U.S. patent application number 10/930452 was filed with the patent office on 2005-02-10 for propylene polymers.
This patent application is currently assigned to Basell Poliolefine Italia S.p.A.. Invention is credited to Balbontin, Giulio, Duijghuisen, Henricus P.B., Gulevich, Yuri.v, Kelder, Remco T., Klusener, Peter A.A., Korndorffer, Franciscus M., Morini, Giampiero.
Application Number | 20050032633 10/930452 |
Document ID | / |
Family ID | 8240100 |
Filed Date | 2005-02-10 |
United States Patent
Application |
20050032633 |
Kind Code |
A1 |
Morini, Giampiero ; et
al. |
February 10, 2005 |
Propylene polymers
Abstract
The present invention relates to a solid catalyst component for
the polymerization of olefins CH.sub.2.dbd.CHR in which R is
hydrogen or a hydrocarbon radical with 1-12 carbon atoms,
comprising Mg, Ti, halogen and an electron donor selected from
substituted succinates of a particular formula. Said catalyst
components when used in the polymerization of olefins, and in
particular of propylene, are capable to give polymers in high
yields and with high isotactic index expressed in terms of high
xylene insolubility.
Inventors: |
Morini, Giampiero; (Padova,
IT) ; Balbontin, Giulio; (Ferrara, IT) ;
Gulevich, Yuri.v; (Elkton, MD) ; Duijghuisen,
Henricus P.B.; (Almere, NL) ; Kelder, Remco T.;
(Hoevelaken, NL) ; Klusener, Peter A.A.; (Utrecht,
NL) ; Korndorffer, Franciscus M.; (Katwijk aan zee,
NL) |
Correspondence
Address: |
BASELL USA INC.
INTELLECTUAL PROPERTY
912 APPLETON ROAD
ELKTON
MD
21921
US
|
Assignee: |
Basell Poliolefine Italia
S.p.A.
Milan
IT
|
Family ID: |
8240100 |
Appl. No.: |
10/930452 |
Filed: |
August 31, 2004 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10930452 |
Aug 31, 2004 |
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09762363 |
Feb 5, 2001 |
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6818583 |
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09762363 |
Feb 5, 2001 |
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PCT/EP00/03333 |
Apr 12, 2000 |
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Current U.S.
Class: |
502/118 ;
502/125; 502/126; 502/127; 526/125.3; 526/128; 526/348.5;
526/348.6; 526/351; 526/352; 526/904 |
Current CPC
Class: |
C08F 210/16 20130101;
C08F 110/06 20130101; C08F 10/00 20130101; C08F 10/00 20130101;
C08F 4/6465 20130101; C08F 10/00 20130101; C08F 4/6492 20130101;
C08F 10/00 20130101; C08F 4/651 20130101; C08F 10/00 20130101; C08F
4/6494 20130101; C08F 110/06 20130101; C08F 2500/12 20130101; C08F
2500/20 20130101; C08F 210/16 20130101; C08F 210/08 20130101; C08F
2500/12 20130101; C08F 2500/20 20130101 |
Class at
Publication: |
502/118 ;
502/125; 502/126; 502/127; 526/125.3; 526/128; 526/904; 526/348.5;
526/348.6; 526/351; 526/352 |
International
Class: |
B01J 031/00; C08F
004/44 |
Foreign Application Data
Date |
Code |
Application Number |
Apr 15, 1999 |
EP |
99201172.6 |
Claims
1-38. (canceled).
39. Propylene polymers characterized in that they have a
polydispersity index of higher than 5, a content of isotactic units
expressed in terms of pentads of higher than 97% and a flexural
modulus of at least 2000 MPa.
40. The propylene polymers according to claim 39 in which the
polydispersity index is higher than 5.1, the flexural modulus is
higher than 2100 MPa and the content of isotactic units expressed
in terms of pentads is higher than 97.5%.
Description
[0001] The present invention relates to catalyst components for the
polymerization of olefins, to the catalyst obtained therefrom and
to the use of said catalysts in the polymerization of olefins
CH.sub.2.dbd.CHR in which R is hydrogen or a hydrocarbyl radical
with 1-12 carbon atoms. In particular the present invention relates
to catalyst components, suitable for the stereospecific
polymerization of olefins, comprising Ti, Mg, halogen and an
electron donor compound selected from esters of substituted
succinic acids (substituted succinates). Said catalyst components
when used in the polymerization of olefins, and in particular of
propylene, are capable to give polymers in high yields and with
high isotactic index expressed in terms of high xylene
insolubility.
[0002] The chemical class of succinates is known in the art.
However, the specific succinates of the present invention have
never been used as internal electron donors in catalysts for the
polymerization of olefins.
[0003] EP-A-86473 mentions the use of unsubstituted succinates as
internal donors in catalyst components for the polymerization of
olefins. The use of diisobutyl succinate and di-n-butyl succinate
is also exemplified. The results obtained in terms of isotactic
index and yields are however poor.
[0004] The use of polycarboxylic acid esters, including succinates,
as internal donors in catalyst components for the polymerization of
olefins, is also generically disclosed in EP 125911. Diethyl
methylsuccinate and diallyl ethylsuccinate are mentioned in the
description although they are not exemplified. Furthermore,
EP263718 mentions, but does not exemplify the use of diethyl
methylsuccinate and di-n-butyl ethylsuccinate as internal donors.
In order to check the performances of these succinates according to
the teaching of the art the applicant has carried out some
polymerization tests employing catalyst components containing
diethyl methylsuccinate and diisobutyl ethylsuccinate,
respectively, as internal donors. As shown in the experimental
section, both the so obtained catalysts gave an unsatisfactory
activity/stereospecificity balance very similar to that obtained
with catalysts containing unsubstituted succinates.
[0005] It has been therefore very surprising to discover that the
specific substitution in the succinates of the invention generates
compounds that, when used as internal donors, give catalyst
components having excellent activity and stereospecificity.
[0006] It is therefore an object of the present invention to
provide a solid catalyst component for the polymerization of
olefins CH.sub.2.dbd.CHR in which R is hydrogen or a hydrocarbon
radical with 1-12 carbon atoms, comprising Mg, Ti, halogen and an
electron donor selected from succinates of formula (I): 1
[0007] wherein the radicals R.sub.1 and R.sub.2, equal to, or
different from, each other are a C.sub.1-C.sub.20 linear or
branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl or alkylaryl
group, optionally containing heteroatoms; the radicals R.sub.3 to
R.sub.6 equal to, or different from, each other, are hydrogen or a
C.sub.1-C.sub.20 linear or branched alkyl, alkenyl, cycloalkyl,
aryl, arylalkyl or alkylaryl group, optionally containing
heteroatoms, and the radicals R.sub.3 to R.sub.6 which are joined
to the same carbon atom can be linked together to form a cycle;
with the proviso that when R.sub.3 to R.sub.5 are contemporaneously
hydrogen R.sub.6 is a radical selected from primary branched,
secondary or tertiary alkyl groups, cycloalkyl, aryl, arylalkyl or
alkylaryl groups having from 3 to 20 carbon atoms.
[0008] R.sub.1 and R.sub.2 are preferably C.sub.1-C.sub.8 alkyl,
cycloalkyl, aryl, arylalkyl and alkylaryl groups. Particularly
preferred are the compounds in which R.sub.1 and R.sub.2 are
selected from primary alkyls and in particular branched primary
alkyls. Examples of suitable R.sub.1 and R.sub.2 groups are methyl,
ethyl, n-propyl, n-butyl, isobutyl, neopentyl, 2-ethylhexyl.
Particularly preferred are ethyl, isobutyl, and neopentyl. One of
the preferred groups of compounds described by the formula (I) is
that in which R.sub.3 to R.sub.5 are hydrogen and R.sub.6 is a
branched alkyl, cycloalkyl, aryl, arylalkyl and alkylaryl radical
having from 3 to 10 carbon atoms. Particularly preferred are the
compounds in which R.sub.6 is a branched primary alkyl group or a
cycloalkyl group having from 3 to 10 carbon atoms.
