.sub.1-C.sub.12-alkyl
group, preferably a linear or branched C.sub.1-C.sub.8-alkyl group,
more preferably a linear or branched C.sub.1-C.sub.4-alkyl group
and most preferably ethyl, whereby R.sub.1 and R.sub.2 are
preferably the same and with R being H or a linear, branched or
cyclic C.sub.1 to C.sub.12-alkyl, preferably a branched or cyclic
C.sub.3 to C.sub.8-alkyl, d) 1-cyclohexene-1,2-dicarboxylic
dialkylester of formula (IV) ##STR00009## with R.sub.1 and R.sub.2
can be identical or different and can be a linear or branched
C.sub.5-C.sub.20-alkyl, and e) 1,3-diethers of formula (V) or (VI)
##STR00010## wherein in formula (V) and (VI) R.sub.1 and R.sub.2
are the same or different and can be a linear or branched
C.sub.1-C.sub.12-alkyl, or R.sub.1 with R.sub.5 and/or R.sub.2 with
R.sub.6 can form a ring with 4 to 6 C-atoms, R.sub.3 and R.sub.4 of
formula (V) are the same or different and can be H or a linear or
branched C.sub.1-C.sub.12-alkyl or R.sub.3 and R.sub.4 can form
together a ring with 5 to 10 C-atoms, which can be part of an
aliphatic or aromatic polycyclic ring system with 9 to 20 C atoms,
R.sub.5 and R.sub.6 in formula (V) are the same or different and
can be H or a linear or branched C.sub.1-C.sub.12-alkyl or can form
together an aliphatic ring with 5 to 8 C-atoms, and R.sub.51,
R.sub.61 and R.sub.7 in formula (VI) are the same or different and
can be H or a linear or branched C.sub.1-C.sub.12-alkyl or two or
three of R.sub.51, R.sub.61 and R.sub.7 can form together with
C.sub.1 to C.sub.3 an aromatic ring or ring system with 6 to 14
C-atoms, or mixtures therefrom.
5. Process according to claim 3, wherein the alkoxy compound (Ax)
is a reaction product of at least one compound of Group 2 metal and
a monohydric alcohol (A) or a reaction product of at least one
compound of Group 2 metal and a mixture of monohydric alcohol (A)
with a further alcohol (B) comprising in addition to the hydroxyl
moiety at least one further oxygen bearing group being different to
a hydroxyl moiety.
6. Process according to claim 3, wherein in addition to the at
least one alkoxy compound (Ax) at least one alkoxy compound (Bx)
being the reaction product of at least one compound of Group 2
metal and an alcohol (B) comprising in addition to the hydroxyl
moiety at least one further oxygen bearing group being different to
a hydroxyl moiety.
7. Process according to claim 3, wherein the monohydric alcohols
(A) are those of formula ROH in which R is a linear or branched
C.sub.1-C.sub.20 alkyl.
8. Process according to claim 5, wherein in the alcohol (B) the one
further oxygen bearing group is an ether moiety.
9. Process according to claim 5, wherein the alcohol (B) is a
C.sub.2 to C.sub.4 glycol monoether, wherein the ether moiety
comprises from 2 to 18 carbon atoms.
10. Process according to claim 3, wherein said Group 2 metal is
magnesium.
11. Process according to claim 3, wherein said transition metal is
a Group 4 metal and/or Group 5 metal.
12. Process according to claim 3, wherein the preparation of the
olefin polymerisation catalyst component in form of solid particles
comprises the steps of (a1) preparing a solution (S1) of at least
one alkoxy compound (Ax), being a reaction product of at least one
compound of a Group 2 metal with at least a monohydric alcohol (A)
and an electron donor as defined in claim 3 or 4, or a
corresponding precursor thereof in an organic liquid reaction
medium (OM1), (b1) combining said solution (S1) with at least one
transition metal compound (CT), and (c1) precipitating said
catalyst component in the form of a solid particle, and (d1)
recovering the solidified particles of the olefin polymerisation
catalyst component.
13. Process according to claim 12, wherein the addition of solution
(S1) to the at least one transition metal compound (CT) in step
(b1) is done at a temperature range of 50 to 110.degree. C., at
which temperature the at least one transition metal compound (CT)
is in a liquid form, resulting in the precipitation of said solid
catalyst components, whereby a surfactant can be added in step (a1)
or step (b1).
14. Process according to claim 12, wherein the solution (S1) is
mixed with at least one transition metal compound (CT) in liquid
form at a temperature of about -20.degree. C. to about 30.degree.
C. and precipitating the solid catalyst components by subsequently
slowly raising the temperature to a temperature range of 50 to
110.degree. C., whereby the rate of temperature increase is in the
range from 0.1.degree. C. to 30.degree. C. per minute and whereby a
surfactant is added to the solution (S1) before step (b1).
15. Process according to claim 3, wherein the preparation of the
catalyst component in form of solid particles comprises the steps
of (a2) preparing a solution of at least one alkoxy compound (Ax),
being a reaction product of at least one compound of a Group 2
metal with at least a monohydric alcohol (A) and an electron donor
of formula (I) or a precursor thereof in an organic liquid reaction
medium, (b2) adding said solution of said alkoxy compound (Ax) to
at least one compound of a transition metal to produce an emulsion,
wherein the dispersed phase of which is in the form of droplets and
contains more than 50 mol % of the Group 2 metal in said alkoxy
compound (Ax), (c2) agitating the emulsion in order to maintain the
droplets of said dispersed phase within said predetermined average
size range of 2 to 500 .mu.m, (d2) solidifying said droplets of the
dispersed phase, (e2) recovering the solidified particles of the
olefin polymerisation catalyst component.
16. Process for preparing propylene random copolymers according to
claim 3, wherein said co-catalyst is an alkyl aluminum
co-catalyst.
17. Process according to claim 4, wherein said aromatic ring or
ring system has 10 to 14 C-atoms.
18. Process according to claim 11, wherein said transition metal is
Ti.
19. Process according to claim 13, wherein the rate of temperature
increase is in the range from 0.5 to 10.degree. C. per minute.
Description
[0001] The present invention relates to specific propylene random
copolymers prepared by copolymerisation of propylene with a
comonomer, the comonomer being ethylene or an alpha-olefin
comprising at least four carbon atoms, in particular ethylene, the
propylene random copolymers being free of from catalyst originating
phthalates and showing low randomness.
[0002] Propylene homopolymers have high resistance to heat and
chemicals as well as beneficial mechanical properties. However,
other properties of propylene homopolymers such as impact strength,
in particular at low temperature, flexibility, clarity or haze need
to be improved for specific applications.
[0003] It is known that mechanical properties such as impact
strength or optical properties can be improved by copolymerising
propylene with ethylene or other alpha-olefins. If these comonomers
are randomly distributed within the polymeric chain, a propylene
random copolymer is obtained.
[0004] Propylene random copolymers, in particular with the
comonomer being ethylene, have found widespread applications for
example in the production of polymer films, of articles produced by
blow moulding or injection moulding, of fibres and of pipes.
[0005] The randomness, which has important effects on the final
properties of the random copolymer, is defined as follows:
Randomness (for random propylene ethylene copolymers)=random
ethylene (--P-E-P--) content/the total ethylene
content.times.100%.
[0006] The used comonomers, preferably ethylene are inserted
randomly between the propylene molecules in the polymer chain and
their incorporation level can be up to 10 wt %. The comonomer
incorporation results in defects in the regularity of chain
configuration causing changes in physical properties. Such polymer
chains are more flexible so their flexural modulus and thus
stiffness is reduced.
[0007] Unfortunately for several applications stiff random
copolymers are needed, as for example for pipes.
[0008] Thus there is still the need for new propylene random
copolymers which have lower randomness and therefore higher
stiffness compared to known propylene random copolymers.
[0009] A further aspect of the present invention is to avoid the
presence of substances which are considered as potential harmful
compounds regarding health as well as environmental aspects. One
class of substances which have been considered as potential harmful
compounds is phthalates, which have been commonly used as internal
electron donors in Ziegler-Natta type catalysts. Although the
amount of these phthalate compounds, used as internal donors in
catalysts, in the final polymer is very small, it is still
desirable to find alternative propylene random copolymers
containing no catalyst originating phthalates and showing the
desired polymer properties, namely low randomness.
[0010] Accordingly it is one object of the present invention to
provide propylene random copolymers being free of from catalyst
originating phthalates and having lower randomness compared to
known Ziegler-Natta catalysts using phthalate compounds as internal
donor.
[0011] Additionally it is one further object of the present
invention to provide a method for preparing such random copolymers
being free of from catalyst originating phthalates and having
desired low randomness using special solid catalyst components
prepared in different ways (e.g. precipitation or
emulsion/solidification method) but with a common mechanism and
without the use of phthalates as internal electron donor.
DESCRIPTION OF THE INVENTION
[0012] Accordingly the present invention provides new propylene
random copolymers as defined in claim 1.
[0013] Furthermore the present invention provides a process for
preparing such propylene random copolymers as defined in claim
1.
[0014] Thus the present invention provides propylene random
copolymers having [0015] a) a comonomer selected from ethylene,
C.sub.4-C.sub.20-alpha olefin, and any combination thereof [0016]
b) a comonomer content in the range of 1.5 to at most 5.0 wt %
[0017] c) a randomness in the range of 55% to at most 95% [0018] d)
a xylene soluble (XS) content of 2 to <12 wt % and the propylene
random copolymers being free of from catalyst originating
phthalates.
[0019] Furthermore the present invention provides a process for
preparing such propylene random copolymers by copolymerising
propylene with a comonomer selected from ethylene,
C.sub.4-C.sub.20-alpha olefin, and any combination thereof using a
catalyst system comprising a co-catalyst, preferably an alkyl
aluminum co-catalyst and optionally an external electron donor and
an olefin polymerisation catalyst component in the form of solid
particles being produced by [0020] a) preparing a solution of at
least one alkoxy compound (Ax) being the reaction product of at
least one compound of a Group 2 metal with at least a monohydric
alcohol (A) in an organic liquid reaction medium, [0021] b) adding
said solution to at least one compound of a transition metal and
[0022] c) preparing the solid catalyst component particles, wherein
an internal electron donor selected from benzoates, alkylene glycol
dibenzoates, maleates, 1-cyclohexene-1,2-dicarboxylic dialkylester,
and 1,3-diethers, or a mixture of any selected donors, or a
corresponding precursor is added at any step prior to step c).
[0023] Preferred embodiments are described in dependent claims as
well in the following description.
[0024] The invention will be described in the following in greater
detail, referring to the particular preferred embodiments.
[0025] The propylene random copolymers according to the invention
comprise units derived from propylene and at least one comonomer
selected from ethylene and C.sub.4-C.sub.20 alpha-olefins,
preferably at least ethylene or a C.sub.4-C.sub.10
alpha-olefin.
[0026] Accordingly the random propylene copolymers (R--PP) comprise
units derived from propylene and at least one comonomer selected
from the group consisting of ethylene, C.sub.4 alpha-olefin,
C.sub.5 alpha-olefin, C.sub.6 alpha-olefin, C.sub.7 alpha-olefin,
C.sub.8 alpha-olefin, C.sub.9 alpha-olefin and C.sub.10
alpha-olefin. More preferably the random propylene copolymers
(R--PP) comprise units derived from propylene and at least one
comonomer selected from the group consisting of ethylene, 1-butene,
1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene and 1-decene,
wherein ethylene, 1-butene and 1-hexene are preferred.
[0027] It is in particular preferred that the random propylene
copolymers (R--PP) consist of units derived from propylene and
ethylene.
[0028] The amount of units derived from C.sub.2-C.sub.20
alpha-olefins other than propylene in the random propylene
copolymers (R--PP) is in the range of 1.5 to at most 5.0 wt %,
preferably 2.0 to 4.9 wt %, more preferably 2.5 to 4.8 wt %, still
more preferably 3.0 to 4.7 wt %.
[0029] One requirement in the present invention is that units
derived from C.sub.2-C.sub.20 alpha-olefins other than propylene
within the propylene copolymer s(R--PP) are randomly distributed.
The randomness indicates the amount of isolated comonomer units,
i.e. those which have no other comonomer units in the neighbour,
compared to the total amount of comonomers in the polymer
chain.
[0030] In a preferred embodiment, the randomness of the random
propylene copolymers (R--PP) is in the range 55% to at most 95%,
preferably 60% to 90%, more preferably in the range of 65% to 85%
and still more preferably in the range of 70% to 80%.
[0031] In addition the randomness of the phthalate free random
propylene copolymers is--at a given comonomer content--at least 3%
lower than the randomness of random propylene copolymers prepared
by comparable Ziegler-Natta catalysts comprising a phthalate
compound as internal donor.
[0032] Further it is appreciated that the xylene soluble (XS)
content of the random propylene copolymers (R--PP) is rather
low.
