U.S. patent application number 10/003105 was filed with the patent office on 2002-06-13 for polyolefin resin modifier, polyolefin resin composition and oriented polyolefin film.
This patent application is currently assigned to Idemitsu Petrochemical Co., Ltd.. Invention is credited to Aoki, Akira, Kaminaka, Manabu, Masada, Isao, Nakayama, Nobuhiko.
Application Number | 20020072569 10/003105 |
Document ID | / |
Family ID | 13940784 |
Filed Date | 2002-06-13 |
United States Patent
Application |
20020072569 |
Kind Code |
A1 |
Nakayama, Nobuhiko ; et
al. |
June 13, 2002 |
Polyolefin resin modifier, polyolefin resin composition and
oriented polyolefin film
Abstract
A crystalline polyolefin resin composition contains: (A1) 4 to
20 wt % of a polyolefin resin component having an elution
temperature of 36 to 104.degree. C. and a molecular weight of
100,000 to 1,000,000 measured by TREF/SEC; and (B) 96 to 80 wt % of
a crystalline polyolefin resin component different from the above
component (A1), the wt % being based on the total weight of the
components (A1) and (B).
Inventors: |
Nakayama, Nobuhiko;
(Tokuyama-shi, JP) ; Masada, Isao; (Tokuyama-shi,
JP) ; Aoki, Akira; (Tokuyama-shi, JP) ;
Kaminaka, Manabu; (Tokuyama-shi, JP) |
Correspondence
Address: |
BIRCH STEWART KOLASCH & BIRCH
PO BOX 747
FALLS CHURCH
VA
22040-0747
US
|
Assignee: |
Idemitsu Petrochemical Co.,
Ltd.
|
Family ID: |
13940784 |
Appl. No.: |
10/003105 |
Filed: |
December 6, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
10003105 |
Dec 6, 2001 |
|
|
|
09536980 |
Mar 29, 2000 |
|
|
|
Current U.S.
Class: |
525/191 |
Current CPC
Class: |
C08L 2666/04 20130101;
C08L 2666/04 20130101; C08L 2666/02 20130101; C08L 2666/04
20130101; C08L 23/06 20130101; C08L 23/06 20130101; C08L 23/08
20130101; C08L 23/0853 20130101; C08L 23/08 20130101; C08L 2205/02
20130101; C08L 23/10 20130101; C08L 23/06 20130101; C08L 23/0869
20130101; C08L 23/10 20130101 |
Class at
Publication: |
525/191 |
International
Class: |
C08F 008/00 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 30, 1999 |
JP |
11-088365 |
Claims
What is claimed is:
1. A modifier for a crystalline polyolefin resin, which modifier
contains a component having an elution temperature of 36 to
104.degree. C. and a molecular weight of 100,000 to 1,000,000
measured by TREF/SEC in an amount of more than 20 wt % to 100 wt
%.
2. The modifier of claim 1 which has an elution temperature of 40
to 88.degree. C.
3. The modifier of claim 1 which contains a component having an
elution temperature of 0.degree. C. or less measured by TREF/SEC in
an amount of 5 wt % or less.
4. The modifier of claim 1 which has a melt flow rate of 1 to 20
g/10 min.
5. The modifier of claim 1 which has a molecular weight
distribution represented by the ratio (Mw/Mn) of weight average
molecular weight (Mw) to number average molecular weight (Mn) of
1.5 to 15.
6. A method of producing the polyolefin resin of claim 1 comprising
the step of polymerizing an olefin in the presence of a catalyst
comprising a metallocene compound and aluminoxane compound, or a
melallocene compound and non-coordination ionized compound.
7. A modifier for a crystalline polyolefin resin, which modifier
contains a component having an elution temperature of more than
116.degree. C. and a molecular weight of 10,000 to 100,000 measured
by TREF/SEC in an amount of 20 to 100 wt %.
8. The modifier of claim 7 which has a melt flow rate of 5 to 100
g/10 min.
9. The modifier of claim 7 which contains a component having an
elution temperature of 0.degree. C. or less measured by TREF/SEC in
an amount of 5 wt % or less.
Description
DETAILED DESCRIPTION OF THE INVENTION
[0001] The present invention relates to a polyolefin resin modifier
and, particularly, to a modifier effective in improving the film
processability, stretchability and heat resistance such as low
thermal shrinkage of a crystalline polyolefin resin used in an
oriented film, for example, a polypropylene-based resin, a modified
polyolefin resin composition and an oriented film formed from the
resin composition.