[0009] Specific examples of suitable monosubstituted succinate
compounds are diethyl sec-butylsuccinate, diethyl thexylsuccinate,
diethyl cyclopropylsuccinate, diethyl norbornylsuccinate, diethyl
(10-)perhydronaphthylsuccinate, diethyl trimethylsilylsuccinate,
diethyl methoxysuccinate, diethyl p-methoxyphenylsuccinate, diethyl
p-chlorophenylsuccinate diethyl phenylsuccinate, diethyl
cyclohexylsuccinate, diethyl benzylsuccinate, diethyl
(cyclohexylmethyl)succinate, diethyl t-butylsuccinate, diethyl
isobutylsuccinate, diethyl isopropylsuccinate, diethyl
neopentylsuccinate, diethyl isopentylsuccinate, diethyl
(1,1,1-trifluoro-2-propyl)succinate, diethyl
(9-fluorenyl)succinate, diisobutyl phenylsuccinate, diisobutyl
sec-butylsuccinate, diisobutyl thexylsuccinate, diisobutyl
cyclopropylsuccinate, diisobutyl (2-norbornyl)succinate, diisobutyl
(10-)perhydronaphthylsuccinate, diisobutyl trimethylsilylsuccinate,
diisobutyl methoxysuccinate, diisobutyl p-methoxyphenylsuccinate,
diisobutyl p-chlorophenylsuccinate, diisobutyl cyclohexylsuccinate,
diisobutyl benzylsuccinate, diisobutyl (cyclohexylmethyl)succinate,
diisobutyl t-butylsuccinate, diisobutyl isobutylsuccinate,
diisobutyl isopropylsuccinate, diisobutyl neopentylsuccinate,
diisobutyl isopentylsuccinate, diisobutyl
(1,1,1-trifluoro-2-propyl)succinate, diisobutyl
(9-fluorenyl)succinate, dineopentyl sec-butylsuccinate, dineopentyl
thexylsuccinate, dineopentyl cyclopropylsuccinate, dineopentyl
(2-norbornyl)succinate, dineopentyl (10-)perhydronaphthylsuccinate,
dineopentyl trimethylsilylsuccinate, dineopentyl methoxysuccinate,
dineopentyl p-methoxyphenylsuccinate, dineopentyl
p-chlorophenylsuccinate, dineopentyl phenylsuccinate, dineopentyl
cyclohexylsuccinate, dineopentyl benzylsuccinate, dineopentyl
(cyclohexylmethyl)succinate, dineopentyl t-butylsuccinate,
dineopentyl isobutylsuccinate, dineopentyl isopropylsuccinate,
dineopentyl neopentylsuccinate, dineopentyl isopentylsuccinate,
dineopentyl (1,1,1-trifluoro-2-propyl)succinate, dineopentyl
(9-fluorenyl)succinate.
[0010] Another preferred group of compounds within those of formula
(I) is that in which at least two radicals from R.sub.3 to R.sub.6
are different from hydrogen and are selected from C.sub.1-C.sub.20
linear or branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl or
alkylaryl group, optionally containing heteroatoms. Particularly
preferred are the compounds in which the two radicals different
from hydrogen are linked to the same carbon atom. Specific examples
of suitable 2,2-disubstituted succinates are: diethyl
2,2-dimethylsuccinate, diethyl 2-ethyl-2-methylsuccinate, diethyl
2-benzyl-2-isopropylsuccinate, diethyl
2-(cyclohexylmethyl)-2-isobutylsuccinate, diethyl
2-cyclopentyl-2-n-propy- lsuccinate, diethyl
2,2-diisobutylsuccinate, diethyl 2-cyclohexyl-2-ethylsuccinate,
diethyl 2-isopropyl-2-methylsuccinate, diethyl 2,2-diisopropyl
diethyl 2-isobutyl-2-ethylsuccinate, diethyl
2-(1,1,1-trifluoro-2-propyl)-2-methylsuccinate, diethyl
2-isopentyl-2-isobutylsuccinate, diethyl
2-phenyl-2-n-butylsuccinate, diisobutyl 2,2-dimethylsuccinate,
diisobutyl 2-ethyl-2-methylsuccinate, diisobutyl
2-benzyl-2-isopropylsuccinate, diisobutyl
2-(cyclohexylmethyl)-2-isobutylsuccinate, diisobutyl
2-cyclopentyl-2-n-propylsuccinate, diisobutyl
2,2-diisobutylsuccinate, diisobutyl 2-cyclohexyl-2-ethylsuccinate,
diisobutyl 2-isopropyl-2-methylsuccinate, diisobutyl
2-isobutyl-2-ethylsuccinate, diisobutyl
2-(1,1,1-trifluoro-2-propyl)-2-methylsuccinate, diisobutyl
2-isopentyl-2-isobutylsuccinate, diisobutyl
2,2-diisopropylsuccinate, diisobutyl 2-phenyl-2-n-propylsuccinate,
dineopentyl 2,2-dimethylsuccinate, dineopentyl
2-ethyl-2-methylsuccinate, dineopentyl
2-benzyl-2-isopropylsuccinate, dineopentyl
2-(cyclohexylmethyl)-2-isobuty- lsuccinate, dineopentyl
2-cyclopentyl-2-n-propylsuccinate, dineopentyl
2,2-diisobutylsuccinate, dineopentyl 2-cyclohexyl-2-ethylsuccinate,
dineopentyl 2-isopropyl-2-methylsuccinate, dineopentyl
2-isobutyl-2-ethylsuccinate, dineopentyl
2-(1,1,1-trifluoro-2-propyl)-2-m- ethylsuccinate, dineopentyl
2,2-diisopropylsuccinate, dineopentyl
2-isopentyl-2-isobutylsuccinate, dineopentyl
2-phenyl-2-n-butylsuccinate.
[0011] Furthermore, also the compounds in which at least two
radicals different from hydrogen are linked to different carbon
atoms, that is R.sub.3 and R.sub.5 or R.sub.6 are particularly
preferred. Specific examples of suitable compounds are: diethyl
2,3-bis(trimethylsilyl)succin- ate, diethyl
2,2-sec-butyl-3-methylsuccinate, diethyl
2-(3,3,3-trifluoropropyl)-3-methylsuccinate, diethyl
2,3-bis(2-ethylbutyl)succinate, diethyl
2,3-diethyl-2-isopropylsuccinate, diethyl
2,3-diisopropyl-2-methylsuccinate, diethyl
2,3-dicyclohexyl-2-methylsuccinate, diethyl 2,3-dibenzylsuccinate,
diethyl 2,3-diisopropylsuccinate, diethyl
2,3-bis(cyclohexylmethyl)succin- ate, diethyl
2,3-di-t-butylsuccinate, diethyl 2,3-diisobutylsuccinate, diethyl
2,3-dineopentylsuccinate, diethyl 2,3-diisopentylsuccinate, diethyl
2,3-(1-trifluoromethyl-ethyl)succinate, diethyl
2,3-(9-fluorenyl)succinate, diethyl
2-isopropyl-3-isobutylsuccinate, diethyl
2-t-butyl-3-isopropylsuccinate, diethyl 2-isopropyl-3-cyclohexyls-
uccinate, diethyl 2-isopentyl-3-cyclohexylsuccinate, diethyl
2-cyclohexyl-3-cyclopentylsuccinate, diethyl
2,2,3,3-tetramethylsuccinate- , diethyl
2,2,3,3-tetraethylsuccinate, diethyl 2,2,3,3-tetrapropylsuccinat-
e, diethyl 2,3-diethyl-2,3-diisopropylsuccinate, diisobutyl
2,3-bis(trimethylsilyl)succinate, diisobutyl
2,2-sec-butyl-3-methylsuccin- ate, diisobutyl
2-(3,3,3-trifluoropropyl)-3-methylsuccinate, diisobutyl
2,3-bis(2-ethylbutyl)succinate, diisobutyl
2,3-diethyl-2-isopropylsuccina- te, diisobutyl
2,3-diisopropyl-2-methylsuccinate, diisobutyl
2,3-dicyclohexyl-2-methylsuccinate, diisobutyl
2,3-dibenzylsuccinate, diisobutyl 2,3-diisopropylsuccinate,
diisobutyl 2,3-bis(cyclohexylmethyl)- succinate, diisobutyl
2,3-di-t-butylsuccinate, diisobutyl 2,3-diisobutylsuccinate,
diisobutyl 2,3-dineopentylsuccinate, diisobutyl
2,3-diisopentylsuccinate, diisobutyl
2,3-(1,1,1-trifluoro-2-propyl)succin- ate, diisobutyl
2,3-n-propylsuccinate, diisobutyl 2,3-(9-fluorenyl)succina- te,
diisobutyl 2-isopropyl-3-ibutylsuccinate, diisobutyl
2-terbutyl-3-ipropylsuccinate, diisobutyl
2-isopropyl-3-cyclohexylsuccina- te, diisobutyl
2-isopentyl-3-cyclohexylsuccinate, diisobutyl
2-n-propyl-3-(cyclohexylmethyl)succinate, diisobutyl
2-cyclohexyl-3-cyclopentylsuccinate, diisobutyl
2,2,3,3-tetramethylsuccin- ate, diisobutyl
2,2,3,3-tetraethylsuccinate, diisobutyl
2,2,3,3-tetrapropylsuccinate, diisobutyl
2,3-diethyl-2,3-diisopropylsucci- nate, dineopentyl
2,3-bis(trimethylsilyl)succinate, dineopentyl
2,2-di-sec-butyl-3-methylsuccinate, dineopentyl
2-(3,3,3-trifluoropropyl)- -3-methylsuccinate, dineopentyl 2,3
bis(2-ethylbutyl)succinate, dineopentyl
2,3-diethyl-2-isopropylsuccinate, dineopentyl