[0033] Accordingly the random propylene copolymers (R--PP) have a
xylene cold soluble fraction (XCS) measured according to ISO 6427
(23.degree. C.) in the range of 2.0 to <12.0 wt %, preferably in
the range of 3.0 to <11.5 wt.-% and more preferably in the range
of 4.0 to <11.0 wt %.
[0034] The random propylene copolymers are further characterized in
that they are free of any phthalate which originates from the
catalyst used during preparation of the random propylene
copolymers.
[0035] The random propylene copolymers of the present invention are
characterized through an excellent balance of comonomer content,
randomness and xylene soluble content, which makes them suitable
for use in many applications where stiffer copolymers are needed,
like for example pipes.
[0036] The random propylene copolymer (R--PP) can be unimodal or
multimodal, like bimodal in view of the molecular weight
distribution and/or the comonomer content distribution.
[0037] When the random propylene copolymer (R--PP) is unimodal with
respect to the molecular weight distribution and/or comonomer
content, it may be prepared in a single stage process e.g. as
slurry or gas phase process in a slurry or gas phase reactor.
Preferably, the unimodal random propylene copolymer (R--PP) is
polymerised as a slurry polymerisation.
[0038] Alternatively, the unimodal the random propylene copolymer
(R--PP) may be produced in a multistage process using at each stage
process conditions which result in similar polymer properties.
[0039] The expression "multimodal" or "bimodal" used herein refers
to the modality of the polymer, i.e. [0040] the form of its
molecular weight distribution curve, which is the graph of the
molecular weight fraction as a function of its molecular weight, or
more preferably [0041] the form of its comonomer content
distribution curve, which is the graph of the comonomer content as
a function of the molecular weight of the polymer fractions.
[0042] As will be explained below, the polymer components of the
random propylene copolymers (R--PP) can be produced in a sequential
step process, using reactors in serial configuration and operating
at different reaction conditions. As a consequence, each fraction
prepared in a specific reactor will have its own molecular weight
distribution and/or comonomer content distribution.
[0043] When the distribution curves (molecular weight or comonomer
content) from these fractions are superimposed to obtain the
molecular weight distribution curve or the comonomer content
distribution curve of the final polymer, these curves may show two
or more maxima or at least be distinctly broadened when compared
with curves for the individual fractions. Such a polymer, produced
in two or more serial steps, is called bimodal or multimodal,
depending on the number of steps.
[0044] Accordingly the random propylene copolymer (R--PP) may be
multimodal, like bimodal, in view of the comonomer content and/or
molecular weight. It is in particular appreciated that the random
propylene copolymers (R--PP) are multimodal, like bimodal, in view
of the comonomer content.
[0045] Further in case the random propylene copolymers (R--PP) are
of multimodal, like bimodal, character, in particular multimodal,
like bimodal, in view of the comonomer content, it is appreciated
that the individual fractions are present in amounts influencing
the properties of the material. Accordingly it is appreciated that
each of these fractions is at least present in the amount of 10 wt
% based on the random propylene copolymers (R--PP). Accordingly in
case of a bimodal system, in particular in view of the comonomer
content, the split of the two fractions is preferably 40:60 to
60:40, like roughly 50:50.
[0046] Polymerisation processes, which are suitable for producing
the random propylene copolymers of the present invention, are known
in the state of the art and comprise at least one polymerisation
stage, where polymerisation is typically carried out in solution,
slurry, bulk or gas phase. Typically the polymerisation process
comprises additional polymerisation stages or reactors. In one
particular embodiment the process contains at least one bulk
reactor zone and at least one gas phase reactor zone, each zone
comprising at least one reactor and all reactors being arranged in
cascade. In one particularly preferred embodiment the
polymerisation process for polymerising olefins, in particular
propylene optionally with comonomers, like ethylene or other
alpha-olefins, comprises at least one bulk reactor and at least one
gas phase reactor arranged in that order. In some preferred
processes the process comprises one bulk reactor and at least two,
e.g. two or three gas phase reactors. The process may further
comprise pre- and post reactors. Pre-reactors comprise typically
prepolymerisation reactors. In these kinds of processes use of
higher polymerisation temperature (70.degree. C. or higher,
preferably 80.degree. C. or higher, even 85.degree. C. or higher)
either in some or all reactors of the reactor cascade, is preferred
in order to achieve some specific properties to the polymers.
[0047] The random propylene copolymers of the present invention are
prepared by polymerising propylene and a comonomer, as defined
above in the presence of a catalyst system.
[0048] The catalyst system being suitable for producing the random
propylene copolymers of the present invention comprises a
cocatalyst, optionally an external donor and a special olefin
polymerisation catalyst component in the form of solid
particles.
[0049] The special olefin polymerisation catalyst component in the
form of solid particles is prepared by [0050] a) preparing a
solution of at least one alkoxy compound (Ax) being the reaction
product of at least one compound of a Group 2 metal with at least a
monohydric alcohol (A) in an organic liquid reaction medium, [0051]
b) adding said solution to at least one compound of a transition
metal and [0052] c) preparing the solid catalyst component
particles, wherein an internal electron donor selected from
benzoates, alkylene glycol dibenzoates, maleates,
1-cyclohexene-1,2-dicarboxylic dialkylester, and 1,3-diethers, or a
mixture of any selected donors, or a corresponding precursor is
added at any step prior to step c).
[0053] The catalyst preparation is based on a liquid/liquid
two-phase system (emulsion/solidification method) or on a
precipitation method where no separate external carrier materials
such as silica or MgCl.sub.2 are needed in order to get solid
catalyst particles.
[0054] This process for preparing solid catalyst particles is in
particular characterized in that the formation of the catalyst
component comprises use of at least one alkoxy compound (Ax) being
the reaction product of at least one compound of Group 2 metal and
at least a monohydric alcohol (A) and further characterized that
non-phthalic compounds as internal electron donor are used in the
catalyst preparation as such or formed in situ.
[0055] According to one embodiment the alkoxy compound (Ax) is a
reaction product of at least one compound of Group 2 metal and a
monohydric alcohol (A) or a reaction product of at least one
compound of Group 2 metal and a mixture of monohydric alcohol (A)
with a further alcohol (B) comprising in addition to the hydroxyl
moiety at least one further oxygen bearing group being different to
a hydroxyl moiety.
[0056] According to a further embodiment in addition to the at
least one alkoxy compound (Ax) being a reaction product of at least
one compound of Group 2 metal and a monohydric alcohol (A) it is
possible to use at least one additional alkoxy compound (Bx) being
a reaction product of at least one compound of Group 2 metal and an
alcohol comprising in addition to the hydroxyl moiety at least one
further oxygen bearing group being different to a hydroxyl moiety,
as defined below (alcohol B).
[0057] Preferably the alkoxy compound is alkoxy compound (Ax) being
a reaction product of at least one compound of Group 2 metal, as
described further below, and said alcohol (A) or said mixture of
alcohol (A) and (B).
[0058] The alkoxy compounds (Ax and Bx) can be prepared in situ in
the first step of the catalyst preparation process by reacting said
compounds of Group 2 metal with the alcohol or alcohol mixture as
described above, or said alkoxy compounds can be separately
prepared reaction products, or they can be even commercially
available as ready compounds and used as such in the catalyst
preparation process of the invention.
[0059] During preparation of the alkoxy compounds (Ax or Bx) from
the at least one compound of Group 2 metal and the alcohol or
alcohol mixture as defined above, a donor or a donor precursor can
be added into the reaction mixture, whereby a Group 2 metal complex
(Complex Ac or Bc) is formed, which is defined in this application
to be a complex of at least the Group 2 metal compound, the alcohol
or alcohol mixture and a donor.
[0060] If the alkoxy compounds (Ax) and/or (Bx) are formed without
using any donor(s) or donor precursor(s), donor(s) as such is added
separately to the reaction product solution or during preparation
of the catalyst component.
[0061] Compounds of Group 2 metal are selected from the group
comprising, preferably consisting of Group 2 metal dialkyls, alkyl
Group 2 metal alkoxides, alkyl Group 2 metal halides and Group 2
metal dihalides. It can further be selected from the group
consisting of dialkyloxy Group 2 metal, diaryloxy Group 2 metal,
alkyloxy Group 2 metal halides, aryloxy Group 2 metal halides,
alkyl Group 2 metal alkoxides, aryl Group 2 metal alkoxides and
alkyl Group 2 metal aryloxides. Preferably Group 2 metal is
magnesium.
[0062] Monohydric alcohols (A) are those of formula ROH in which R
is a linear or branched C.sub.1-C.sub.20 alkyl.
[0063] Typical C.sub.1-C.sub.5 monohydric alcohols are methanol,
ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol,
sec.butanol, tert.butanol, n-amyl alcohol, iso-amyl alcohol, sec.
amyl alcohol, tert. amyl alcohol, diethyl carbinol, sec. isoamyl
alcohol, tert. butyl carbinol.
[0064] Typical C.sub.6-C.sub.10 monohydric alcohols are hexanol,
2-ethyl-1-butanol, 4-methyl-2-pentanol, 1-heptanol, 2-heptanol,
4-heptanol, 2,4-dimethyl-3-pentanol, 1-octanol, 2-octanol,
2-ethyl-1-hexanol, 1-nonanol, 5-nonanol, diisobutyl carbinol,
1-decanol and 2,7-dimethyl-2-octanol. Typical >C.sub.10
monohydric alcohols are n-1-undecanol, n-1-dodecanol,
n-1-tridecanol, n-1-tetradecanol, n-1-pentadecanol, 1-hexadecanol,
n-1-heptadecanol and n-1 octadecanol. The monohydric alcohols may
be unsaturated, as long as they do not act as catalyst poisons.
[0065] Preferable monohydric alcohols are those of formula ROH in
which R is a C.sub.2-C.sub.16 alkyl group, most preferably a
C.sub.4-C.sub.12 alkyl group, particularly 2-ethyl-1-hexanol.
[0066] Alcohol (B) is an alcohol which comprises in addition to the
hydroxyl moiety at least one further oxygen bearing group being
different to a hydroxyl moiety
[0067] Typically, such further oxygen bearing group is an ether
moiety. The alcohol (B) as defined above may be aliphatic or
aromatic although aliphatic compounds are preferred. The aliphatic
compounds may be linear, branched or cyclic or any combination
thereof and in particular preferred alcohols are those comprising
one ether moiety.
[0068] Illustrative examples of such preferred ether moiety
containing alcohols (B) to be employed in accordance with the
present invention are glycol monoethers, in particular C.sub.2 to
C.sub.4 glycol monoethers, such as ethylene or propylene glycol
monoethers wherein the ether moieties comprise from 2 to 18 carbon
atoms, preferably from 2 to 12 carbon atoms. Preferred monoethers
are C.sub.2 to C.sub.4 glycol monoethers and derivatives thereof.
Illustrative and preferred examples are ethylene glycol butyl
ether, ethylene glycol hexyl ether, ethylene glycol 2-ethylhexyl
ether, propylene glycol n-butyl ether, propylene glycol methyl
ether, propylene glycol ethyl ether, propylene glycol n-hexyl
ether, propylene glycol 2-ethylhexyl ether, with ethylene glycol
hexyl ether, 1,3-propylene glycol ethyl ether and 1,3-propylene
glycol n-butyl ether, being particularly preferred.
[0069] The most preferred alcohol (B) is 1,3-propylene glycol ethyl
ether or 1,3-propylene glycol n-butyl ether.
[0070] Usually the different complexes or alcohols are usually
employed in a mole ratio of from 10:1 to 1:10, preferably this mole
ratio is from 8:1 to 1:8, more preferably 6:1 to 1:6, even more
preferably 4:1 to 1:4 and in embodiments also 2:1 to 1:2. This
ratio can be adjusted depending on the used donor e.g. donors with
short chains require longer chain alcohols and vice versa.
[0071] The reaction for the preparation of the alkoxy compounds
(Ax) and (Bx) may in embodiments, be carried out preferably in an
aromatic or aromatic/aliphatic medium at a temperature of
20.degree. to 80.degree. C., and in case that the Group 2 metal is
magnesium, the preparation of the alkoxy magnesium compound may be
carried out at a temperature of 50.degree. to 70.degree. C.
[0072] The reaction medium used as solvent can be aromatic or a
mixture of aromatic and aliphatic hydrocarbons, the latter one
containing 5-20 carbon atoms, preferably 5-16 carbon atoms more
preferably 5-12 carbon atoms and most preferably 5 to 9 carbon
atoms. Preferably, the aromatic hydrocarbon is selected substituted
and unsubstituted benzenes, preferably from alkylated benzenes,
even more preferably from toluene and xylenes, and is most
preferably toluene.
[0073] The molar ratio of said reaction medium to magnesium is
preferably less than 10, for instance from 4 to 10, preferably from
5 to 9.
[0074] Alkoxy compounds (Ax) and (Bx) are preferably alkoxy
magnesium compounds.