[0002] An oriented polyolefin film, particularly a biaxially
oriented polyolefin film is widely used as a packaging material and
the like thanks to its excellent mechanical and optical properties.
To produce the film, sequential biaxial orientation using a tenter
system is generally employed.
[0003] In recent years, the production equipment of biaxially
oriented polyolefin films has been becoming larger in size and
higher in speed. When a biaxially oriented film is to be produced
from a conventional general polyolefin resin with the equipment,
such problems as a rise in mechanical load to a stretching machine,
a reduction in the thickness accuracy of a film and the breakage of
a film by stretching have arisen. Therefore, various methods for
improving stretchability have been proposed. For example, JP-A
9-324014 (the term "JP-A" as used herein means an "unexamined
published Japanese patent application") proposes a technology in
which an amorphous component is contained in a specific amount and
an isotacticity distribution is made wide. However, there still
remains room for the improvement of the obtained film to produce an
oriented polyolefin film having excellent film formability at the
time of high-speed film formation and excellent mechanical
properties and heat resistance.
[0004] Therefore, the development of a polyolefin resin having
excellent stretchability which can be produced with large-sized and
high-speed oriented polyolefin film production equipment has been
desired.
[0005] It is therefore an object of the present invention to
provide a polyolefin resin composition which has a wide temperature
control range for film formation at the time of stretching and a
small mechanical load, is excellent in the thickness accuracy of
the formed film and stretchability, can be produced stably without
being broken by stretching or the like, and is suitable for the
production of a uniaxially or biaxially oriented film having
excellent heat resistance such as the thermal shrinkage of the
formed film.
[0006] It is another object of the present invention to provide a
polyolefin resin which can provide the above excellent
characteristic properties to a polyolefin resin composition
obtained by mixing a crystalline polyolefin resin and a modifier
comprising the same.
[0007] It is still another object of the present invention to
provide an oriented film formed from the above polyolefin resin
composition of the present invention.
[0008] The other objects and advantages of the present invention
will become apparent from the following description.
[0009] According to the present invention, firstly, the above
objects and advantages of the present invention are attained by a
crystalline polyolefin resin composition comprising:
[0010] (A1) 4 to 20 wt % of a polyolefin resin component having an
elution temperature of 36 to 104.degree. C. and a molecular weight
of 100,000 to 1,000,000 measured by a direct coupling method
(TREF/SEC) of size exclusion chromatography (SEC) to temperature
rising elution fractionation (TREF); and
[0011] (B) 96 to 80 wt % of a crystalline polyolefin resin
component different from the above component (A1), the wt % being
based on the total of the components (A1) and the above (B).
[0012] According to the present invention, secondly, the above
objects and advantages of the present invention are attained by an
oriented film formed from the above crystalline polyolefin resin
composition of the present invention.
[0013] According to the present invention, thirdly, the above
objects and advantages of the present invention are attained by a
modifier for a crystalline polyolefin resin comprising more than 20
wt % to 100 wt % of a component having an elution temperature of 36
to 104.degree. C. and a molecular weight of 100,000 to 1,000,000
measured by the direct coupling method (TREF/SEC) of size exclusion
chromatography (SEC) to temperature rising elution fractionation
(TREF) and by a modifier comprising the same.
[0014] According to the present invention, fourthly, the above
objects and advantages of the present invention are attained by a
modifier for a crystalline polyolefin resin comprising 20 to 100 wt
% of a component having an elution temperature of more than
116.degree. C. and a molecular weight of 10,000 to 100,000 measured
by the direct coupling method (TREF/SEC) of size exclusion
chromatography (SEC) to temperature rising elution fractionation
(TREF) and by a modifier comprising the same.
[0015] The present invention will be descried in detail
hereinunder.