2,3-diisopropyl-2-methylsuccinate, dineopentyl
2,3-dicyclohexyl-2-methyls- uccinate, dineopentyl
2,3-dibenzylsuccinate, dineopentyl 2,3-diisopropylsuccinate,
dineopentyl 2,3-bis(cyclohexylmethyl)succinate, dineopentyl
2,3-di-t-butylsuccinate, dineopentyl 2,3-diisobutylsuccinate,
dineopentyl 2,3-dineopentylsuccinate, dineopentyl
2,3-diisopentylsuccinat- e, dineopentyl
2,3-(1,1,1-trifluoro-2-propyl)succinate, dineopentyl
2,3-n-propylsuccinate, dineopentyl 2,3(9-fluorenyl)succinate,
dineopentyl 2-isopropyl-3-isobutylsuccinate, dineopentyl
2-t-butyl-3-isopropylsuccina- te, dineopentyl
2-isopropyl-3-cyclohexylsuccinate, dineopentyl
2-isopentyl-3-cyclohexylsuccinate, dineopentyl
2-n-propyl-3-(cyclohexylme- thyl)succinate, dineopentyl
2-cyclohexyl-3-cyclopentylsuccinate, dineopentyl
2,2,3,3-tetramethylsuccinate, dineopentyl
2,2,3,3-tetraethylsuccinate, dineopentyl
2,2,3,3-tetrapropylsuccinate, dineopentyl
2,3-diethyl-2,3-diisopropylsuccinate.
[0012] As mentioned above the compounds according to formula (I) in
which two or four of the radicals R.sub.3 to R.sub.6 which are
joined to the same carbon atom are linked together to form a cycle
are also preferred.
[0013] Specific examples of suitable compounds are
1-(ethoxycarbonyl)-1-(e- thoxyacetyl)-2,6-dimethylcyclohexane,
1-(ethoxycarbonyl)-1-(ethoxyacetyl)-- 2,5-dimethylcyclopentane,
1-(ethoxycarbonyl)-1-(ethoxyacetylmethyl)-2-meth- ylcyclohexane,
1-(ethoxycarbonyl-1-(ethoxy(cyclohexyl)acetyl)cyclohexane.
[0014] It is easily derivable for the ones skilled in the art that
all the above mentioned compounds can be used either in form of
pure stereoisomers or in the form of mixtures of enantiomers, or
mixture of diastereoisomers and enantiomers. When a pure isomer is
to be used it is normally isolated using the common techniques
known in the art. In particular some of the succinates of the
present invention can be used as a pure rac or meso forms, or as
mixtures thereof, respectively.
[0015] As explained above, the catalyst components of the invention
comprise, in addition to the above electron donors, Ti, Mg and
halogen. In particular, the catalyst components comprise a titanium
compound, having at least a Ti-halogen bond and the above mentioned
electron donor compound supported on a Mg halide. The magnesium
halide is preferably MgCl.sub.2 in active form which is widely
known from the patent literature as a support for Ziegler-Natta
catalysts. Patents U.S. Pat. No. 4,298,718 and U.S. Pat. No.
4,495,338 were the first to describe the use of these compounds in
Ziegler-Natta catalysis. It is known from these patents that the
magnesium dihalides in active form used as support or co-support in
components of catalysts for the polymerization of olefins are
characterized by X-ray spectra in which the most intense
diffraction line that appears in the spectrum of the non-active
halide is diminished in intensity and is broadened to form a
halo.
[0016] The preferred titanium compounds used in the catalyst
component of the present invention are TiCl.sub.4 and TiCl.sub.3;
furthermore, also Ti-haloalcoholates of formula
Ti(OR).sub.n-yX.sub.y, where n is the valence of titanium, X is
halogen and y is a number between 1 and n, can be used.
[0017] The preparation of the solid catalyst component can be
carried out according to several methods. According to one of these
methods, the magnesium dichloride in an anhydrous state and the
succinate of formula (I) are milled together under conditions in
which activation of the magnesium dichloride occurs. The so
obtained product can be treated one or more times with an excess of
TiCl.sub.4 at a temperature between 80 and 135.degree. C. This
treatment is followed by washings with hydrocarbon solvents until
chloride ions disappeared. According to a further method, the
product obtained by co-milling the magnesium chloride in an
anhydrous state, the titanium compound and the .beta.-substituted
succinate is treated with halogenated hydrocarbons such as
1,2-dichloroethane, chlorobenzene, dichloromethane, etc. The
treatment is carried out for a time between 1 and 4 hours and at
temperature of from 40.degree. C. to the boiling point of the
halogenated hydrocarbon. The product obtained is then generally
washed with inert hydrocarbon solvents such as hexane.
[0018] According to another method, magnesium dichloride is
preactivated according to well known methods and then treated with
an excess of TiCl.sub.4 at a temperature of about 80 to 135.degree.
C. which contains, in solution, a succinate of formula (I). The
treatment with TiCl.sub.4 is repeated and the solid is washed with
hexane in order to eliminate any non-reacted TiCl.sub.4.
[0019] A further method comprises the reaction between magnesium
alcoholates or chloroalcoholates (in particular chloroalcoholates
prepared according to U.S. Pat. No. 4,220,554) and an excess of
TiCl.sub.4 comprising the succinate of formula (I) in solution at a
temperature of about 80 to 120.degree. C.
[0020] According to a preferred method, the solid catalyst
component can be prepared by reacting a titanium compound of
formula Ti(OR).sub.n-yX.sub.y, where n is the valence of titanium
and y is a number between 1 and n, preferably TiCl.sub.4, with a
magnesium chloride deriving from an adduct of formula
MgCl.sub.2.pROH, where p is a number between 0.1 and 6, preferably
from 2 to 3.5, and R is a hydrocarbon radical having 1-18 carbon
atoms. The adduct can be suitably prepared in spherical form by
mixing alcohol and magnesium chloride in the presence of an inert
hydrocarbon immiscible with the adduct, operating under stirring
conditions at the melting temperature of the adduct
(100-130.degree. C.). Then, the emulsion is quickly quenched,
thereby causing the solidification of the adduct in form of
spherical particles. Examples of spherical adducts prepared
according to this procedure are described in U.S. Pat. Nos.
4,399,054 and 4,469,648. The so obtained adduct can be directly
reacted with the Ti compound or it can be previously subjected to
thermally controlled dealcoholation (80-130.degree. C.) so as to
obtain an adduct in which the number of moles of alcohol is
generally lower than 3 preferably between 0.1 and 2.5. The reaction
with the Ti compound can be carried out by suspending the adduct
(dealcoholated or as such) in cold TiCl.sub.4 (generally 0.degree.
C.); the mixture is heated up to 80-130.degree. C. and kept at this
temperature for 0.5-2 hours. The treatment with TiCl.sub.4 can be
carried out one or more times. The succinate of formula (I) can be
added during the treatment with TiCl.sub.4. The treatment with the
electron donor compound can be repeated one or more times.
[0021] The preparation of catalyst components in spherical form is
described for example in European Patent Applications EP-A-395083,
EP-A-553805, EP-A-553806, EPA-601525 and WO98/44009.