[0075] The alkoxy magnesium compound group is preferably selected
from the group consisting of magnesium dialkoxides, complexes of a
magnesium dihalide and an alcohol, and complexes of a magnesium
dihalide and a magnesium dialkoxide, or mixtures therefrom. More
preferably the alkoxy magnesium compound is a magnesium dialkoxide
compound.
[0076] The alkoxy magnesium compound group is the a reaction
product of an alcohol (A) respectively alcohol (B) or a mixture of
alcohol (A) and alcohol (B) with a magnesium compound selected from
the group consisting of dialkyl magnesiums, alkyl magnesium
alkoxides, alkyl magnesium halides and magnesium dihalides. It can
further be selected from the group consisting of dialkyloxy
magnesium, diaryloxy magnesium, alkyloxy magnesium halides, aryloxy
magnesium halides, alkyl magnesium alkoxides, aryl magnesium
alkoxides and alkyl magnesium aryloxides.
[0077] The magnesium dialkoxide may be the reaction product of
dialkyl magnesium of the formula R.sub.2Mg, wherein each one of the
two Rs is a similar or different C.sub.1-C.sub.20 alkyl, preferably
a similar or different C.sub.2-C.sub.10 alkyl, and a monohydric
alcohol of formula ROH, with R being C.sub.1-C.sub.20 alkyl,
preferably C.sub.2-C.sub.16 alkyl.
[0078] Typical magnesium alkyls are ethylbutyl magnesium, dibutyl
magnesium, dipropyl magnesium, propylbutyl magnesium, dipentyl
magnesium, butylpentylmagnesium, butyloctyl magnesium and dioctyl
magnesium. Most preferably, one R of the formula R.sub.2Mg is a
butyl group and the other R is an ethyl or octyl group, i.e. the
dialkyl magnesium compound is butyl octyl magnesium or ethyl butyl
magnesium.
[0079] Typical alkyl-alkoxy magnesium compounds RMgOR, when used,
are ethyl magnesium butoxide, butyl magnesium pentoxide, octyl
magnesium butoxide and octyl magnesium octoxide.
[0080] The phthalate free electron donor compound used in the
preparation of the catalyst of the present invention is preferably
selected from benzoates, alkylene glycol dibenzoates, maleates,
1-cyclohexene-1,2-dicarboxylic dialkylester, and 1,3-diethers or
mixtures therefrom.
[0081] Preferably the phthalate free internal donors are selected
from: [0082] a) benzoates of the formula (I)
##STR00001##
[0082] with R being a linear or branched C.sub.1-C.sub.12-alkyl
group, preferably a linear or branched C.sub.2-C.sub.10-alkyl
group, more preferably a linear or branched C.sub.4-C.sub.9-alkyl
group and most preferably a branched C.sub.6-C.sub.8-alkyl group,
like 2-ethylhexyl, and R' being H or a linear or branched
C.sub.1-C.sub.12-alkyl group, preferably a linear or branched
C.sub.2-C.sub.10-alkyl group more preferably a linear or branched
C.sub.4-C.sub.8-alkyl group, like tert.-butyl or n-hexyl, whereby
the alkyl group can contain one or more heteroatoms selected from
O, N or S, preferably O or N, more preferably O, in the alkyl
chain, or can be substituted by one or more substituents selected
from .dbd.O, halogen, like chlorine, fluorine or bromine, or
optionally substituted C.sub.6-C.sub.14-aryl.
[0083] The C.sub.6-C.sub.14-aryl group is preferably a phenyl
group, the optional substituents on the aryl group can be linear or
branched C.sub.1-C.sub.12-alkyl, preferably linear or branched
C.sub.1-C.sub.10-alkyl and more preferably linear or branched
C.sub.1-C.sub.8-alkyl or halogen, like chlorine, fluorine or
bromine, preferably chlorine or bromine and more preferably
chlorine. The number of substituents on the aryl group can be 0 to
4, preferably 0 to 2, more preferably 0 or 1.
[0084] R' being not H can be in ortho-meta or para position,
preferably in para or ortho-position.
[0085] More preferred compounds are 2-ethylhexyl benzoate,
2-ethylhexyl (4-n-hexylbenzoate), 2-ethylhexyl
(4-tert.-butylbenzoate), 2-ethylhexyl
((2-(4-chlorobenzoyl)benzoate). [0086] b) alkylene glycol
dibenzoates of the formula (II)
##STR00002##
[0086] with n being 1 or 2, if n=1 then R.dbd.CH.sub.3 and if n=2
then R.dbd.H.
[0087] More preferred compounds are ethylene glycol dibenzoate,
1,2-propylene glycol dibenzoate and 1,3-propylene glycol
dibenzoate. [0088] c) maleates of formula (III)
##STR00003##
[0088] with R.sub.1 and R.sub.2 being the same or different and
being a linear or branched C.sub.1-C.sub.12-alkyl group, preferably
a linear or branched C.sub.1-C.sub.8-alkyl group, more preferably a
linear or branched C.sub.1-C.sub.4-alkyl group and most preferably
ethyl, whereby R.sub.1 and R.sub.2 are preferably the same and with
R being H or a linear, branched or cyclic C.sub.1 to
C.sub.12-alkyl, preferably a branched or cyclic C.sub.3 to
C.sub.8-alkyl, like iso-butyl, cyclopentyl or cyclohexyl, whereby
it is preferred that R is not H.
[0089] More preferred compounds are diethyl-2-isobutyl maleate,
diethyl-2-cyclopentyl maleate and diethyl-2-cyclohexyl maleate.
[0090] d) 1-cyclohexene-1,2-dicarboxylic dialkylester of formula
(IV)
##STR00004##
[0090] with R.sub.1 and R.sub.2 can be identical or different and
can be a linear or branched C.sub.5-C.sub.20-alkyl, preferably a
C.sub.6-C.sub.16-alkyl and more preferably linear or branched
C.sub.8-C.sub.12-alkyl. Preferably R.sub.1 and R.sub.2 are
identical.
[0091] More preferred compound is
1-cyclohexene-1,2-(bis-(2-ethylhexyl)dicarboxylate. [0092] e)
1,3-diethers of formula (V) or (VI)
##STR00005##
[0092] wherein in formula (V) and (VI) R.sub.1 and R.sub.2 are the
same or different and can be a linear or branched
C.sub.1-C.sub.12-alkyl, or R.sub.1 with R.sub.5 and/or R.sub.2 with
R.sub.6 can form a ring with 4 to 6 C-atoms, R.sub.3 and R.sub.4 of
formula (V) are the same or different and can be H or a linear or
branched C.sub.1-C.sub.12-alkyl or R.sub.3 and R.sub.4 can form
together a ring with 5 to 10 C-atoms, which can be part of an
aliphatic or aromatic polycyclic ring system with 9 to 20 C atoms,
R.sub.5 and R.sub.6 in formula (V) are the same or different and
can be H or a linear or branched C.sub.1-C.sub.12-alkyl or can form
together an aliphatic ring with 5 to 8 C-atoms, and R.sub.51,
R.sub.61 and R.sub.7 in formula (VI) are the same or different and
can be H or a linear or branched C.sub.1-C.sub.12-alkyl or two or
three of R.sub.51, R.sub.61 and R.sub.7 can form together with
C.sub.1 to C.sub.3 an aromatic ring or ring system with 6 to 14
C-atoms, preferably 10 to 14 C-atoms.
[0093] R.sub.1 and R.sub.2 are preferably the same in formula (V)
and (VI) and can be a linear or branched C.sub.1-C.sub.10-alkyl,
more preferably C.sub.1-C.sub.8-alkyl, like methyl, ethyl,
n-propyl, i-propyl, n-butyl or tert.-butyl or 2-ethylhexyl.
[0094] In formula (V) is further possible that R.sub.1 with R.sub.5
and/or R.sub.2 with R.sub.6 can form together with the oxygen atom
a ring with 4 to 6 C-atoms, preferably 4 to 5 C-atoms, like a
tetrahydrofuran ring or a tetrahydropyrane ring.
[0095] R.sub.3 is preferably a linear or branched
C.sub.1-C.sub.10-alkyl, more preferably a C.sub.1-C.sub.9-alkyl,
like methyl, ethyl, i-propyl, i-butyl or n-nonyl.
[0096] R.sub.4 is preferably H or a linear or branched
C.sub.1-C.sub.10-alkyl, more preferably a C.sub.1-C.sub.6-alkyl,
like methyl, i-propyl, n-butyl, i-butyl, i-pentyl.
[0097] It is also possible that R.sub.3 and R.sub.4 can form
together a ring, preferably an alicyclic ring with preferably 5 to
7 C-atoms, more preferably 5 to 6 C-atoms, like cyclopentan, 2- or
3-cyclopenten, cyclohexene, 2- or 3- or 4-cyclohexene.
[0098] It is further possible that this ring is part of an
alicyclic or aromatic polycyclic ring system with 9 to 18 C-atoms,
like decaline, hydroindane, fluorene or indane.
[0099] R.sub.5 in formula (V) can be preferably H or a linear or
branched C.sub.2-C.sub.8-alkyl, more preferably can be H or
C.sub.2-C.sub.6-alkyl and most preferably H.
[0100] R.sub.6 in formula (V) can be preferably H or a linear or
branched C.sub.2-C.sub.8-alkyl, preferably H or a linear
C.sub.3-C.sub.6-alkyl, like i-propyl or i-butyl.
[0101] In formula (V) it is further possible that R.sub.5 and
R.sub.6 can form together an aliphatic ring with 5 to 8 C-atoms,
like cyclopentan, cyclohexene or cycloheptane.
[0102] In formula (VI) R.sub.51, R.sub.61 and R.sub.7 are the same
or different and are preferably H or a linear or branched
C.sub.1-C.sub.10-alkyl, more preferably H or a linear or branched
C.sub.1-C.sub.8-alkyl like methyl, i-propyl, n-butyl, i-butyl,
i-pentyl.
[0103] In formula (VI) it is further possible that two or three of
R.sub.51, R.sub.61 and R.sub.7 form together with C.sub.1 to
C.sub.3 an aromatic ring or ring system with 6 to 14 C-atoms,
preferably 10 to 14 C-atoms. Such aromatic rings or ring systems
are phenyl, naphthalene, anthracene or phenanthrene. Preferably
such ring system is naphthalene.
[0104] More preferred compounds are
1,8-bis(2-ethylhexyloxy)naphthalene,
3,3-bis(ethoxymethyl)-2-methyldodecane and
3,3-bis(ethoxymethyl)-2,6-dimethylheptane.
[0105] Most preferably the phthalate free internal donors are
selected from 3,3-bis(ethoxymethyl)-2,6-dimethylheptane,
diethyl-2-isobutyl maleate, diethyl-2-cyclopentyl maleate,
diethyl-2-cyclohexyl maleate, 2-ethylhexyl (4-tert.-butylbenzoate),
2-ethylhexyl ((2-(4-chlorobenzoyl)benzoate) and
1-cyclohexene-1,2-(bis-(2-ethylhexyl)dicarboxylate or mixtures
therefrom.
[0106] The compound of a transition metal is preferably a compound
of a Group 4 metal. The Group 4 metal is preferably titanium, and
its compound to be reacted with the complex of a Group 2 is
preferably a halide. Equivalent to titanium tetrahalide is the
combination of an alkoxy titanium halide and a halogenation agent
therefore, which are able to form a titanium tetrahalide in situ.
The most preferred halide is the chloride.
[0107] In a further embodiment of the invention, a compound of a
transition metal used in the process can also contain organic
ligands typically used in the field known as a single site
catalyst.
[0108] In a still further embodiment of the invention, a compound
of a transition metal can also be selected from Group 5 metals,
Group 6 metals, Cu, Fe, Co, Ni and/or Pd compounds.
[0109] In principle said olefin polymerisation catalyst components
can be obtained in several ways all based on the same
mechanism.
[0110] In one embodiment the preparation of the olefin
polymerisation catalyst component in form of solid particles
comprises the steps of [0111] (a1) preparing a solution (S1) of at
least one alkoxy compound (Ax), being a reaction product of at
least one compound of a Group 2 metal with at least a monohydric
alcohol (A) and an electron donor as defined above or a mixture
therefrom or a corresponding precursor thereof in an organic liquid
reaction medium (OM1), [0112] (b1) combining said solution (S1)
with at least one transition metal compound (CT), [0113] (c1)
precipitating said catalyst component in the form of a solid
particle, and [0114] (d1) recovering the solidified particles of
the olefin polymerisation catalyst component.
[0115] In step (a1) it is possible to use an alkoxy compound (Ax)
being a reaction product of at least one Group 2 metal compound and
a monohydric alcohol (A), as defined above.
[0116] It is further possible to use an alkoxy compound (Ax) being
a reaction product of at least one Group 2 metal compound and a
mixture of alcohol (A) with alcohol (B) comprising in addition to
the hydroxyl moiety at least one further oxygen bearing group being
different to a hydroxyl moiety, as defined above.