[0016] In the present invention, the direct coupling method
(TREF/SEC) of size exclusion chromatography (SEC) to temperature
rising elution fraction (TREF) is an analytical method which
directly couples temperature rising elution fractionation (TREF) to
size exclusion chromatography (SEC) on an on-line basis and will be
simply referred to as "TREF/SEC" hereinafter. TREF/SEC is a method
of evaluating the composition distribution of a polyolefin by
dissolving the polyolefin (such as a polypropylene resin)
crystallized in a solution in a solvent at different temperatures
and continuously measuring the molecular weight distribution and
the elution (concentration) of the polyolefin at each dissolution
temperature. That is, an inert carrier such as diatomaceous earth
or silica beads are used as a filler, a sample solution dissolved
an amount of a polyolefin in a solvent such as orthodichlorobenzene
as a sample is injected into the TREF column of the filler, the
temperature of the TREF column is lowered to adhere the sample to
the surface of the filler, the temperature of the column is
elevated stepwise to a desired level, the orthodichlorobenzene
solvent is passed through the column, the polyolefin component
eluted at the above temperature is continuously introduced into a
high-temperature SEC column, and the elution (wt %) and molecular
weight distribution of the polyolefin are measured. The composition
distribution of the polyolefin can be seen from a graph (the
relationship between crystallizability and molecular weight is
expressed by a contour or a bird's-eye view) drawn based on the
elution temperature (.degree. C.) and the molecular weight
distribution of the polyolefin by this operation. A projection
diagram of elution temperature shows a crystallizability
distribution and the crystallinity distribution of the polymer can
be obtained from the relationship between elution temperature and
the elution (wt %) of a polymer because the elution temperature
becomes higher as the elution component is crystallized more
easily.
[0017] In the above method, the cooling rate of the TREF column
must be adjusted to a speed required for the crystallization of a
crystalline portion contained in the polyolefin sample at a
predetermined temperature and can be determined experimentally in
advance. The cooling rate of the column is generally set to a range
of 5.degree. C./min or less.
[0018] Crystalline Polyolefin Resin Composition
[0019] In the present invention, it is important that the component
(A1) having an elution temperature of 36 to 104.degree. C. and a
molecular weight of 100,000 to 1,000,000 measured by TREF/SEC
should be contained in the crystalline polyolefin resin composition
in an amount of 4 to 20 wt %, preferably 5 to 18 wt %, more
preferably 6 to 15 wt %. When the amount of the above effective
component (A1) contained in the crystalline polyolefin resin
composition is smaller than 4 wt %, stretchability at the time of
film formation lowers, the range of film processable temperature
narrows and a mechanical load rises, thereby increasing the
breakage of a film by stretching and deteriorating the thickness
accuracy of a film. When the amount of the above effective
component (A1) is larger than 20 wt %, the thermal shrinkage of an
oriented film increases with the result of a reduction in heat
resistance.
[0020] Preferably, the above effective component (A1) has an
elution temperature of 40 to 88.degree. C. and a molecular weight
of the elution component at a temperature range of 44 to 68.degree.
C. of 100,000 to 1,000,000 measured by TREF/SEC.
[0021] The crystalline polyolefin resin composition of the present
invention is produced by the following methods: one in which a
polyolefin containing the effective component (A1) in an amount of
20 to 100 wt % (to be referred to as "the modifier (A1)" herein
after) is produced and mixed with a crystalline polyolefin resin
mechanically and one in which a catalyst used for the
polymerization of a crystalline polyolefin resin is suitably
selected and the crystalline polyolefin resin and the effective
component are produced in a polymerization system and obtained as a
mixture. That is, to obtain the polyolefin resin composition of the
present invention with ease, the former method is preferred but the
latter method is effective in many cases to obtain a uniform
mixture of the modifier of the present invention and a crystalline
polyolefin resin.
[0022] In the description of the present invention, a substantially
uniformly united product of the effective component (A1) and the
crystalline polyolefin resin is referred to as "polyolefin resin
composition of the present invention" irrespective of the method of
mixing the modifier (A1) and the crystalline polyolefin resin
component.
[0023] The polyolefin resin composition of the present invention
has a melt flow rate (MFR) of preferably 0.1 to 20 g/10 min, more
preferably 1 to 10 g/10 min in consideration of its moldability
into a film. The weight average molecular weight (Mw) of the
polyolefin resin composition is preferably 200,000 to 800, 000,
more preferably 250,000 to 450,000. The molecular weight
distribution expressed by the Mw/Mn ratio of weight average
molecular weight (Mw) to number average molecular weight (Mn) is
preferably in the range of 2 to 20, more preferably 4 to 10 in
consideration of film processing ease and the improvement of
workability caused by an increase in melt tension. The above
molecular weight distribution is obtained from weight average and
number average molecular weights calculated from the universal
calibration curve of polypropylene measured by SEC at 145.degree.