[0022] The solid catalyst components obtained according to the
above method show a surface area (by B.E.T. method) generally
between 20 and 500 m.sup.2/g and preferably between 50 and 400
m.sup.2/g, and a total porosity (by B.E.T. method) higher than 0.2
cm.sup.3/g preferably between 0.2 and 0.6 cm.sup.3/g. The porosity
(Hg method) due to pores with radius up to 10000 .ANG. generally
ranges from 0.3 to 1.5 cm.sup.3/g, preferably from 0.45 to 1
cm.sup.3/g.
[0023] A further method to prepare the solid catalyst component of
the invention comprises halogenating magnesium dihydrocarbyloxide
compounds, such as magnesium dialkoxide or diaryloxide, with
solution of TiCl.sub.4 in aromatic hydrocarbon (such as toluene,
xylene, etc.) at temperatures between 80 and 130.degree. C. The
treatment with TiCl.sub.4 in aromatic hydrocarbon solution can be
repeated one or more times, and the .beta.-substituted succinate is
added during one or more of these treatments.
[0024] In any of these preparation methods the desired succinate of
formula (I) can be added as such or, in an alternative way, it can
be obtained in situ by using an appropriate precursor capable to be
transformed in the desired electron donor compound by means, for
example, of known chemical reactions such as esterification,
transesterification, etc. Generally, the succinate of formula (I)
is used in molar ratio with respect to the MgCl.sub.2 of from 0.01
to 1 preferably from 0.05 to 0.5. Moreover, and this constitutes
another object of the present invention, it has been found that
interesting results are obtained when others internal electron
donor compounds are used together with the succinates of formula
(I). The additional electron donor compound can be the same as the
electron donor (d) disclosed below. In particular very good results
have been obtained when the 1,3-diethers of formula (II) below are
used as internal donors together with a succinate of formula
(I).
[0025] The solid catalyst components according to the present
invention are converted into catalysts for the polymerization of
olefins by reacting them with organoaluminum compounds according to
known methods.
[0026] In particular, it is an object of the present invention a
catalyst for the polymerization of olefins CH.sub.2.dbd.CHR, in
which R is hydrogen or a hydrocarbyl radical with 1-12 carbon
atoms, comprising the product of the reaction between:
[0027] (a) a solid catalyst component comprising a Mg, Ti and
halogen and an electron donor selected from succinates of formula
(I);
[0028] (b) an alkylaluminum compound and, optionally,
[0029] (c) one or more electron donor compounds (external
donor).
[0030] The alkylaluminum compound (b) is preferably selected from
the trialkyl aluminum compounds such as for example
triethylaluminum, triisobutylaluminum, tri-n-butylaluminum,
tri-n-hexylaluminum, tri-n-octylaluminum. It is also possible to
use mixtures of trialkylaluminum's with alkylaluminum halides,
alkylaluminum hydrides or alkylaluminum sesquichlorides such as
AlEt.sub.2Cl and Al.sub.2Et.sub.3Cl.sub.3. Also alkylalumoxanes can
be used.
[0031] It is a particular interesting aspect of the invention the
fact that the above described catalysts are able to give polymers
with high isotactic index even when the polymerization is carried
out in the absence of an external donor (c). In particular,
operating for example according to the working examples described
below propylene polymers having an isotactic index around 96% are
obtained without using an external donor compound. These kind of
products are very interesting for applications in which the
crystallinity of the polymer should not be at its maximum level.
This particular behavior is very surprising in view of the fact
that the esters of dicarboxylic acids known in the art, when used
as internal donors, give polymers with a poor isotactic index when
the polymerization is carried out in the absence of an external
electron donor compound.
[0032] For applications in which a very high isotactic index is
required the use of an external donor compound is normally
advisable. The external donor (c) can be of the same type or it can
be different from the succinate of formula (I). Preferred external
electron donor compounds include silicon compounds, ethers, esters,
such as ethyl 4-ethoxybenzoate, amines, heterocyclic compounds and
particularly 2,2,6,6-tetramethylpiperidine, ketones and the
1,3-diethers of the general formula (II): 2
[0033] wherein R.sup.I, R.sup.II, R.sup.III, R.sup.IV, R.sup.V and
R.sup.VI are equal or different to each other, are hydrogen or
hydrocarbon radicals having from 1 to 18 carbon atoms, and
R.sup.VII and R.sup.VIII, equal or different from each other, have
the same meaning of R.sup.I-R.sup.VI except that they cannot be
hydrogen; one or more of the R.sup.I-R.sup.VIII groups can be
linked to form a cycle. Particularly preferred are the 1,3-diethers
in which R.sup.VII and R.sup.VIII are selected from C.sub.1-C.sub.4
alkyl radicals, R.sup.III and R.sup.IV form a condensed unsaturated
cycle and R.sup.I, R.sup.II, R.sup.V and R.sup.VI are hydrogen. The
use of 9,9-bis(methoxymethyl)fluorene is particularly
preferred.
[0034] Another class of preferred external donor compounds is that
of silicon compounds of formula
R.sub.a.sup.7R.sup.b.sup.8Si(OR.sup.9).sub.c- , where a and b are
integer from 0 to 2, c is an integer from 1 to 3 and the sum
(a+b+c) is 4; R.sup.7, R.sup.8, and R.sup.9, are C1-C18 hydrocarbon
groups optionally containing heteroatoms. Particularly preferred
are the silicon compounds in which a is 1, b is 1, c is 2, at least
one of R.sup.7 and R.sup.8 is selected from branched alkyl,
alkenyl, alkylene, cycloalkyl or aryl groups with 3-10 carbon atoms
optionally containing heteroatoms and R.sup.9 is a C.sub.1-C.sub.10
alkyl group, in particular methyl. Examples of such preferred
silicon compounds are cyclohexylmethyldimethoxysilane,
diphenyldimethoxysilane, methyl-t-butyldimethoxysilane,
dicyclopentyldimethoxysilane,
2-ethylpiperidinyl-2-t-butyldimethoxysilane and
(1,1,1-trifluoro-2-propyl- )-2-ethylpiperidinyldimethoxysilane and
(1,1,1-trifluoro-2-propyl)-methyld- imethoxysilane. Moreover, are
also preferred the silicon compounds in which a is 0, c is 3,
R.sup.8 is a branched alkyl or cycloalkyl group, optionally
containing heteroatoms, and R.sup.9 is methyl. Examples of such
preferred silicon compounds are cyclohexyltrimethoxysilane,
t-butyltrimethoxysilane and thexyltrimethoxysilane.
[0035] The electron donor compound (c) is used in such an amount to
give a molar ratio between the organoaluminum compound and said
electron donor compound (c) of from 0.1 to 500, preferably from 1
to 300 and more preferably from 3 to 100. As previously indicated,
when used in the (co)polymerization of olefins, and in particular
of propylene, the catalysts of the invention allow to obtain, with
high yields, polymers having a high isotactic index (expressed by
high xylene insolubility X.I.), thus showing an excellent balance
of properties. This is particularly surprising in view of the fact
that, as it can be seen from the comparative examples here below
reported, the use as internal electron donors of
.alpha.-substituted or unsubstituted succinate compounds gives
worse results in term of yields and/or xylene insolubility.
[0036] As mentioned above, the succinates of formula (I) can be
used also as external donors with good results. In particular, it
has been found that they are able to give very good results even
when they are used as external electron donor compounds in
combination with catalyst components containing an internal donor
different from the succinates of formula (I). This is very
surprising because the esters of dicarboxylic acids known in the
art are normally not able to give satisfactory results when used as
external donors. On the contrary, the succinates of the formula (I)
are able to give polymers still having a good balance between
isotactic index and yields. It is therefore another object of the
present invention a catalyst system for the polymerization of
olefins CH.sub.2.dbd.CHR, in which R is hydrogen or a hydrocarbyl
radical with 1-12 carbon atoms, comprising the product of the
reaction between:
[0037] (i) a solid catalyst component comprising a Mg, Ti and
halogen and an electron donor (d);
[0038] (ii) an alkylaluminum compound and,
[0039] (iii) a succinate of formula (I).