[0117] The third possibility is to use a mixture of an alkoxy
compound (Ax) being a reaction product of at least one Group 2
metal compound and a monohydric alcohol (A) and an alkoxy compound
(Bx) being a reaction product of at least one Group 2 metal
compound and an alcohol (B) comprising in addition to the hydroxyl
moiety at least one further oxygen bearing group being different to
a hydroxyl moiety, as defined above.
[0118] It is possible to dissolve the transition metal compound
(CT) in step (b1) in an organic liquid reaction medium (OM2),
whereby solution (S2) is formed.
[0119] The process of solids precipitation can be carried out by
several methods:
[0120] In one embodiment the addition of solution (S1) to the at
least one transition metal compound (CT) in step (b1) is done at a
temperature of at least 50.degree. C., preferably in the
temperature range of 50 to 110.degree. C., more preferably in the
range of 70 to 100.degree. C., most preferably in the range of 85
to 95.degree. C., at which temperature the at least one transition
metal compound (CT) is in a liquid form, resulting in the
precipitation of said solid catalyst components.
[0121] In this case it is especially appreciated that after having
combined the solution (S1) with at least one transition metal
compound (CT) the whole reaction mixture is kept at least at
50.degree. C., more preferably is kept in the temperature range of
50 to 110.degree. C., more preferably in the range of 70 to
100.degree. C., most preferably in the range of 85 to 95.degree.
C., to secure full precipitation of the catalyst component in form
of a solid particle.
[0122] In this case it is possible that a surfactant is added in
step (a1) or step (b1).
[0123] General examples of surfactants include polymer surfactants,
such as poly(alkyl methacrylate) and poly(alkyl acrylate), and the
like. A polyalkyl methacrylate is a polymer that may contain one or
more methacrylate monomers, such as at least two different
methacrylate monomers, at least three different methacrylate
monomers, etc. Moreover, the acrylate and methacrylate polymers may
contain monomers other than acrylate and methacrylate monomers, so
long as the polymer surfactant contains at least about 40% by
weight acrylate and methacrylate monomers.
[0124] Examples of surfactants that are commercially available
include those under the trade marks VISCOPLEX.RTM. available from
RohMax Additives, GmbH, especially those having product
designations 1-254, 1-256 and those under the trade designations
CARBOPOL.RTM. and PEMULEN.RTM. available from Noveon/Lubrizol.
[0125] In a second embodiment the solution (S1) is mixed with at
least one transition metal compound (CT) in liquid form at a
temperature of about -20.degree. C. to about 30.degree. C. and
precipitating the solid catalyst components by subsequently slowly
raising the temperature to at least 50.degree. C., preferably in
the temperature range of 50 to 110.degree. C., more preferably in
the range of 70 to 100.degree. C., most preferably in the range of
85 to 95.degree. C., whereby the rate of temperature increase is in
the range from 0.1.degree. C. to 30.degree. C. per minute,
preferably 0.5 to 10.degree. C. per minute.
[0126] In this case it is especially appreciated that a surfactant
is added to the solution (S1) before step (b1). Suitable
surfactants are described above.
[0127] In both cases it is possible, but not necessary, to add some
precipitating agent into the system. Such precipitating agents are
able to effect morphology of the particles formed during the
precipitation step. In a specific process no precipitating agent
has been used. A precipitating agent according to this invention is
an agent which promotes the precipitation of the catalyst component
in form of a solid particle. The organic liquid medium used as
(OM2), as defined later in this application, can promote the
precipitating and thus act and used as a precipitating agent.
However, the final catalyst does not contain any such medium.
[0128] Moreover it is preferred that no precipitating agent has
been used in the process as stated above.
[0129] Preferably, the catalyst component as prepared in the
previous paragraphs is a precipitated solid particle.
[0130] "Precipitation" according to this invention means that
during the catalyst component preparation a chemical reaction in a
solution takes place leading to the desired catalyst component
insoluble in said solution.
[0131] Suitable alkoxy compounds (Ax) and (Bx) and their
preparation have been described above.
[0132] Suitable electron donors and their precursors as well as
suitable transition metal compounds are also described above.
[0133] Preferably TiCl.sub.4 is used as transition metal
compound.
[0134] If the electron donor is used as such, it is added to the
alkoxy compound (Ax), or alkoxy compound (Bx) if present, or to the
mixture of the alkoxy compounds (Ax) and (Bx), obtained by mixing
alkoxy compound (Ax) being a reaction product of at least one Group
2 metal compound as described above with the monohydric alcohol (A)
as described above and alkoxy compound (Bx) being a reaction
product of at least one Group 2 metal compound as described above
and the alcohol (B), as described above, whereby the reaction
medium used as solvent for the Group 2 metal compound can be
aromatic or a mixture of aromatic and aliphatic hydrocarbons, the
latter one containing 5-20 carbon atoms, preferably 5-16 carbon
atoms more preferably 5-12 carbon atoms and most preferably 5 to 9
carbon atoms. Preferably, the aromatic hydrocarbon is selected from
substituted and unsubstituted benzenes, preferably from alkylated
benzenes, even more preferably from toluene and xylenes, and is
most preferably toluene.
[0135] The electron donor can also be introduced in form of a
precursor as described above, which is then transformed in situ to
the electron donor by reaction with a corresponding Mg-alkoxide.
The Mg-alkoxide is prepared as described above by reacting a
magnesium compound with the corresponding alcohol (A) or alcohol
(B).
[0136] Additional donors can be added, if so desired into the
catalyst preparation in any of steps (a1) to (b1). Preferably
additional donors, if used, are non-phthalic acid ester as
well.
[0137] It is also possible to use mixtures of the above described
donors.
[0138] The reaction medium corresponds to the organic liquid
reaction medium (OM1) of step (a1).
[0139] The organic liquid reaction medium (OM2), where TiCl.sub.4
can be solved, can be the same as the organic liquid reaction
medium (OM1) or can be different thereto, the latter being
preferred.
[0140] Preferably the organic liquid reaction medium (OM2) is
C.sub.5 to C.sub.10 hydrocarbon, more preferably of a C.sub.6 to
C.sub.10 alkane, like heptane, octane or nonane, or any mixtures
thereof.
[0141] It is in particular appreciated that the organic liquid
reaction medium (OM1) is a C.sub.6 to C.sub.10 aromatic
hydrocarbon, most preferably toluene, and the organic liquid
reaction medium (OM2) is a C.sub.6 to C.sub.10 alkane, most
preferably heptane.
[0142] Further it is appreciated that the organic liquid reaction
media (OM1) and (OM2) are selected in a way which supports the
precipitation of the solid catalyst particle.
[0143] When adding the solution (S1) to the at least one transition
metal compound (CT) mixing is appreciated. Suitable mixing
techniques include the use of mechanical as well as the use of
ultrasound for mixing, as known to the skilled person.
[0144] After precipitation the solid catalyst particle is washed in
a known manner.
[0145] Accordingly it is preferred that solid catalyst particle is
washed at least once up to 6 times, preferably at least twice, most
preferably at least three times with a hydrocarbon, which
preferably is selected from aromatic and aliphatic hydrocarbons,
preferably with toluene, heptane or pentane, more preferably
toluene, particularly with hot (e.g. 80 to 100.degree. C.) toluene,
which might include a smaller or higher amount of TiCl.sub.4 in it.
The amount of TiCl.sub.4 can vary from a few vol % to more than
50-vol %, such as from 5-vol % to 50-vol %, preferably from 5 to
15-vol %. It is also possible that at least one wash is done with
100-vol % TiCl.sub.4.
[0146] One or several further washes after aromatic and/or
TiCl.sub.4 washes can be run with aliphatic hydrocarbons of 4 to 8
carbon atoms. Preferable these latter washings are performed with
heptane and/or pentane. Washings can be done with hot (e.g.
90.degree. C.) or cold (room temperature) hydrocarbons or
combinations thereof. It is also possible that all washings will be
done with the same solvent, e.g. toluene.
[0147] In addition, during the catalyst component preparation a
reducing agent, which decreases the amount of titanium present in
said solidified particles of the olefin polymerisation catalyst
component being present in the oxidation state +4, can be
added.
[0148] Suitable reducing agents are aluminium alkyl compounds,
aluminium alkyl alkoxy compounds as well as magnesium compounds as
defined in the present specification.
[0149] Suitable aluminium compounds have a general formula
AlR.sub.3-nX.sub.n, wherein R stands for a straight chain or
branched alkyl or alkoxy group having 1 to 20, preferably 1 to 10
and more preferably 1 to 6 carbon atoms, X independently represents
a residue selected from the group of halogen, preferably chloride,
and n stands for 0, 1 or 2. At least one of the R residues has to
be an alkyl group.
[0150] The compound can be added as an optional compound to the
catalyst component synthesis and can be added at any step (b1) to
(c1), or during the washing step as described above, however,
before step (d1).
[0151] Preferably the reducing compound is added during the washing
step, more preferably during the first washing step with hot
toluene.
[0152] Illustrative examples of aluminium alkyl and alkoxy
compounds to be employed in accordance with the present invention
are: [0153] Tri-(C.sub.1-C.sub.6)-alkyl aluminium compounds and
chlorinated aluminium alkyl compounds, especially diethyl aluminium
chloride; [0154] diethyl aluminium ethoxide, ethyl aluminium
diethoxide, diethyl aluminium methoxide, diethyl aluminium
propoxide, diethyl aluminium butoxide, dimethyl aluminium ethoxide,
of which in particular diethyl aluminium ethoxide is preferred.
[0155] Suitable magnesium compounds are magnesium compounds as
defined herein in connection with the complex of a Group 2 metal.
The respective disclosure is incorporated herein by reference with
respect to the magnesium compound to be added in accordance with
the process of the present invention. In particular, suitable
magnesium compounds are dialkyl magnesium compounds or halogenated
alkyl magnesium compounds of the general formula
MgR.sub.2-nX.sub.n, where each n is 0 or 1, and each R are same or
different alkyl groups with 1 to 8 carbon atoms and X is halogen,
preferably Cl. One preferred magnesium compound is butyloctyl
magnesium (commercially available under the trade name BOMAG),
which is already preferably used in the preparation of the Mg
complex.
[0156] The added amount of the optional Al compound depends on the
desired degree of reduction of amount of titanium present in the
solidified particles of the olefin polymerisation catalyst
component being present in the oxidation state +4. The preferred
amounts of Al in the catalyst component depend to some extent on
the Al compound, e.g. if an Al alkoxy compound is used, the
preferred final Al amounts seem to be lower than if e.g. Al alkyl
chloride compounds are used.
[0157] The final catalyst component particles have an Al content of
0.0 to 0.8 wt %, preferably 0.0 to 0.5 wt % or 0.0 to 0.4 wt %.
[0158] The magnesium compound to be added in accordance with the
present invention is added in corresponding amounts.
[0159] Preferably a chlorinated aluminium alkyl compounds,
especially diethyl aluminium chloride; is added.
[0160] In the second way the preparation of the catalyst component
in form of solid particles comprises the steps of [0161] (a2)
preparing a solution of at least one alkoxy compound (Ax), being a
reaction product of at least one compound of a Group 2 metal with
at least a monohydric alcohol (A) and an electron donor as
described above or a precursor thereof in an organic liquid
reaction medium, [0162] (b2) adding said solution of said alkoxy
compound (Ax) to at least one compound of a transition metal to
produce an emulsion, wherein the dispersed phase of which is in the
form of droplets and contains more than 50 mol % of the Group 2
metal in said alkoxy compound (Ax), [0163] (c2) agitating the
emulsion in order to maintain the droplets of said dispersed phase
within said predetermined average size range of 2 to 500 .mu.m,
[0164] (d2) solidifying said droplets of the dispersed phase,
[0165] (e2) recovering the solidified particles of the olefin
polymerisation catalyst component.
[0166] In step (a2) it is possible to use an alkoxy compound (Ax)
being a reaction product of at least one Group 2 metal compound and
a monohydric alcohol (A), as defined above.
[0167] It is further possible to use an alkoxy compound (Ax) being
a reaction product of at least one Group 2 metal compound and a
mixture of alcohol (A) with alcohol (B) comprising in addition to
the hydroxyl moiety at least one further oxygen bearing group being
different to a hydroxyl moiety, as defined above.
[0168] The third possibility is to use a mixture of an alkoxy
compound (Ax) being a reaction product of at least one Group 2
metal compound and a monohydric alcohol (A) and an alkoxy compound
(Bx) being a reaction product of at least one Group 2 metal
compound and an alcohol (B) comprising in addition to the hydroxyl
moiety at least one further oxygen bearing group being different to
a hydroxyl moiety, as defined above.
[0169] Suitable alkoxy compounds (Ax) and (Bx) and their
preparation have been described above.