C. using orthodichlorobenzene as a solvent from an elution profile
measured under the same measurement conditions. The melting point
of the polyolefin resin is preferably 130.degree. C. or more, more
preferably 135 to 170.degree. C., particularly preferably 140 to
160.degree. C. The expression "melting point" as used herein
denotes the peak temperature of a crystal melting curve at the time
of temperature elevation measured with a differential scanning
calorimeter (to be simply abbreviated as DSC hereinafter).
[0024] The peak temperature of an elution curve measured by the
TREF of the above polyolefin resin composition is preferably in the
range of 100 to 130.degree. C., more preferably 110 to 125.degree.
C., particularly preferably 115 to 120.degree. C. in consideration
of the rigidity and heat resistance of an oriented film obtained
from the polyolefin resin composition. TREF is a method of
evaluating the crystallizabillity distribution of a polyolefin by
dissolving the polyolefin (such as a polypropylene resin)
crystallized in a solution in a solvent at different temperatures
and continuously measuring the elution (concentration) of the
polyolefin at each dissolution temperature. That is, a sample
solution having a certain concentration prepared by dissolving a
sample polyolefin in an orthodichlorobenzene solvent is injected
into the TREF column of an inert carrier such as diatomaceous earth
or silica beads as a filler, the temperature of the TREF column is
lowered to adhere the sample to the surface of the filler, the
column temperature is elevated to a desired temperature linearly,
the orthodichlorobenzene solvent is passed through the column, and
the elution (wt %) of the polyolefin component eluted at the above
temperature is measured. The crystallizabillity distribution of the
polyolefin at the elution temperature can be seen by this
operation. In this method, the descending speed of the temperature
of the TREF column must be adjusted to a speed required for the
crystallization of a crystalline portion contained in the sample
polyolefin at a predetermined temperature. The cooling rate of the
TREF column can be determined experimentally in advance. The
cooling rate of the column is generally set to a range of 5.degree.
C./min or less.
[0025] The amount of the component having an elution temperature of
0.degree. C. or less measured by TREF/SEC of the above polyolefin
resin composition is preferably 10 wt % or less, more preferably 7
wt % or less, particularly preferably 5 wt % or less in
consideration of the surface properties such as anti-blocking
properties, scratch resistance and slipperiness of the formed
polyolefin film.
[0026] Further, the molecular weight of the elution component
measured at 0.degree. C. by TREF/SEC of the above polyolefin resin
composition is preferably 10,000 to 400,000, more preferably
150,000 to 300,000 in terms of molecular weight at the peak top of
a molecular weight distribution curve of the elution component at
0.degree. C. measured by SEC in consideration of bleed-out to the
surface of a film and the formation of a fish-eye.
[0027] When the polyolefin resin composition of the present
invention contains a component having an elution temperature of 36
to 104.degree. C. and a molecular weight of 100,000 to 1,000,000
measured by TREF/SEC in an amount of 4 to 20 wt %, it achieves
excellent thickness accuracy and stretchability. The polyolefin
resin composition of the present invention contains a polyolefin
component having an elution temperature of more than 116.degree. C.
and a molecular weight of 10,000 to 100,000 measured by TREF/SEC in
an amount of preferably 4 to 20 wt %, more preferably 5 to 15 wt %,
particularly preferably 6 to 10 wt % to further improve heat
resistance such as the thermal shrinkage of the formed oriented
film. The polyolefin component is the same olefin polymer or
copolymer as the modifier.
[0028] Crystalline Polyolefin Resin
[0029] The crystalline polyolefin resin used in the present
invention is preferably a propylene homopolymer, a
propylene-.alpha.-olefin copolymer containing an .alpha.-olefin
other than propylene as a comonomer or a mixture thereof.
[0030] The above propylene-.alpha.-olefin copolymer is preferably a
propylene-.alpha.-olefin copolymer containing one or more
.alpha.-olefin monomer units other than propylene in an amount of
10 mol % or less, more preferably 5 mol % or less, or a mixture
thereof. Examples of the .alpha.-olefin include .alpha.-olefins
having 2 or 4 to 20 carbon atoms such as ethylene, butene-1,
pentene-1, 3-methyl-1-butene, hexene-1, 3-methyl-1-pentene,
4-methyl-1-pentene, heptene-1, octene-1, nonene-1, decene-1,
dodecene-1, tetradecene-1, hexadecene-1, octadecene-1 and
eicosene-1. The above propylene-.alpha.-olefin copolymer may be
either an random copolymer or block copolymer. Out of these, a
random copolymer is preferred.