[0040] The aluminum alkyl compound (ii) has the same meanings of
the aluminum compound (b) given above. The electron donor compound
(d) can be selected from ethers, esters of organic mono or
bicarboxylic acids, such as phthalates, benzoates, glutarates,
succinates having a different structure from those of formula (I),
amines. Preferably, it is selected from 1,3-propanediethers of
formula (II) and esters of organic mono or bicarboxylic acids in
particular phthalates.
[0041] As mentioned above all these catalysts can be used in the
processes for the polymerization of olefins CH.sub.2.dbd.CHR, in
which R is hydrogen or a hydrocarbyl radical with 1-12 carbon
atoms. The preferred .alpha.-olefins to be (co)polymerized are
ethene, propene, 1-butene, 4-methyl-1-pentene, 1-hexene and
1-octene. In particular, the above-described catalysts have been
used in the (co)polymerization of propene and ethylene to prepare
different kinds of products. For example the following products can
be prepared: high density ethylene polymers (HDPE, having a density
higher than 0.940 g/cm.sup.3), comprising ethylene homopolymers and
copolymers of ethylene with .alpha.-olefins having 3-12 carbon
atoms; linear low density polyethylenes (LLDPE, having a density
lower than 0.940 g/cm.sup.3) and very low density and ultra low
density (VLDPE and ULDPE, having a density lower than 0.920
g/cm.sup.3, to 0.880 g/cm.sup.3) consisting of copolymers of
ethylene with one or more .alpha.-olefins having from 3 to 12
carbon atoms, having a mole content of units derived from the
ethylene higher than 80%; elastomeric copolymers of ethylene and
propylene and elastomeric terpolymers of ethylene and propylene
with smaller proportions of a diene having a content by weight of
units derived from the ethylene comprised between about 30 and 70%,
isotactic polypropylenes and crystalline copolymers of propylene
and ethylene and/or other .alpha.-olefins having a content of units
derived from propylene higher than 85% by weight (random
copolymers); shock resistant polymers of propylene obtained by
sequential polymerization of propylene and mixtures of propylene
with ethylene, containing up to 30% by weight of ethylene;
copolymers of propylene and 1-butene having a number of units
derived from 1-butene comprised between 10 and 40% by weight.
Particularly interesting are the propylene polymers obtainable with
the catalyst of the invention showing broad MWD coupled with high
isotactic index and high modulus. In fact, said polymers having a
polydispersity index of higher than 5, a content of isotactic units
expressed in terms of pentads of higher than 97% and a flexural
modulus of at least 2000 MPa. Preferably, the polydispersity index
is higher than 5.1, the flexural modulus is higher than 2100 and
the percent of propylene units in form of pentads is higher than
97.5%.
[0042] Any kind of polymerization process can be used with the
catalysts of the invention that are very versatile. The
polymerization can be carried out for example in slurry using as
diluent an inert hydrocarbon solvent, or in bulk using the liquid
monomer (for example propylene) as a reaction medium. Moreover, it
is possible to carry out the polymerization process in gas-phase
operating in one or more fluidized or mechanically agitated bed
reactors.
[0043] The catalyst of the present invention can be used as such in
the polymerization process by introducing it directly into the
reactor. In the alternative, the catalyst can be pre-polymerized
before being introduced into the first polymerization reactor. The
term pre-polymerized, as used in the art, means a catalyst which
has been subject to a polymerization step at a low conversion
degree. According to the present invention a catalyst is considered
to be pre-polymerized when the amount the polymer produced is from
about 0.1 up to about 1000 g per gram of solid catalyst
component.
[0044] The pre-polymerization can be carried out with the
.alpha.-olefins selected from the same group of olefins disclosed
before. In particular, it is especially preferred pre-polymerizing
ethylene or mixtures thereof with one or more .alpha.-olefins in an
amount up to 20% by mole. Preferably, the conversion of the
pre-polymerized catalyst component is from about 0.2 g up to about
500 g per gram of solid catalyst component.
[0045] The pre-polymerization step can be carried out at
temperatures from 0 to 80.degree. C. preferably from 5 to
50.degree. C. in liquid or gas-phase. The pre-polymerization step
can be performed in-line as a part of a continuous polymerization
process or separately in a batch process. The batch
pre-polymerization of the catalyst of the invention with ethylene
in order to produce an amount of polymer ranging from 0.5 to 20 g
per gram of catalyst component is particularly preferred.
[0046] The polymerization is generally carried out at temperature
of from 20 to 120.degree. C., preferably of from 40 to 80.degree.
C. When the polymerization is carried out in gas-phase the
operating pressure is generally between 0.5 and 10 MPa, preferably
between 1 and 5 MPa In the bulk polymerization the operating
pressure is generally between 1 and 6 MPa preferably between 1.5
and 4 MPa Hydrogen or other compounds capable to act as chain
transfer agents can be used to control the molecular weight of
polymer.
[0047] The following examples are given in order to better
illustrate the invention without limiting it.
[0048] General Procedures and Characterizations
[0049] Preparation of Succinates: General Procedures
[0050] Succinates can be prepared according to known methods
described in the literature. Descriptive examples of procedures for
the synthesis of the succinates exemplified in Table 1 are given
below.
[0051] Alkylation
[0052] For literature see for example: N. R. Long and M. W. Rathke,
Synth. Commun., 11 (1981) 687; W. G. Kofron and L. G. Wideman, J.
Org. Chem., 37 (1972) 555.
[0053] Diethyl 2,3-diethyl-2-isopropylsuccinate (ex. 23)
[0054] To a mixture of 10 mL (72 mmol) of diisopropylamine in 250
mL of tetrahydrofuran (THF) was added 28.6 mL (72 mmol) of BuLi
(2.5 molar in cyclohexanes) at -20.degree. C. After 20 minutes
stirring, 9.2 g (83% pure) (28.3 mmol) of diethyl
2,3-diethylsuccinate was added at -40.degree. C. and after addition
the mixture was stirred for 2 h at room temperature. Then this
mixture was cooled to -70.degree. C. and a mixture of 4.3 mL (43
mmol) of 2-iodopropane and 7.4 mL (43 mmol) of
hexamethylphosphoramide (HMPA) was added. After addition the
cooling was removed and the mixture was stirred for four days. The
volatiles were removed and 250 mL of ether was added. The organic
layer was washed twice with 100 mL of water. The organic layer was
isolated, dried over MgSO.sub.4, filtered and concentrated in vacuo
yielding an orange oil. This oil was chromatographed over silica
with CH.sub.2Cl.sub.2 yielding 2.3 g (30%) of a 96% pure product.
According to gas-chromatography (GC) only one isomer was
present.
[0055] Oxidative Coupling
[0056] For literature see for example: T. J. Brocksom, N.
Petragnani, R. Rodrigues and H. La Scala Teixeira, Synthesis,
(1975) 396; E. N. Jacobsen, G. E. Totten, G. Wenke, A. C. Karydas,
Y. E. Rhodes, Synth. Commun., (1985) 301.
[0057] Diethyl 2,3-dipropylsuccinate (ex 18)
[0058] To a mixture of 46 mL (0.33 mol) of diisopropylamine in 250
mL of THF was added 132 mL (0.33 mol) of BuLi (2.5 molar in
cyclohexanes) at -20.degree. C. After 20 minutes stirring, 39 g
(0.3 mol) of ethyl pentanoate was added at -70.degree. C. and after
addition the mixture was stirred for 1 h at this temperature. Then
this mixture was added to a mixture of 33 mL (0.30 mol) of
TiCl.sub.4 and 200 mL of CH.sub.2Cl.sub.2 at -70.degree. C. keeping
the temperature below -55.degree. C. After addition and
subsequently 1 h stirring, the reaction mixture was quenched with
10 mL of water and then the temperature was slowly raised to room
temperature. The volatiles were removed and 250 mL of ether was
added. The organic layer was washed twice with 100 mL of water. The
organic layer was isolated, dried over MgSO.sub.4, filtered and
concentrated in vacuo yielding an orange oil (contained yield was
77%). This oil was distilled which gave two fractions. The best
fraction that was obtained was 13.5 g (35%) and 98% pure. The
second fraction was 7.5 g and 74% pure.