[0170] Suitable electron donors and their precursors as well as
suitable transition metal compounds are also described above.
[0171] In step (a2) the solution (S1) is typically a solution of at
least one alkoxy compound (Ax) and optionally an alkoxy compound
(Bx) in liquid hydrocarbon reaction medium, which can be provided
in situ by reacting an alcohol (A) or a mixture of alcohol (A) and
alcohol (B) with the Group 2 metal compound in a liquid hydrocarbon
medium to form alkoxy compound (Ax), as described above, and
optionally mixing alkoxy compound (Ax) with alkoxy compound (Bx),
prepared by reacting an alcohol (B) with the Group 2 metal compound
in a liquid hydrocarbon medium.
[0172] The internal donor or precursor thereof as defined above is
added preferably in step (a2) to said solution. The solution of
step (a2) is then typically added to the at least one compound of a
transition metal, such as titanium tetrachloride. This addition
preferably is carried out at a low temperature, such as from -10 to
40.degree. C., preferably from -5 to 30.degree. C., such as about
0.degree. C. to 25.degree. C.
[0173] During any of these steps an organic reaction medium or
solvent may be present, typically selected among aromatic and/or
aliphatic hydrocarbons as described above.
[0174] Additional donors can be added, if so desired into the
catalyst preparation in any of steps (a2) to (c2). Preferably
additional donors, if used, are non-phthalic acid ester as well. It
is also possible to use mixtures of the above described
mixtures.
[0175] The process in accordance with the present invention yields
as intermediate stage, as identified above an emulsion of a denser,
transition metal compound/toluene-insoluble, oil dispersed phase
typically having a transition metal metal/Group 2 mol ratio of 0.1
to 10 in an oil disperse phase having a transition metal/Group 2
mol ratio of 10 to 100.
[0176] Transition metal compound is preferably Group 4 metal
compound, and is most preferably TiCl.sub.4. Group 2 metal is
preferably Mg. This emulsion is then typically agitated, optionally
in the presence of an emulsion stabilizer and/or a turbulence
minimizing agent, in order to maintain the droplets of said
dispersed phase, typically within an average size range of 2 to 500
.mu.m. The catalyst particles are obtained after solidifying said
particles of the dispersed phase e.g. by heating.
[0177] The said disperse and dispersed phases are thus
distinguishable from one another by the fact that the denser oil,
if contacted with a solution of Group 4 metal compound preferably
TiCl.sub.4 in toluene, will not dissolve in it. A suitable solution
for establishing this criterion would be one having a toluene mol
ratio of 0.1 to 0.3. They are also distinguishable by the fact that
the great preponderance of the Mg provided (as complex) for the
reaction with the Group 4 metal compound is present in the
dispersed phase, as revealed by comparison of the respective Group
4 metal/Mg mol ratios.
[0178] In effect, therefore, virtually the entirety of the reaction
product of the Mg complex with the Group 4 metal--which is the
precursor of the ultimate catalyst component--becomes the dispersed
phase, and proceeds through the further processing steps to the
final particulate form. The disperse phase, still containing a
useful quantity of Group 4 metal, can be reprocessed for recovery
of that metal.
[0179] The production of a two-phase reaction product is encouraged
by carrying out the Mg complex/Group 4 metal compound reaction at
low temperature, specifically above -10.degree. C. but below
50.degree. C., preferably between above -5.degree. C. and below
40.degree. C. Since the two phases will naturally tend to separate
into a lower, denser phase and supernatant lighter phase, it is
necessary to maintain the reaction product as an emulsion by
agitation, preferably in the presence of an emulsion
stabilizer.
[0180] The emulsion, i.e. the two phase liquid-liquid system may be
formed in all embodiments of the present invention by simple
stirring and optionally adding (further) solvent(s) and additives,
such as the turbulence minimizing agent (TMA) and/or the
emulsifying agents described further below.
[0181] Emulsifying agents/emulsion stabilizers can be used
additionally in a manner known in the art for facilitating the
formation and/or stability of the emulsion. For the said purposes
e.g. surfactants, e.g. a class based on acrylic or methacrylic
polymers can be used. Preferably, said emulsion stabilizers are
acrylic or methacrylic polymers, in particular those with medium
sized ester side chains having more than 10, preferably more than
12 carbon atoms and preferably less than 30, and preferably 12 to
20 carbon atoms in the ester side chain. Particular preferred are
unbranched C.sub.12 to C.sub.20 (meth)acrylates such as
poly(hexadecyl)-methacrylate and poly(octadecyl)-methacrylate.
Suitable examples of commercially available surfactants are e.g.
those sold under the name of Viscoplex.RTM., like Viscoplex.RTM.,
1-124 and 1-126, as indicated earlier in this application.
[0182] As mentioned above a turbulence minimizing agent (TMA) can
be added to the reaction mixture in order to improve the emulsion
formation and maintain the emulsion structure. Said TMA agent has
to be inert and soluble in the reaction mixture under the reaction
conditions, which means that polymers without polar groups are
preferred, like polymers having linear or branched aliphatic carbon
backbone chains.
[0183] Said TMA is in particular preferably selected from
alpha-olefin polymers of alpha-olefin monomers with 6 to 20 carbon
atoms, like polyoctene, polynonene, polydecene, polyundecene or
polydodecene or mixtures thereof. Most preferable it is
polydecene.
[0184] TMA can be added to the emulsion in an amount of e.g. Ito
1.000 ppm, preferably 5 to 100 ppm and more preferable 5 to 50 ppm,
based on the total weight of the reaction mixture.
[0185] It has been found that the best results are obtained when
the Group 4 metal/Mg mol ratio of the denser oil is 1 to 5,
preferably 2 to 4, and that of the disperse phase oil is 55 to
65.
[0186] Generally the ratio of the mol ratio Group 4 metal/Mg in the
disperse phase oil to that in the denser oil is at least 10.
[0187] Solidification of the dispersed phase droplets by heating is
suitably carried out at a temperature of 70 to 150.degree. C.,
usually at 80 to 110.degree. C., preferably at 90 to 110.degree.
C.
[0188] For isolating the solidified particles the reaction mixture
is allowed to settle and the solidified particles are recovered
from this reaction mixture for example by syphoning or by an
in-stream filtering unit.
[0189] The solidified particulate product may be washed at least
once up to 6 times, preferably at least twice, most preferably at
least three times with a hydrocarbon, which preferably is selected
from aromatic and aliphatic hydrocarbons, preferably with toluene,
heptane or pentane, more preferably toluene, particularly with hot
(e.g. 80 to 100.degree. C.) toluene, which might include a smaller
or higher amount of TiCl.sub.4 in it. The amount of TiCl.sub.4 can
vary from a few vol % to more than 50-vol %, such as from 5-vol %
to 50-vol %, preferably from 5 to 15-vol %. It is also possible
that at least one wash is done with 100-vol % TiCl.sub.4.
[0190] One or several further washes after aromatic and/or
TiCl.sub.4 washes can be run with aliphatic hydrocarbons of 4 to 8
carbon atoms. Preferable these latter washings are performed with
heptane and/or pentane. Washings can be done with hot (e.g.
90.degree. C.) or cold (room temperature) hydrocarbons or
combinations thereof. It is also possible that all washings will be
done with the same solvent, e.g. toluene.
[0191] The washing can be optimized to give a catalyst component
with novel and desirable properties.
[0192] Finally, the washed catalyst component is recovered.
[0193] It can further be dried, as by evaporation or flushing with
nitrogen or it can be slurred to an oily liquid with or without any
drying step.
[0194] In addition, during the catalyst component preparation a
reducing agent, which decreases the amount of titanium present in
said solidified particles of the olefin polymerisation catalyst
component being present in the oxidation state +4, can be
added.
[0195] Suitable reducing agents are aluminium alkyl compounds,
aluminium alkyl alkoxy compounds as well as magnesium compounds as
defined in the present specification. Suitable aluminium compounds
have a general formula AlR.sub.3-nX.sub.n, wherein R stands for a
straight chain or branched alkyl or alkoxy group having 1 to 20,
preferably 1 to 10 and more preferably 1 to 6 carbon atoms, X
independently represents a residue selected from the group of
halogen, preferably chloride, and n stands for 0, 1 or 2. At least
one of the R residues has to be an alkyl group.
[0196] The compound can be added as an optional compound to the
catalyst component synthesis and brought into contact with the
droplets of the dispersed phase of the agitated emulsion before
recovering the solidified particles in step (e2). I.e. the Al
compound can be added at any step (b2) to (d2), or during the
washing step as described above, however, before step (e2).
Reference is made to WO 2004/029112, EP-A-1 862 480 and to EP-A-1
862 481.
[0197] Illustrative examples of aluminium alkyl and alkoxy
compounds to be employed in accordance with the present invention
are:
Tri-(C.sub.1-C.sub.6)-alkyl aluminium compounds and chlorinated
aluminium (C.sub.1-C.sub.6)-alkyl compounds, preferably tri-ethyl
aluminium, ethyl aluminium dichloride, diethyl aluminium chloride,
especially diethyl aluminium chloride; Diethyl aluminium ethoxide,
ethyl aluminium diethoxide, diethyl aluminium methoxide, diethyl
aluminium propoxide, diethyl aluminium butoxide, dimethyl aluminium
ethoxide, of which in particular diethyl aluminium ethoxide is
preferred.
[0198] Suitable magnesium compounds are magnesium compounds as
defined herein in connection with the complex of a Group 2 metal.
The respective disclosure is incorporated herein by reference with
respect to the magnesium compound to be added in accordance with
the process of the present invention. In particular, suitable
magnesium compounds are dialkyl magnesium compounds or halogenated
alkyl magnesium compounds of the general formula MgR.sub.2X.sub.n,
where each n is 0 or 1, and each R are same or different alkyl
groups with 1 to 8 carbon atoms and X is halogen, preferably Cl.
One preferred magnesium compound is butyloctyl magnesium
(commercially available under the trade name BOMAG), which is
already preferably used in the preparation of the Mg complex.
[0199] The added amount of the optional Al compound depends on the
desired degree of reduction of amount of titanium present in the
solidified particles of the olefin polymerisation catalyst
component being present in the oxidation state +4. The preferred
amounts of Al in the catalyst component depend to some extent on
the Al compound, e.g. if an Al alkoxy compound is used, the
preferred final Al amounts seem to be lower than if e.g. Al alkyl
chloride compounds are used.
[0200] The final catalyst component particles have an Al content of
0.0 to 0.8 wt %, preferably 0.0 to 0.5 wt % or 0.0 to 0.4 wt %.
[0201] The magnesium compound to be added in accordance with the
present invention is added in corresponding amounts.
[0202] Preferably an Al alkyl or Al alkyl alkoxy compound, as
defined above, is added.
[0203] The aluminium alkyl or alkoxy compound and the magnesium
compound can be used alone or in combination.
[0204] The optional Al or Mg compound or a mixture thereof is
preferably added before step (e2), more preferably during the
washing step, which comprises at least one, preferably two and more
preferably three washing procedures with the same or preferably
different hydrocarbons as washing medium.
[0205] The aluminium alkyl or alkoxy compound and/or magnesium
compound to be used in the catalyst component preparation of the
invention can be added to any of the washing mediums, which are, as
described above, preferably toluene, heptane and/or pentane.
[0206] Though the procatalyst preparation according to the
inventive method can be carried out batch-wise, it is also
preferable and possible to prepare the catalyst component
semi-continuously or continuously. In such semi-continuous or
continuous process, the solution of the alkoxy compound of the
group 2 metal and said electron donor, which is prepared by
reacting the alkoxy compound with said electron donor in an organic
liquid reaction medium, is mixed with at least one compound of a
transition metal, which might be solved in the same or different
organic liquid reaction medium. The so obtained solution is then
agitated, possibly in the presence of an emulsion stabilizer, and
then the so-agitated emulsion is fed into a temperature gradient
reactor, in which the emulsion is subjected a temperature gradient,
thus leading to solidifying the droplets of a dispersed phase of
the emulsion. The optional TMA is preferably contained in the
solution of the complex or added to the solution before feeding the
agitated solution to the temperature gradient reactor.
[0207] When feeding said agitated emulsion to the temperature
gradient reactor, an inert solvent, in which the droplets are not
soluble, can additionally be fed into that gradient reactor in
order to improve the droplet formation and thus leading to a
uniform grain size of the particles of the catalyst component,
which are formed in the temperature gradient reactor when passing
through said line. Such additional solvent might be the same as the
organic liquid reaction medium, which is used for preparing the
solution of the alkoxy compound of the group 2 metal as explained
above in more detail.