[0059] Reduction
[0060] meso Diethyl 2,3-dicyclohexylsuccinate (ex 22)
[0061] A stainless-steel autoclave was charged with a mixture of
6.7 g (0.02 mol) of meso diethyl 2,3-diphenylsuccinate, 180 mL of
isopropanol, and 0.23 g of a 5 wt. % Rh/C catalyst. The mixture was
hydrogenated for 18 h at 70.degree. C. under a hydrogen pressure of
20 bar. The mixture was filtered over Celite and concentrated under
reduced pressure yielding 6.8 g (yield 97%) of 99% pure
product.
[0062] Esterification
[0063] For literature see for example: "Vogel's textbook of
practical organic chemistry", 5.sup.th Edition (1989), pages
695-707.
[0064] Diethyl 2-phenylsuccinate (ex 1)
[0065] A mixture of 50 g of DL-phenylsuccinic acid (0.257 mol), 90
mL (1.59 mol) of ethanol, 46 mL of toluene and 0.39 g of
concentrated H.sub.2SO.sub.4 was heated to 115.degree. C. An
azeotropic mixture of ethanol, toluene and water was distilled over
a column of 10 cm. When the distillation stopped the same amounts
of ethanol and toluene was added. To obtain a complete conversion
this was repeated twice. The resulting oil was distilled at
114.degree. C. (2.multidot.10.sup.-2 mbar); yield 60.82 g (95%),
purity 100% S.sub.N2 Coupling
[0066] For literature see for example: N. Petragnani and M.
Yonashiro, Synthesis, (1980) 710; J. L. Belletire, E. G. Spletzer,
and A. R. Pinhas, Tetrahedron Lett., 25 (1984) 5969.
[0067] Diisobutyl 2,2,3-trimethylsuccinate (ex 14)
[0068] Isobutyric acid (14.6 mL, 157 mmol) was added to a freshly
prepared lithium disopropyl amide (LDA) solution (see synthesis of
succinate ex 23 , 41 mL, 314 mmol of diisopropylamine and 126 mL of
BuLi (2.5 M in hexanes; 314 mmol) and 1 L of THF) at 0.degree. C.
This mixture was stirred at 0.degree. C. for 15 minutes and
subsequently for 4 h at 45.degree. C.
[0069] Meanwhile in a separate reaction vessel, a mixture of 14.1
mL (157 mmol) of 2-bromopropionic acid and 28 g (157 mmol) of HMPA
was added to a suspension of 3.8 g (157 mmol) of NaH in 500 mL of
THF at 0.degree. C. while controlling the gas formation. After
addition the mixture was stirred for 15 minutes at 0.degree. C.
Then this mixture was added to the mixture of the lithium salt of
isobutyric acid (described above) at 0.degree. C. After addition
the mixture was stirred for 2 h at 35.degree. C. This mixture was
quenched with 150 mL of a NaCl saturated 1 N HCl solution at
0.degree. C. This mixture was extracted twice with 100 mL of
diethyl ether and the combined ether layers were extracted with 50
mL of a saturated NaCl solution. The organic layer was dried over
MgSO.sub.4 and concentrated in vacuo yielding a yellow oil. This
oil was dissolved in 150 mL of isobutanol, 100 mL of toluene and 2
mL of concentrated H.sub.2SO.sub.4. This mixture was heated to
reflux with a Dean Stark set-up to remove the water. After two days
the conversion was complete. The reaction mixture was concentrated
in vacuo and the resulting oil was distilled at 155.degree. C. (75
mbar); yield 5.1 g (12%), purity 98%.
[0070] Combined Methods
[0071] Most of the succinates were prepared by a combination of
methods described above. The different methods used for the
synthesis of the succinates exemplified in Table 1 are further
specified in Table A. The sequential order in which the methods
were used is indicated alphabetically by a, b and c.
1TABLE A Succinate (for Methods of synthesis type see oxidative
S.sub.N2 Table 1) Esterification Alkylation Reduction coupling
coupling 1 A 2 A b 3 A b 4 A 5 A b 12 A 13 A b 14 a 15 a B 16 a B c
18 a 22 a b 23 B a 24 B a 25 B a 26 a C b 27 a 30 a
[0072] Polymerization
[0073] Propylene Polymerization: General Procedure
[0074] In a 4 liter autoclave, purged with nitrogen flow at
70.degree. C. for one our, 75 mL of anhydrous hexane containing 800
mg of AlEt.sub.3, 79.8 mg of dicyclopentyldimethoxysilane and 10 mg
of solid catalyst component were introduced in propylene flow at
30.degree. C. The autoclave was closed. 1.5 NL of hydrogen were
added and then, under stirring, 1.2 kg of liquid propene were fed.
The temperature was raised to 70.degree. C. in five minutes and the
polymerization was carried out at this temperature for two hours.
The nonreacted propylene was removed, the polymer was collected,
dried at 70.degree. C. under vacuum for three hours, weighed, and
fractionated with o-xylene to determine the amount of the xylene
insoluble (X.I.) fraction at 25.degree. C.
[0075] Ethylene/1-butene Polymerization: General Procedure
[0076] A 4.0 liter stainless-steel autoclave equipped with a
magnetic stirrer, temperature, pressure indicator, feeding line for
ethene, propane, 1-butene, hydrogen, and a steel vial for the
injection of the catalyst, was purified by fluxing pure nitrogen at
70.degree. C. for 60 minutes. It was then washed with propane,
heated to 75.degree. C. and finally loaded with 800 g of propane,
1-butene (as reported in Table 4), ethene (7.0 bar, partial
pressure) and hydrogen (2.0 bar, partial pressure).
[0077] In a 100 mL three neck glass flask were introduced in the
following order, 50 mL of anhydrous hexane, 9.6 mL of 10% by
wt/vol, TEAL/hexane solution, optionally an external donor (E.D.,
as reported in Table 4) and the solid catalyst. They were mixed
together and stirred at room temperature for 20 minutes and then
introduced in the reactor through the steel vial by using a
nitrogen overpressure.
[0078] Under continuous stirring, the total pressure was maintained
constant at 75.degree. C. for 120 minutes by feeding ethene. At the
end the reactor was depressurised and the temperature was dropped
to 30.degree. C. The collected polymer was dried at 70.degree. C.
under a nitrogen flow and weighted.
[0079] Determination of Xylene Insolubles (X.I.)
[0080] 2.5 g of polymer were dissolved in 250 mL of o-xylene under
stirring at 135.degree. C. for 30 minutes, then the solution was
cooled to 25.degree. C. and after 30 minutes the insoluble polymer
was filtered. The resulting solution was evaporated in nitrogen
flow and the residue was dried and weighed to determine the
percentage of soluble polymer and then, by difference the xylene
insoluble fraction (%).
[0081] Determination of Comonomer Content in the Copolymer:
[0082] 1-Butylene was determined via infrared spectrometry.
[0083] Thermal Analysis:
[0084] Calorimetric measurements were performed by using a
differential scanning calorimeter DSC Mettler. The instrument is
calibrated with indium and tin standards. The weighted sample (5-10
mg), obtained from the melt index determination, was sealed into
aluminum pans, heated to 200.degree. C. and kept at that
temperature for a time long enough (5 minutes) to allow a complete
melting of all the crystallites. Successively, after cooling at
20.degree. C./min to -20.degree. C., the peak temperature was
assumed as crystallization temperature (Tc). After standing 5
minutes at 0.degree. C., the sample was heated to 200.degree. C. at
a rate of 10.degree. C./min. In this second heating run, the peak
temperature was assumed as melting temperature (Tm) and the area as
the global melting enthalpy (.DELTA.H).
[0085] Determination of Melt Index (M.I.):
[0086] Melt index was measured at 190.degree. C. following ASTM
D-1238 over a load of:
[0087] 2.16 kg, MI E=MI2.16.
[0088] 21.6 kg, MI F=MI21.6.
[0089] The ratio: F/E=MI F/MI E=MI21.6/MI2.16 is then defined as
melt flow ratio (MFR)
[0090] Determination of Density:
[0091] Density was determined on the homogenized polymers (from the
M.I. determination) by using a gradient column and following the
ASTM D-1505 procedure.
[0092] Determination of Polydispersity Index (P.I.)
[0093] This property is strictly connected with the molecular
weight distribution of the polymer under examination. In particular
it is inversely proportional to the creep resistance of the polymer
in the molten state. Said resistance called modulus separation at
low modulus value (500 Pa), was determined at a temperature of
200.degree. C. by using a parallel plates rheometer model RMS-800
marketed by RHEOMETRICS (USA), operating at an oscillation
frequency which increases from 0.1 rad/sec to 100 rad/sec. From the
modulus separation value, one can derive the P.I. by way of the
equation:
P.I.=54.6*(modulus separation).sup.-1.76
[0094] in which the modulus separation is defined as:
modulus separation=frequency at G'=500 Pa/frequency at G"=500
Pa
[0095] wherein G' is storage modulus and G" is the loss
modulus.
EXAMPLES
Examples 1-27 and Comparative Examples 28-30
[0096] Preparation of Solid Catalyst Components.
[0097] Into a 500 mL four-necked round flask, purged with nitrogen,
250 mL of TiCl.sub.4 were introduced at 0.degree. C. While
stirring, 10.0 g of microspheroidal MgCl.sub.2*2.8C.sub.2H.sub.5OH
(prepared according to the method described in ex.2 of U.S. Pat.
No. 4,399,054 but operating at 3000 rpm instead of 10000 rpm) and
7.4 mmol of succinate were added. The temperature was raised to
100.degree. C. and maintained for 120 min. Then, the stirring was
discontinued, the solid product was allowed to settle and the
supernatant liquid was siphoned off. Then 250 mL of fresh
TiCl.sub.4 were added. The mixture was reacted at 120.degree. C.
for 60 min and, then, the supernatant liquid was siphoned off. The
solid was washed six times with anhydrous hexane (6.times.100 mL)
at 60.degree. C. Finally, the solid was dried under vacuum and
analyzed. The type and amount of succinate (wt %) and the amount of
Ti (wt %) contained in the solid catalyst component are reported in
Table 1. Polymerization results are reported in Table 2. The
polymer obtained in the example 10 was characterized and it showed
a polydispersity index of 6, a content of isotactic units expressed
in terms of pentads of 98% and a flexural modulus of 2150 MPa.
2 TABLE 1 Succinate Ti Ex. no. Type Wt % Wt % 1 Diethyl
phenylsuccinate 15.3 4.0 2 Diethyl cyclohexylsuccinate 16.4 3.3 3
Diisobutyl cyclohexylsuccinate 11.9 3.1 4 Diethyl benzylsuccinate
12.8 2.1 5 Diethyl cyclohexylmethylsuccinate 15.3 3.2 6 Diethyl
2,2-dimethylsuccinate 13.0 2.6 7 Diisobutyl 2,2-dimethylsuccinate
12.1 3.2 8 Diethyl 2-ethyl-2-methylsuccinate 13.3 1.9 9 Diisobutyl
2-ethyl-2-methylsuccinate 15.2 3.3 10 Diethyl
2,3-diisopropylsuccinate 18.9 4.2 11 Diisobutyl
2,3-diisopropylsuccinate 17.2 4.2 12 Diethyl 2,3-dibenzylsuccinate
24.1 3.2 13 Diethyl 2,3-bis(cyclohexylmethyl)succinate 21.5 4.7 14
Diisobutyl 2,2,3-trimethylsuccinate 8.0 4.4 15 Diethyl
2-benzyl-3-ethyl-3-methylsuccinate 14.9 3.2 16 Diethyl
2-(cyclohexylmethyl)-3-ethyl- 17.9 2.9 3-methylsuccinate 17 Diethyl
t-butylsuccinate 14.0 2.9 18 Diethyl 2,3-di-n-propylsuccinate 13.1
3.9 19 Dimethyl 2,3-diisoproylsuccinate 17.7 4.1 20 Diisopropyl
2,3-diisopropylsuccinate 13.7 4.3 21 Di-n-butyl
2,3-diisopropylsuccinate 17.4 4.6 22 meso Diethyl
2,3-dicyclohexylsuccinate 12.5 4.3 23 Diethyl
2,3-diethyl-2-isopropylsuccinate 17.0 4.4 24 Diethyl
2,3-diisopropyl-2-methylsuccinate 17.2 5.1 25 Diethyl
2,3-diisopropyl-2-ethylsuccinate 12.0 5.4 26 Diethyl
2,3-dicyclohexyl-2-methylsuccinate 20.0 5.3 27 Diethyl
2,2,3,3-tetramethylsuccinate 9.0 4.0 Comp. 28 Di-n-butyl succinate
7.4 2.1 Comp. 29 Diethyl methylsuccinate 10.9 3.4 Comp. 30
Diisobutyl ethylsuccinate 7.7 3.0
[0098]
3TABLE 2 Example Yield X.I. no. kgPP/gCat Wt % 1 20 98.3 2 35 97.4
3 28 97.3 4 22 96.6 5 33 97.8 6 37 97.2 7 44 97.0 8 44 98.6 9 42
97.3 10 61 98.4 11 69 98.8 12 42 96.1 13 39 97.0 14 29 96.6 15 36
96.0 16 42 96.8 17 25 97.0 18 41 96.7 19 37 98.4 20 40 97.4 21 62
98.5 22 58 95.0 23 43 96.2 24 50 94.9 25 40 95.0 26 50 96.0 27 36
95.5 Comp. 28 9 96.0 Comp. 29 11 95.8 Comp. 30 12 96.0
Example 31
[0099] The procedure of examples 1-27 and comparative examples
28-30 was used, but, preparing the solid catalyst component rac
diethyl 2,3-diisopropylsuccinate was added as succinate. The
resulting solid catalyst component contained: Ti=4.8% by weight,
rac diethyl 2,3-diisopropylsuccinate 16.8% by weight.
[0100] The above mentioned solid catalyst component was polymerized
according to the general polymerization procedure but without using
dicyclopentyldimethoxysilane. The polymer yield was 65 kg of
polypropylene/g of solid catalyst component with X.I.=96.1%.
Examples 32-38
[0101] The solid catalyst component of example 10 was polymerized
according to the general polymerization procedure but instead of
dicyclopentyldimethoxysilane the electron donors of Table 3 were
used. The amount and type of electron donor and the polymerization
results are reported in Table 3
Comparative Example 39
[0102] The procedure of examples 1-27 and comparative examples
28-30 was used, but, preparing the solid catalyst component, 14
mmol of ethyl benzoate were added instead of the succinate
compound. The resulting solid catalyst component contained: Ti=3.5%
by weight, ethyl benzoate 9.1% by weight.
[0103] The above mentioned solid catalyst component was polymerized
with the same procedure of example 38.
[0104] The polymerization result is reported in Table 3
4TABLE 3 Ex External donor Yield X.I. no. Type mmol kg/g % 32
Cyclohexylmethyldimethoxysilane 0.35 61 97.9 33 3,3,3- 0.35 58 96.8
trifluoropropylmethyldimeth- oxysilane 34 3,3,3-trifluoropropyl(2-
0.35 70 98.2 ethylpiperidyl)dimethoxysilane 35
Diisopropyldimethoxysilane 0.35 62 97.6 36
9,9-bis(methoxymethyl)fluorene 0.35 70 98.0 37 Diethyl
2,3-diisopropylsuccinate 0.35 59 96.4 38 Ethyl p-ethoxybenzoate
3.00 20 98.1 Comp. Ethyl p-ethoxybenzoate 3.00 23 96.1 39
Example 40
[0105] The procedure of examples 1-27 and comparative examples
28-30 was used, but, preparing the solid catalyst component 7.4
mmol of diethyl 2,3-diisopropylsuccinate and 7.4 mmol of
9,9-bis(methoxymethyl)fluorene were added.
[0106] The resulting solid catalyst component contained: Ti=3.5% by
weight, diethyl 2,3-diisopropylsuccinate=11.5% by weight and
9,9-bis(methoxymethyl)fluorene=6.9% by weight.
[0107] The above mentioned solid catalyst component was polymerized
as in the general polymerization procedure. The polymer yield was
74 kg of polypropylene/g of solid catalyst component with
X.I.=99.3%.
Example 41
[0108] The solid catalyst component of example 40 was polymerized
according to the general polymerization procedure but without using
dicyclopentyldimethoxysilane. The polymer yield was 100 kg of
polypropylene/g of solid catalyst component with X.I.=98.6%.
Example 42
[0109] The procedure of examples 1-27 and comparative examples
28-30 was used, but, preparing the solid catalyst component, 7.4
mmol of 9,9-bis(methoxymethyl)fluorene were added instead of the
succinate compound. The resulting solid catalyst component
contained: Ti=3.5% by weight, 9,9-bis(methoxymethyl)fluorene=18.1%
by weight.