[0208] The solidified particles of the olefin polymerisation
catalyst component can subsequently be recovered by an in-stream
filtering unit and then, optionally after some additional washing
and drying steps in order to remove unreacted starting components,
can be stored for further use. In one embodiment the catalyst can
be fed after washing steps into the olefin polymerisation reactor,
so that a continuous preparation and feed to the reactor is
guaranteed. It is also possible to mix the solidified and washed
catalyst component with an oily fluidic liquid and store and use
the catalyst component as catalyst component-oil slurry. In this
way the drying steps can be avoided, which might be sometimes
detrimental to the catalyst components morphology. This oil-slurry
method is described in general in EP-A-1489110 of the applicant,
incorporated herein by reference.
[0209] As it can be seen from the above description of the
semi-continuous or continuous process, it is thus possible to use
separated reaction vessels for the different process steps and to
transfer the reaction products which are prepared in the respective
reaction vessels and to feed them in-line into further reaction
vessels for formation of the emulsion and, subsequently, of the
solidified particles.
[0210] It is preferred to use a full-continuous process as the time
saving in said process is remarkable. In such fully continuous
process, the formation of the solidified particles could be carried
out in the temperature gradient line in the kind of pipe reactor,
which is sufficiently long and which is subjected said temperature
gradient from the starting temperature in the lower range of 20 to
80.degree. C. up to a "solidifying" temperature of 70 to
150.degree. C. The temperature gradient is preferably obtained by
means of heating the pipe reactor from the outside by applying
normal heaters, microwaves, etc.
[0211] As mentioned before, a filtering unit might preferably be
used for filtering the solidified particles from the solvent
stream. For said filtering unit, various drums and sieving systems
can be used, depending on the specific particle sizes.
[0212] With both production ways, the finally obtained solid
catalyst component is desirably in the form of particles having
generally an average size range, determined by using a Coulter
Counter LS200 at room temperature (20.degree. C.) with n-heptane as
medium, of 2 to 500 .mu.m, preferably 5 to 200 .mu.m and more
preferably 10 to 100, even an average size range of 20 to 60 .mu.m
is possible.
[0213] The particle size distribution, measured by Coulter method
and defined as SPAN of the catalysts of the invention depends on
the way of preparation. With the emulsion/solidification method the
particle size distribution is usually lower than with the
precipitation method. Nevertheless it is desired that the particle
size distribution of the solid catalyst components prepared
according to the precipitation method is as low as possible and
even more preferred similar to that of solid catalyst components
prepared according to the emulsion/solidification method.
[0214] Preferably the particle size distribution is in the range of
0.5 to at most 4.0, more preferable from 0.5 to at most 3.0 and
even more preferably 0.5 to at most 2.0. SPAN is defined as
d 90 [ m ] - d 10 [ m ] d 50 [ m ] ##EQU00001##
where d90 indicates the particle diameter at 90% cumulative size,
d10 indicates the particle diameter at 10% cumulative size, and d50
indicates the particle diameter at 50% cumulative size.
[0215] Preferably the catalyst component in form of solid particles
is prepared by the emulsion/solidification method. By using this
method the catalyst has a narrow particle size distribution (PSD),
below 1.5, preferably below 1.2.
[0216] The catalyst components according to the invention have good
morphology, good particle size distribution and result in
polymerisation catalysts having highly suitable polymerisation
activities.
[0217] Not only the catalyst morphology, but also the catalyst
composition, is of importance in getting the desired properties for
the polymers, like low randomness.
[0218] The catalysts of the invention have, as mentioned above, a
Group 4 metal, preferably Ti content in the range of 1.0 to 10.0 wt
%, preferably 1.5 to 8.5 wt % and more preferably 2.0 to 7.0 wt %;
a Group 2 metal, preferably Mg content in the range of 5.0 to 22.0
wt %, preferably 6.0 to 20.0 wt % and more preferably 6.5 to 18.0
wt %; an Al content in the range of 0.0 to 0.8 wt %, preferably 0.0
to 0.5 wt % and more preferably 0.0 to 0.4 wt %.
[0219] The amount of Ti, Mg and Al is determined by ICP Analysis as
described in the Experimental Part.
[0220] The amount of internal donor is in the range of 1.0 to 60.0
wt %, preferably 10 to 58 wt % and more preferably 20 to 55 wt %
and is determined by HPLC or by GC.
[0221] The maximum amount of donor being possible in the solid
catalyst components can be calculated according to the formula
100-(3.917.times.Mg %+4.941.times.Al %+3.962.times.Ti %)=max amount
of donor (%)
which is based on the assumption that all Mg is in the form of
MgCl.sub.2, all Al is in the form of AlCl.sub.3 and all Ti is in
the form of TiCl.sub.4 and no hydrocarbons are present.
[0222] In addition to the above describe special solid catalyst
component a cocatalyst is used for producing the random propylene
copolymers of the present invention. It is preferred to select the
cocatalyst from the group consisting of trialkylaluminium, like
triethylaluminium (TEA), triisobutylaluminium,
tri-n-butylaluminium; dialkyl aluminium chloride, like dimethyl- or
diethyl aluminium chloride; and alkyl aluminium sesquichloride.
More preferably the cocatalyst is triethylaluminium or
diethylaluminium chloride, most preferably triethylaluminium is
used as cocatalyst.
[0223] Optionally one or more external donor are used, which may be
typically selected e.g. from silanes or any other well known
external donors in the field. External donors are known in the art
and are used as stereoregulating agent in propylene polymerisation.
The external donors are preferably selected from hydrocarbyloxy
silane compounds, amino silane compounds and hydrocarbyloxy alkane
compounds.
[0224] Typical hydrocarbyloxy silane compounds have the formula
(II)
R.sup.7.sub.pSi(OR.sup.8).sub.4-p (II)
wherein R.sup.7 is an alpha- or beta-branched
C.sub.3-C.sub.12-hydrocarbyl, R.sup.8 a
C.sub.1-C.sub.12-hydrocarbyl, and p is an integer 1-3.
[0225] More specific examples of the hydrocarbyloxy silane
compounds which are useful as external electron donors in the
invention are diphenyldimethoxy silane, dicyclopentyldimethoxy
silane, dicyclopentyldiethoxy silane, cyclopentylmethyldimethoxy
silane, cyclopentylmethyldiethoxy silane, dicyclohexyldimethoxy
silane, dicyclohexyldiethoxy silane, cyclohexylmethyldimethoxy
silane, cyclohexylmethyldiethoxy silane, methylphenyldimethoxy
silane, diphenyldiethoxy silane, cyclopentyltrimethoxy silane,
phenyltrimethoxy silane, cyclopentyltriethoxy silane,
phenyltriethoxy silane.
[0226] Most preferably, the alkoxy silane compound having the
formula (II) is dicyclopentyl dimethoxy silane or cyclohexylmethyl
dimethoxy silane.
[0227] Typical amino silane compounds have the formula (III)
Si(OR.sup.9).sub.3(NR.sup.10R.sup.11) (III)
wherein R.sup.9 is a hydrocarbon group having 1 to 6 carbon atoms,
R.sup.10 is a hydrocarbon group having 1 to 12 carbon atoms or
hydrogen atom, and R.sup.11 is a hydrocarbon group having 1 to 12
carbon atoms.
[0228] Preferably these compounds have the formula (IV)
Si(OCH.sub.2CH.sub.3).sub.3(NR.sup.10R.sup.11) (IV)
wherein R.sup.10 and R.sup.11 are independently selected from the
group consisting of linear aliphatic hydrocarbon group having 1 to
12 carbon atoms, branched aliphatic hydrocarbon group having 1 to
12 carbon atoms and cyclic aliphatic hydrocarbon group having 1 to
12 carbon atoms.
[0229] It is in particular preferred that R.sup.10 and R.sup.11 are
independently selected from the group consisting of methyl, ethyl,
n-propyl, n-butyl, octyl, decanyl, iso-propyl, iso-butyl,
iso-pentyl, tert.-butyl, tert.-amyl, neopentyl, cyclopentyl,
cyclohexyl, methylcyclopentyl and cycloheptyl.
[0230] More preferably both R.sup.10 and R.sup.11 are the same and
have 1 to 6 carbon atoms, yet more preferably both R.sup.10 and
R.sup.11 are a C.sub.1-C.sub.4-alkyl group.
[0231] Most preferably the external donor represented by the
formula (III) or (IV) is diethylaminotriethoxy silane.
[0232] The external donor used for the catalyst system is therefore
preferably diethyl aminotriethoxy silane, dicyclopentyl dimethoxy
silane or cyclohexyl methyldimethoxy silane.
EXPERIMENTAL PART
1. Methods
[0233] Melt Flow Rate MFR: ISO 1133; 230.degree. C., 2.16 kg load
Particle Size Distribution PSD: Coulter Counter LS 200 at room
temperature with heptane as medium Mean particle size is given in
.mu.m and measured with Coulter Counter LS200 at room temperature
with n-heptane as medium; particle sizes below 100 .mu.m by
transmission electron microscopy. Median particle size (d50) is
given in .mu.m and measured with Coulter Counter LS200 at room
temperature with n-heptane as medium. Particle size (d10) is given
in .mu.m and measured with Coulter Counter LS200 at room
temperature with n-heptane as medium. Particle size (d90) is given
in .mu.m and measured with Coulter Counter LS200 at room
temperature with n-heptane as medium. SPAN is defined as
follows:
d 90 [ m ] - d 10 [ m ] d 50 [ m ] ##EQU00002##
ICP Analysis (Al, Mg, Ti)
[0234] The elemental analysis of a catalyst was performed by taking
a solid sample of mass, M, cooling over dry ice. Samples were
diluted up to a known volume, V, by dissolving in nitric acid
(HNO.sub.3, 65%, 5% of V) and freshly deionised (DI) water (5% of
V). The solution was further diluted with DI water up to the final
volume, V, and left to stabilize for two hours. The analysis was
run at room temperature using a Thermo Elemental iCAP 6300
Inductively Coupled Plasma--Optical Emmision Spectrometer (ICP-OES)
which was calibrated using a blank (a solution of 5% HNO.sub.3),
and standards of 0.5 ppm, 1 ppm, 10 ppm, 50 ppm, 100 ppm and 300
ppm of Al, Mg and Ti in solutions of 5% HNO.sub.3.
[0235] Immediately before analysis the calibration is `resloped`
using the blank and 100 ppm standard, a quality control sample (20
ppm Al, Mg and Ti in a solution of 5% HNO.sub.3, 3% HF in DI water)
is run to confirm the reslope. The QC sample is also run after
every 5.sup.th sample and at the end of a scheduled analysis
set.
[0236] The content of Mg was monitored using the 285.213 nm line
and the content for Ti using 336.121 nm line. The content of
aluminium was monitored via the 167.079 nm line, when Al
concentration in ICP sample was between 0-10 ppm (calibrated only
to 100 ppm) and via the 396.152 nm line for Al concentrations above
10 ppm.
[0237] The reported values are an average of three successive
aliquots taken from the same sample and are related back to the
original catalyst by inputting the original mass of sample and the
dilution volume into the software.
Determination of Donor Amounts in the Catalyst Components
[0238] The determination of donor amounts in the catalyst
components is performed using HPLC (UV-detector, RP-8 column, 250
mm.times.4 mm). Pure donor compounds are used to prepare standard
solutions. 50-100 mg of the catalyst component is weighed in a 20
ml vial (accuracy of weighing 0.1 mg). 10 ml acetonitrile is added
and the sample suspension is sonicated for 5-10 min in an
ultrasound bath. The acetonitrile suspension is diluted
appropriately and a liquid sample is filtered using 0.45 .mu.m
filter to the sample vial of HPLC instrument. Peak heights are
obtained from HPLC.
[0239] The percentage of donor in the catalyst component is
calculated using the following equation:
Percentage (%)=A.sub.1cVA.sub.2.sup.-1m.sup.-10.1%
where A.sub.1=height of the sample peak c=concentration of the
standard solution (mg/l) V=volume of the sample solution (ml)
A.sub.2=height of the standard peak m=weight of the sample (mg)
Donor Analysis Via GC
[0240] The donor analysis of a catalyst was performed by taking a
solid sample of mass, M, approximately 2 ml of solvent,
dichloromethane, was added. Following this approximately 1 ml of
deionised water was added to the vial. Finally, a known mass, N, of
an internal standard, nonane, was added. The mixture was then
sonicated for 15 min, to ensure full dissolution. After sonication
the sample is left to settle into two phases and an aliquot of the
organic phase is removed, this is then filtered through a 0.45
.mu.m nylon filter into a vial suitable for the gas chromatography
instrument.
[0241] The analysis is performed on a Perkin Elmer Auto System XL
Gas Chromatograph containing a split loop injector and flame
ionization detector. The column is a DB-1, 30 m long with an inner
diameter of 0.32 mm and a phase thickness of 0.25 .mu.m. The system
stays at 40.degree. C. for 5 minutes before ramping at 10.degree.
C./min up to 250.degree. C., the system is kept at temperature for
a further 4 minutes. If required the peak temperature could be
raised to 300.degree. C.
[0242] The results are calculated in the following manner:
Component ( wt % ) = Ax .times. F .times. N Ay .times. Fistd
.times. M .times. 100 ##EQU00003##
where: Ax=component area F=component factor N mass of internal
standard (nonane), mg Ay=area of internal standard (nonane)
Fistd=factor of internal standard (nonane) M=mass of the sample, mg
Xylene solubles XS: Xylene soluble fraction of product at
25.degree. C.
[0243] 2.0 g of polymer are dissolved in 250 ml p-xylene at
135.degree. C. under agitation. After 30.+-.2 minutes the solution
is allowed to cool for 15 minutes at ambient temperature and then
allowed to settle for 30 minutes at 25.+-.0.5.degree. C. The
solution is filtered with filter paper into two 100 ml flasks.
[0244] The solution from the first 100 ml vessel is evaporated in
nitrogen flow and the residue is dried under vacuum at 90.degree.
C. until constant weight is reached.
XS %=(100.times.ml.times.v0)/(m0.times.v1)
m0=initial polymer amount (g) m1=weight of residue (g) v0=initial
volume (ml) v1=volume of analyzed sample (ml)
Randomness
[0245] Infrared (IR) spectroscopy was undertaken on Nicolet Magna
IR Spectrometer 550. A 220-250 .mu.m film was prepared from the
polymer powder at 230.degree. C. followed by rapid cooling to room
temperature. All IR analysis was done within two hours of film
preparation. Quantitative comonomer contents were obtained using
peak areas normalised to the peak height of an internal reference
band calibrated to previous .sup.13C NMR results. Ethylene was
quantified using the band at 733 cm.sup.-1 (baseline 690-780
cm.sup.-1) the reference band at 809 cm.sup.-1 (baseline 750-890
cm.sup.-1). The amount of isolated ethylene units (randomness) was
estimated using the peak height of the band at 733 cm.sup.-1
(baseline 690-780 cm.sup.-1) and the same reference band described
above. Calibration was made to previously obtained .sup.13C NMR
results.
Randomness=random ethylene (--P-E-P--) content/the total ethylene
content.times.100%.
All reactions in the examples as described are carried out under
inert conditions.
EXAMPLES
Example 1
Diether as Internal Donor
Preparation of Mg-Alkoxide
[0246] A magnesium alkoxide solution was prepared by adding, with
stirring, 220.0 ml of a 20% solution in toluene of BOMAG
(Mg(Bu).sub.1,5(Oct).sub.0,5, from Crompton GmbH) to a mixture of
50.0 ml 2-ethylhexanol (from Merck Chemicals) and 25.0 ml
butoxypropanol (from Sigma-Aldrich) (molar ratio
2-ethylhexanol/butoxypropanol=1.9, and molar ratio alcohol/Mg=2,2)
in a 300 ml glass reactor during 80 minutes. During the addition
the reactor contents were maintained below 25.degree. C. After
addition of the BOMAG was completed, mixing of the reaction mixture
at 25.degree. C. was continued for another 60 minutes. The
temperature of the reaction mixture was then raised to 60.degree.
C. within 14 minutes and held at that temperature for 60 minutes
with stirring, at which time reaction was complete.
Preparation of Solid Catalyst Component:
[0247] In a 300 ml glass reactor 20 ml of TiCl.sub.4 and 10 ml of
heptane were heated to 90.degree. C. Mixing speed was set to 150
rpm. Then a mixture of 30 ml Mg-alkoxide, prepared as described
above, 2.0 ml 3,3-bis(ethoxymethyl)-2,6-dimethylheptane as donor
and 2 ml of Viscoplex was slowly added. After 30 minutes mixing was
stopped and the catalyst particles were allowed to settle down.
After settling, liquid was syphonated away to about 20 ml level.
Then the catalyst particles were washed with 100 ml of toluene at
90.degree. C. for 0.5 h, followed by two heptane (each: 100 ml, 30
min) washes and finally one pentane wash (100 ml, 30 min).
[0248] During the second heptane wash temperature was decreased to
room temperature.
Example 2
Maleate as Internal Donor
2a) Preparation of Mg-Alkoxide
[0249] 43.9 ml of 2-ethylhexanol were added to a 300 ml glass
reactor. 123.9 ml of a 20% solution in toluene of BOMAG (butyl
octyl magnesium) provided by Crompton GmbH were slowly added to the
well stirred 2-ethyl hexanol. During the addition the temperature
was kept below 40.degree. C. Then the temperature of the reaction
mixture was raised to 60.degree. C. and mixing was continued at
this temperature for 60 minutes. Finally the Mg-alkoxide was
transferred to septa bottles after cooling to room temperature.
2b) Preparation of Mg-Complex
[0250] 10.04 ml (8.87 g) of the Mg-alkoxide prepared according to
Example 2a) were placed in a septa bottle (N.sub.2 atmosphere,
equipped with a magnetic stir bar). 4.96 ml (4.33 g) of the
Mg-alkoxide prepared according to Example 5 were added at room
temperature. Then 1.19 g of diethyl-2-cyclohexyl maleate were added
at room temperature and the reaction mixture was mixed for 10
minutes at room temperature.
2c) Preparation of Catalyst Component
[0251] 6.5 ml titanium tetrachloride were placed in a 50 ml glass
reactor equipped with a mechanical stirrer at 25.degree. C. Mixing
speed was adjusted to 400 rpm. 4.2 ml of a mixture consisting of
0.30 ml of a solution in toluene of 0.60 mg Necadd 447, 0.6 ml of a
50 wt % solution in toluene of Viscoplex 1-254 and 3.30 ml heptane
was added at once. Then the reactor temperature was raised to
90.degree. C. within 5 minutes. When the temperature is reached
11.0 ml of the Mg-complex prepared according to Example 2b were
added within 15 minutes with constant feed rate, whereby the
temperature was kept at 90.degree. C. during the addition. The
reaction mixture was stirred for further 30 minutes at 90.degree.
C. Afterwards stirring was stopped and the reaction mixture was
allowed to settle for 15 minutes at 90.degree. C.
[0252] After settling and siphoning the solids underwent 3 washing
steps:
Wash 1: Toluene/DEAC Wash
[0253] Washing with a mixture of 0.03 ml diethyl aluminum chloride
and 33 ml of toluene at 90.degree. C. for 30 minutes under stirring
with 300 rpm. Afterwards stirring was stopped and the reaction
mixture was allowed to settle for 15 minutes at 90.degree. C. with
subsequent siphoning.
Wash 2: 1.sup.st Heptane Wash
[0254] Washing with 20 ml of heptane at 90.degree. C. for 7 minutes
under stirring with 300 rpm. Afterwards the reaction temperature is
decreased to 25.degree. C. during 13 minutes. Then stirring was
stopped and the reaction mixture was allowed to settle for 15
minutes at 25.degree. C. with subsequent siphoning.
Wash 3: 2.sup.nd Heptane Wash
[0255] Washing with 20 ml of heptane at 25.degree. C. for 20
minutes under stirring with 300 rpm. Afterwards stirring was
stopped and the reaction mixture was allowed to settle for 10
minutes at 25.degree. C. with subsequent siphoning.
[0256] Finally, the temperature was increased to 70.degree. C.
during 7 minutes followed by N.sub.2 sparging for 20 minutes, to
yield an airsensitive powder.
Example 3
Maleate as Internal Donor
3a) Preparation of Mg-Alkoxide
[0257] 43.9 ml of 2-ethylhexanol were added to a 300 ml glass
reactor. 123.9 ml of a 20% solution in toluene of BOMAG (butyl
octyl magnesium) provided by Crompton GmbH were slowly added to the
well stirred 2-ethyl hexanol. During the addition the temperature
was kept below 40.degree. C. Then the temperature of the reaction
mixture was raised to 60.degree. C. and mixing was continued at
this temperature for 60 minutes. Finally the Mg-alkoxide was
transferred to septa bottles after cooling to room temperature.
3b) Preparation of Mg-Alkoxide
[0258] 41.4 ml of propylene glycol butyl ether were added to a 300
ml glass reactor. 123.9 ml of a 20% solution in toluene of BOMAG
provided by Crompton GmbH were slowly added to the well stirred
propylene glycol butyl ether. During the addition the temperature
was kept below 40.degree. C. Then the temperature of the reaction
mixture was raised to 60.degree. C. and mixing was continued at
this temperature for 60 minutes. Finally the Mg-alkoxide was
transferred to septa bottles after cooling to room temperature.
3c) Preparation of Mg-Complex
[0259] 10.04 ml (8.87 g) of the Mg-alkoxide prepared according to
Example 3a were placed in a septa bottle (N.sub.2 atmosphere,
equipped with a magnetic stir bar). 4.96 ml (4.33 g) of the
Mg-alkoxide prepared according to Example 3b) were added at room
temperature. Then 1.07 g of diethyl-2-isobutyl maleate were added
slowly at room temperature and the reaction mixture was mixed for
10 minutes at room temperature
3d) Preparation of Catalyst Component
[0260] 6.5 ml titanium tetrachloride was placed in a 50 ml glass
reactor equipped with a mechanical stirrer at 25.degree. C. Mixing
speed was adjusted to 400 rpm. 4.2 ml of a mixture consisting of
0.30 ml of a solution in toluene of 0.60 mg Necadd 447, 0.6 ml of a
50 wt % solution in toluene of Viscoplex 1-254 and 3.30 ml heptane
was added at once. Then the reactor temperature was raised to
90.degree. C. within 5 minutes. When the temperature is reached
11.0 ml of the Mg-complex prepared according to Example 3c were
added within 15 minutes with constant feed rate, whereby the
temperature was kept at 90.degree. C. during the addition. The
reaction mixture was stirred for further 30 minutes at 90.degree.
C. Afterwards stirring was stopped and the reaction mixture was
allowed to settle for 15 minutes at 90.degree. C.
[0261] After settling and siphoning the solids underwent 3 washing
steps:
Wash 1: Toluene/DEAC Wash
[0262] Washing with a mixture of 0.03 ml diethyl aluminum chloride
and 33 ml of toluene at 90.degree. C. for 30 minutes under stirring
with 300 rpm. Afterwards stirring was stopped and the reaction
mixture was allowed to settle for 15 minutes at 90.degree. C. with
subsequent siphoning.
Wash 2: 1.sup.st Heptane Wash
[0263] Washing with 20 ml of heptane at 90.degree. C. for 7 minutes
under stirring with 300 rpm. Afterwards the reaction temperature is
decreased to 25.degree. C. during 13 minutes. Then stirring was
stopped and the reaction mixture was allowed to settle for 15
minutes at 25.degree. C. with subsequent siphoning.
[0264] Wash 3: 2.sup.nd Heptane Wash
[0265] Washing with 20 ml of heptane at 25.degree. C. for 20
minutes under stirring with 300 rpm. Afterwards stirring was
stopped and the reaction mixture was allowed to settle for 10
minutes at 25.degree. C. with subsequent siphoning.
[0266] Finally, the temperature was increased to 70.degree. C.
during 7 minutes followed by N.sub.2 sparging for 20 minutes, to
yield an airsensitive powder.
Example 4
Benzoate as Internal Donor
4a) Preparation of Mg-Alkoxide
[0267] 43.9 ml of 2-ethylhexanol were added to a 300 ml glass
reactor. 123.9 ml of a 20% solution in toluene of BOMAG (butyl
octyl magnesium) provided by Crompton GmbH were slowly added to the
well stirred 2-ethyl hexanol. During the addition the temperature
was kept below 40.degree. C. Then the temperature of the reaction
mixture was raised to 60.degree. C. and mixing was continued at
this temperature for 60 minutes. Finally the Mg-alkoxide was
transferred to septa bottles after cooling to room temperature.
4b) Preparation of Mg-Complex
[0268] 14.0 ml (12.32 g) of the Mg-alkoxide prepared according to
Example 4a were placed in a septa bottle (N.sub.2 atmosphere,
equipped with a magnetic stir bar). 1.28 ml (1.29 g) of
4-tert.-butylbenzoylchloride were slowly added at room temperature.
Then the reaction mixture was mixed for 1 hour at room temperature,
followed by mixing at 60.degree. C. for one further hour.
4c) Preparation of Catalyst Component
[0269] 6.5 ml titanium tetrachloride were placed in a 50 ml glass
reactor equipped with a mechanical stirrer at 25.degree. C. Mixing
speed was adjusted to 400 rpm. 4.2 ml of a mixture consisting of
0.30 ml of a solution in toluene of 0.60 mg Necadd 447, 0.6 ml of a
50 wt % solution in toluene of Viscoplex 1-254 and 3.30 ml heptane
was added at once. Then the reactor temperature was raised to
90.degree. C. within 5 minutes. When the temperature is reached
11.0 ml of the Mg-complex prepared according to Example 4b) were
added within 15 minutes with constant feed rate, whereby the
temperature was kept at 90.degree. C. during the addition. The
reaction mixture was stirred for further 30 minutes at 90.degree.