[0110] The above mentioned solid catalyst component was polymerized
according to the general polymerization procedure but instead of
dicyclopentyldimethoxysilane, 0.35 mmol of diethyl
2,3-diisopropylsuccinate were used. The polymer yield was 84 kg of
polypropylene/g of solid catalyst component with X.I.=98.6%.
Example 43
[0111] Preparation of Solid Catalyst Component
[0112] The spherical support, prepared according to the general
method described in Ex. 2 of U.S. Pat. No. 4,399,054 (but operating
at 3000 rpm instead of 10000 rpm) was subjected to thermal
treatment, under nitrogen flow, within the temperature range of
50-150.degree. C., until spherical particles having a residual
alcohol content of about 35 wt. % (1.1 mol of alcohol per mol of
MgCl.sub.2) were obtained.
[0113] 16 g of this support were charged, under stirring at
0.degree. C., to a 750 mL reactor containing 320 mL of pure
TiCl.sub.4. 3.1 mL of diethyl 2,3-diisopropylsuccinate, were slowly
added and the temperature was raised to 100.degree. C. in 90
minutes and kept constant for 120 minutes. Stirring was
discontinued, settling was allowed to occur and the liquid phase
was removed at the temperature of 80.degree. C. Further 320 mL of
fresh TiCl.sub.4 were added and the temperature was raised to
120.degree. C. and kept constant for 60 minutes. After 10 minutes
settling the liquid phase was removed at the temperature of
100.degree. C. The residue was washed with anhydrous heptane (300
mL at 70.degree. C. then 3 times (250 mL each time) then with
anhydrous hexane at 60.degree. C. The component in spherical form
was vacuum dried at 50.degree. C.
[0114] The catalyst composition was as follow:
5 Ti 2.9 wt. % diethyl 2,3-diisopropylsuccinate 3.8 wt. % Solvent
13.5 wt. %
[0115] Ethylene Polymerization:
[0116] A 4.0 liter stainless-steel autoclave equipped with a
magnetic stirrer, temperature and pressure indicator, feeding line
for ethene, propane, hydrogen, and a steel vial for the injection
of the catalyst was used and purified by fluxing pure nitrogen at
70.degree. C. for 60 minutes and than washed with propane.
[0117] In the following order 50 mL of anhydrous hexane, 5 mL of
10% by wt/vol, TEAL/hexane solution and 0.019 g of the solid
catalyst were mixed together at room temperature, aged 20 minutes
and introduced in the empty reactor in propane flow. The autoclave
was closed and 800 g of propane were introduced, then the
temperature was raised to 75.degree. C. and ethylene (7.0 bar,
partial pressure) and hydrogen (3.0 bar, partial pressure) were
added.
[0118] Under continuous stirring, the total pressure was maintained
at 75.degree. C. for 180 minutes by feeding ethene. At the end the
reactor was depressurised and the temperature was dropped to
30.degree. C. The collected polymer was dried at 70.degree. C.
under a nitrogen flow. 375 g of polyethylene were collected. The
polymer characteristics are reported in Table 5.
Example 44
[0119] The solid catalyst of the example 43 was used in the
ethylene/1-butene copolymerization as reported in the general
procedure but without using any external donor.
[0120] The other polymerization conditions are reported in Table 4
while the polymer characteristics are collected in Table 5.
Example 45
[0121] The solid catalyst of the example 43 was used in the
ethylene/1-butene copolymerization as reported in the general
procedure but by using 0.56 mmol of cyclohexylmethyldimethoxysilane
as external donor.
[0122] The other polymerization conditions are reported in Table 4
while the polymer characteristics are collected in Table 5.
Example 46
[0123] The solid catalyst of the example 43 was used in the
ethylene/1-butene copolymerization as reported in the general
procedure but by using 0.56 mmol of diethyl
2,3-diisopropylsuccinate as external donor.
[0124] The other polymerization conditions are reported in Table 4
while the polymer characteristics are collected in Table 5.
Example 47
[0125] The solid catalyst of the example 43 was used in the
ethylene/1-butene copolymerization in a fluidized gas-phase reactor
as described below.
[0126] A 15.0 liter stainless-steel fluidized reactor equipped with
gas-circulation system, cyclone separator, thermal exchanger,
temperature and pressure indicator, feeding line for ethylene,
propane, 1-butene, hydrogen, and a 1 L steel reactor for the
catalyst prepolymerization and injection of the prepolymer. The
gas-phase apparatus was purified by fluxing pure nitrogen at
40.degree. C. for 12 hours and then was circulated a propane (10
bar, partial pressure) mixture containing 1.5 g of TEAL at
80.degree. C. for 30 minutes. It was then depressurized and the
reactor washed with pure propane, heated to 75.degree. C. and
finally loaded with propane (2 bar partial pressure), 1-butene (as
reported in Table 4), ethylene (7.1 bar, partial pressure) and
hydrogen (2.1 bar, partial pressure).
[0127] In a 100 mL three neck glass flask were introduced in the
following order, 20 mL of anhydrous hexane, 9.6 mL of 10% by
wt/vol, TEAL/hexane solution and the solid catalyst of the example
43 (in the amount reported in Table 4). They were mixed together
and stirred at room temperature for 5 minutes and then introduced
in the prepolymerization reactor maintained in a propane flow.
[0128] The autoclave was closed and 80 g of propane and 90 g of
propene were introduced at 40.degree. C. The mixture was allowed
stirring at 40.degree. C. for 30 minutes. The autoclave was then
depressurized to eliminate the excess of unreacted propene, and the
obtained prepolymer was injected into the gas-phase reactor by
using a propane overpressure (1 bar increase in the gas-phase
reactor). The final pressure, in the fluidized reactor, was
maintained constant at 75.degree. C. for 180 minutes by feeding a
10 wt. % 1-butene/ethene mixture.
[0129] At the end, the reactor was depressurised and the
temperature was dropped to 30.degree. C. The collected polymer was
dried at 70.degree. C. under a nitrogen flow and weighted.
[0130] The polymer characteristics are collected in Table 5.
Example 48
[0131] Preparation of Solid Catalyst Component
[0132] The procedure of example 43 was repeated but instead of
diethyl 2,3-diisopropylsuccinate was used diisobutyl phthalate
(11.8 mmol). The characteristics of the dried catalyst were as
follow:
6 Ti 2.3 wt. % diisobutyl phthalate 4.4 wt. % Solvent 5.5 wt. %
[0133] The solid catalyst was then used in the ethylene/1-butene
copolymerization as reported in the general procedure but using
diethyl 2,3-diisopropylsuccinate as E.D.
[0134] The other polymerization conditions are reported in Table 4
while the polymer characteristics are collected in Table 5.
7TABLE 4 Ethylene (co)polymerization Polymer Catalyst E.D. time
Yield Example Mg Type Mmol AI/E.D. 1-butene G min g kg/gcat 43 19.0
-- -- -- -- 180 375 19.7 44 21.0 -- -- -- 170 120 300 14.3 45 38.8
CHMMS 0.56 15 200 120 470 12.1 46 22.0 Diethyl 2,3- 0.56 15 200 120
255 11.6 diisopropyl- succinate 47 46.0 -- -- -- 330* 180 815 17.7
48 39.5 Diethyl 2,3- 0.56 15 200 120 290 7.3 diisopropyl- succinate
CHMMS = Cyclohexyl-methyl-dimethoxysilane
[0135]
8TABLE 5 Copolymer characterization Melt Index 1-C4- D. S. C.
Polymer E F (I.R.) Density Tc Tm X.S. Example dg/min dg/min F/E Wt.
% g/mL .degree.C. .degree.C. DH J/g wt. % 43 0.44 13.9 31.6 -- --
-- -- -- -- 44 0.86 26.7 31.5 10.1 0.9174 105 124.8 126 14.9 45 1.0
28.1 28.1 9.8 0.9170 105 123.7 125 14.8 46 0.79 25.8 32.6 8.4
0.9199 n.d. n.d. n.d. n.d. 47 2.3 77.1 33.5 10.5 0.9136 106 123.9
118 n.d. 48 0.84 29.5 35.1 12.8 0.9165 107 126.0 116 n.d. n.d. =
not determined
* * * * *