C. Afterwards stirring was stopped and the reaction mixture was
allowed to settle for 15 minutes at 90.degree. C.
[0270] After settling and siphoning the solids underwent 3 washing
steps:
Wash 1: Toluene/DEAC Wash
[0271] Washing with a mixture of 0.03 ml diethyl aluminum chloride
and 33 ml of toluene at 90.degree. C. for 30 minutes under stirring
with 300 rpm. Afterwards stirring was stopped and the reaction
mixture was allowed to settle for 15 minutes at 90.degree. C. with
subsequent siphoning.
Wash 2: 1.sup.st Heptane Wash
[0272] Washing with 20 ml of heptane at 90.degree. C. for 7 minutes
under stirring with 300 rpm. Afterwards the reaction temperature is
decreased to 25.degree. C. during 13 minutes. Then stirring was
stopped and the reaction mixture was allowed to settle for 15
minutes at 25.degree. C. with subsequent siphoning.
Wash 3: 2.sup.nd Heptane Wash
[0273] Washing with 20 ml of heptane at 25.degree. C. for 20
minutes under stirring with 300 rpm. Afterwards stirring was
stopped and the reaction mixture was allowed to settle for 10
minutes at 25.degree. C. with subsequent siphoning.
[0274] Finally, the temperature was increased to 70.degree. C.
during 7 minutes followed by N.sub.2 sparging for 20 minutes, to
yield an airsensitive powder.
Example 5
Benzoate as Internal Donor
5a) Preparation of Mg-Alkoxide
[0275] 43.9 ml of 2-ethylhexanol were added to a 300 ml glass
reactor. 123.9 ml of a 20% solution in toluene of BOMAG (butyl
octyl magnesium) provided by Crompton GmbH were slowly added to the
well stirred 2-ethyl hexanol. During the addition the temperature
was kept below 40.degree. C. Then the temperature of the reaction
mixture was raised to 60.degree. C. and mixing was continued at
this temperature for 60 minutes. Finally the Mg-alkoxide was
transferred to septa bottles after cooling to room temperature.
5b) Preparation of Mg-Alkoxide
[0276] 41.4 ml of propylene glycol butyl ether were added to a 300
ml glass reactor. 123.9 ml of a 20% solution in toluene of BOMAG
provided by Crompton GmbH were slowly added to the well stirred
propylene glycol butyl ether. During the addition the temperature
was kept below 40.degree. C. Then the temperature of the reaction
mixture was raised to 60.degree. C. and mixing was continued at
this temperature for 60 minutes. Finally the Mg-alkoxide was
transferred to septa bottles after cooling to room temperature.
5c) Preparation of Mg-Complex
[0277] 6.10 ml (5.35 g) of the Mg-alkoxide prepared according to
Example 5a) were placed in a septa bottle (N.sub.2 atmosphere,
equipped with a magnetic stir bar). 0.50 g of the donor precursor
2-(4-chlorobenzoyl)benzoylchloride (95%, obtained from StruChem)
were added at room temperature, followed by addition of 3.01 ml
(2.68 g) of the Mg-alkoxide prepared according to Example 5b). The
temperature of the reaction was then raised to 60.degree. C. and
mixing was continued for one hour. After cooling to room
temperature the Mg-complex was transferred to septa bottles.
5d) Preparation of Catalyst Component
[0278] 6.5 ml titanium tetrachloride were placed in a 50 ml glass
reactor equipped with a mechanical stirrer at 25.degree. C. Mixing
speed was adjusted to 400 rpm. 4.2 ml of a mixture consisting of
0.30 ml of a solution in toluene of 0.60 mg Necadd 447, 0.6 ml of a
50 wt % solution in toluene of Viscoplex 1-254 and 3.30 ml heptane
was added at once. Then the reactor temperature was raised to
90.degree. C. within 5 minutes. When the temperature is reached
11.0 ml of the Mg-complex prepared according to Example 5c) were
added within 15 minutes with constant feed rate, whereby the
temperature was kept at 90.degree. C. during the addition. The
reaction mixture was stirred for further 30 minutes at 90.degree.
C. Afterwards stirring was stopped and the reaction mixture was
allowed to settle for 15 minutes at 90.degree. C. After settling
and siphoning the solids underwent 3 washing steps:
Wash 1: Toluene/DEAC Wash
[0279] Washing with a mixture of 0.03 ml diethyl aluminum chloride
and 33 ml of toluene at 90.degree. C. for 30 minutes under stirring
with 300 rpm. Afterwards stirring was stopped and the reaction
mixture was allowed to settle for 15 minutes at 90.degree. C. with
subsequent siphoning.
Wash 2: 1.sup.st Heptane Wash
[0280] Washing with 20 ml of heptane at 90.degree. C. for 7 minutes
under stirring with 300 rpm. Afterwards the reaction temperature is
decreased to 25.degree. C. during 13 minutes. Then stirring was
stopped and the reaction mixture was allowed to settle for 15
minutes at 25.degree. C. with subsequent siphoning.
Wash 3: 2.sup.nd Heptane Wash
[0281] Washing with 20 ml of heptane at 25.degree. C. for 20
minutes under stirring with 300 rpm. Afterwards stirring was
stopped and the reaction mixture was allowed to settle for 10
minutes at 25.degree. C. with subsequent siphoning.
[0282] Finally, the temperature was increased to 70.degree. C.
during 7 minutes followed by N.sub.2 sparging for 20 minutes, to
yield an airsensitive powder.
Example 6
Cyclohexene as Internal Donor
6a) Preparation of a Soluble Mg-Alkoxy Compound (Ax):
[0283] 43.9 ml of 2-ethyl hexanol (from Merck Chemicals) were added
to a 300 ml glass reactor equipped with a mechanical stirrer. 123.9
ml of a 20% solution in toluene of BOMAG
(Mg(Bu).sub.1,5(Oct).sub.0,5, from Crompton GmbH) were then added
within 125 minutes to the well stirred 2-ethyl hexanol, whereby the
temperature was kept below 30.degree. C. The temperature was then
increased to 60.degree. C. and mixing was continued at this
temperature for 1 hour. Finally, the Mg-alkoxide was transferred to
a septa bottle after cooling to room temperature.
6b) Preparation of Mg Complex (Ac):
[0284] 19.3 g of the Mg-alkoxide prepared according to Example 6a)
were placed in a 50 ml glass reactor (N.sub.2 atmosphere, equipped
with a magnetic stir bar). 1.10 ml of cyclohex-1-ene-1,2-dicarbonly
dichloride was then added at room temperature within 15 minutes.
The reaction mixture was stirred over night at room temperature to
ensure complete reaction.
6c) Preparation of the Catalyst According to the
Emulsion-Solidification Method
[0285] 6.5 ml TiCl.sub.4 were placed in a 50 ml glass reactor
equipped with a mechanical stirrer and the reactor temperature was
set to 0.degree. C. Mixing speed was adjusted to 300 rpm. 11.0 ml
of the Mg-complex prepared according to Example 6b were added
within 15 minutes with constant feed rate. During the addition the
temperature was kept at 0.degree. C. The temperature was raised to
25.degree. C. and 4.2 ml of a mixture consisting of 0.30 ml of a
solution in toluene of 0.60 mg Necadd 447, 0.6 ml of a 50 wt %
solution in toluene of Viscoplex 1-254 and 3.30 ml heptane was
added at once. The thus obtained reaction mixture was stirred for
20 minutes at 25.degree. C. The temperature of the reaction mixture
was then increased to 90.degree. C. over a period of 20 minutes
(linear heat-up profile) and held at that level for 30 minutes with
stirring. Afterwards stirring was stopped, and the reaction mixture
was allowed to settle for 15 minutes at 90.degree. C.
[0286] After settling and removing of the supernatant liquid the
solids underwent 3 washing steps:
Wash 1: Toluene/Diethylaluminium Chloride (DEAC) Wash
[0287] Washing with a mixture of 0.03 ml diethyl aluminum chloride
and 33 ml of toluene at 90.degree. C. for 30 minutes under stirring
with 300 rpm. Afterwards stirring was stopped and the reaction
mixture was allowed to settle for 15 minutes at 90.degree. C. with
subsequent siphoning.
Wash 2: 1.sup.st Heptane Wash
[0288] Washing with 20 ml of heptane at 90.degree. C. for 7 minutes
under stirring with 300 rpm. Afterwards the reaction temperature is
decreased to 25.degree. C. during 13 minutes. Then stirring was
stopped and the reaction mixture was allowed to settle for 15
minutes at 25.degree. C. with subsequent siphoning.
Wash 3: 2.sup.nd Heptane Wash
[0289] Washing with 20 ml of heptane at 25.degree. C. for 20
minutes under stirring with 300 rpm. Afterwards stirring was
stopped and the reaction mixture was allowed to settle for 10
minutes at 25.degree. C. with subsequent siphoning
[0290] Finally, the catalyst slurry was dried at room temperature
by N.sub.2 sparging for 2 hours, to yield a brown, air sensitive
powder.
Comparative Example 1: CE1
[0291] As Comparative Example a catalyst prepared by the
emulsion/solidification method according to Example 5 of EP 1403292
using phthaloyl dichloride as internal catalyst precursor
(Mg-complex was prepared according to Example 1 of EP 1403292). The
resulting internal donor is diethylhexyl phthalate
TABLE-US-00001 TABLE 1 Composition of the catalyst components
Catalyst Ti [wt %] Mg [wt %] Al [wt %] Donor [wt %] Example 1 3.31
14.7 -- 17.6.sup.1 Example 2 2.98 13.5 0.50 35.1.sup.2 Example 3
4.24 15.1 0.12 38.1.sup.2 Example 4 3.34 11.0 0.07 43.3.sup.2
Example 5 2.68 10.9 0.27 45.4.sup.2 Example 6 2.4 12.8 0.36
38.6.sup.2 CE1 3.5 13.2 0.4 29.9.sup.3 .sup.1measured amount using
GC. .sup.2The maximum amount of donor being possible in the solid
catalyst components can be calculated according to the formula 100
- (3.917 * Mg % + 4.941 * Al % + 3.962 * Ti %) = max amount of
donor (%) which is based on the assumption that all Mg is in the
form of MgCl.sub.2, all Al is in the form of AlCl.sub.3 and all Ti
is in the form of TiCl.sub.4 and no hydrocarbons are present.
.sup.3measured amount of bis(2-ethylhexyl)phthalate using HPLC
Example 7
Copolymerisation
[0292] A 5 litre stainless steel reactor was used for propylene
polymerisations.
[0293] Triethyl aluminium (TEA) (from Witco, used as received) as a
co-catalyst, dicyclopentyl dimethoxy silane (DCDS) (from Wacker,
dried with molecular sieves) as an external donor and 30 ml
n-pentane were mixed and allowed to react for 5 minutes. Half of
the mixture was then added to the polymerisation reactor and the
other half was mixed with the catalyst. After additional 5 minutes
the catalyst/TEA/donor/n-pentane mixture was added to the reactor.
Hydrogen and 1400 g propylene were introduced into the reactor and
the temperature was raised within ca 15 minutes to the
polymerisation temperature (70.degree. C.). Ethylene feed was
started 5 minutes after starting the temperature increase (at about
40.degree. C.) and ethylene was fed continuously throughout the
polymerisation. The polymerisation time at 70.degree. C. was 60
minutes, after which the polymer formed was taken out from the
reactor.
TABLE-US-00002 TABLE 3 Polymerisation results Catalyst Ex 1 Ex 2 Ex
3 Ex 4 Ex 5 Ex 6 Catalyst amount [mg] 11.2 18.1 24.2 30.2 18.1 50.4
Al/Ti [mol/mol] 250 250 250 150 250 150 TEAL [.mu.l] 264 496 724
431 348 510 DCDS [.mu.l] 45 84 123 73 59 86 H.sub.2 [mmol] 130 300
300 300 300 300 C.sub.2-feed in total [g] 26.6 26.6 26.6 26.6 26.6
26.6 C.sub.2-content [wt %] 4.2 3.5 4.7 4.2 3.5 4.0 MFR.sub.2 [g/10
min] 9.3 5.8 5.7 7.6 8.0 12.0 Randomness [%] 71.3 71.9 67.0 71.2
74.0 71.9 XS [wt %] 9.0 6.9 10.7 9.6 5.3 8.3
Comparative Example 2
[0294] As Comparative Example 2 the catalyst from CE1 was used and
polymerisation was performed using different amounts of
ethylene.
[0295] The results compared to the polymers according to the
invention can be seen in FIG. 1 (XS vs. C.sub.2) and FIG. 2
(randomness vs. C.sub.2)
[0296] As can be seen from the figures, especially FIG. 2 the
randomness of the random propylene copolymers is--at a given
comonomer content--at least 3% lower than the randomness of the
comparative random propylene copolymer produced with a phthalate
containing donor.
* * * * *