[0031] When the above crystalline polyolefin resin is a propylene
homopolymer or a propylene-.alpha.-olefin copolymer which contains
an .alpha.-olefin other than propylene in an amount of less than 1
mol %, the fraction of isotactic pentad sequence measured by
.sup.13C-NMR indicating crystallizability is preferably 0.80 to
0.99, more preferably 0.85 to 0.98, particularly preferably 0.87 to
0.97. The fraction of isotactic pentad sequence is a fraction at
which 5 propylene units determined based on the assignment of the
peak of the .sup.13C-NMR spectrum take equal configuration
continuously, as reported by A. Zambelli et al in Macromolecules
13, 267, 1980.
[0032] The crystalline polyolefin resin used in the present
invention is not limited to the above polypropylene-based resin and
may be a polyolefin resin which is an olefin polymer or copolymer
other than a polypropylene-based resin and contains a crystal
portion measured by X-ray diffraction in an amount of 30 % or more,
preferably 40 % or more.
[0033] Modifier (A1)
[0034] The modifier (A1) used in the present invention contains a
component (A1) having an elution temperature of 36 to 104.degree.
C. and a molecular weight of 100,000 to 1,000,000 measured by
TREF/SEC in an amount of 20 to 100 wt % as described above. The
amount of the above component is preferably 40 to 100 wt %, more
preferably 50 to 100 wt %. It is more preferred that a component
having an elution temperature of 40 to 88.degree. C. and a
molecular weight of 100,000 to 1,000,000 measured by TREF/SEC
should be contained in an amount of 50 to 100 wt %. It is the most
preferred that a component having an elution temperature of 44 to
68.degree. C. and a molecular weight of 100,000 to 1,000,000 should
be contained in an amount of 50 to 100 wt %.
[0035] A crystalline polyolefin resin having lower crystallinity
than the above crystalline polyolefin resin may be used as the
modifier (A1) without restriction. The modifier (A1) is, for
example, an .alpha.-olefin homopolymer, a copolymer of two or more
.alpha.-olefins, or a mixture thereof. The .alpha.-olefin copolymer
may be either a random copolymer or block copolymer. Out of these,
a random copolymer is preferred. Examples of the .alpha.-olefin
include ethylene, propylene, butene-1, pentene-1,
3-methyl-1-butene, hexene-1, 3-methyl-1-pentene,
4-methyl-1-pentene, heptene-1, octene-1, nonene-1 and the like. Out
of these modifiers (A1), a propylene homopolymer,
ethylene-propylene copolymer, ethylene-1-hexene copolymer,
ethylene-1-octene copolymer, propylene-1-butene copolymer,
propylene-1-hexene copolymer, propylene-ethylene-1-butene copolymer
and mixtures thereof are particularly preferred.
[0036] The melt flow rate of the modifier (A1) is preferably 1 to
20 g/10 min. The weight average molecular weight (Mw) of the
modifier (A1) is preferably in the range of 100,000 to 400,000.
Further, the molecular weight distribution (Mw/Mn) of the modifier
(A1) is preferably in the range of 1.5 to 15.
[0037] Preferably, the modifier (A1) has at least one melting peak
at a range of 60 to 150.degree. C.
[0038] The component having an elution temperature of 0.degree. C.
or less measured by TREF/SEC of the above modifier (A1) is
preferably contained in an amount of 5 wt % or less, more
preferably 4 wt % or less, particularly preferably 3 wt % or less
in consideration of the surface properties such as anti-blocking
properties, scratch resistance and slipperiness of the formed
polyolefin film.
[0039] The modifier (A1) can be prepared by polymerizing eluting
components forming the modifier (A1) separately and mixing these.
Alternatively, it can be prepared as a block copolymer which can
attain a state in which a polypropylene component and a
propylene-ethylene random copolymer component are arranged in a
single molecular chain and/or a microscopically mixed state
unattainable by mechanical mixing of the molecular chains of the
polypropylene component and the propylene-ethylene random copolymer
component. The block copolymer is preferred because it has an
excellent stretchability improving effect and a more transparent
oriented film is obtained.
[0040] A preferred production method for obtaining the modifier
(A1) as a block copolymer comprises forming a polypropylene
component (a) and a propylene-ethylene copolymer component (b)
stepwise in the presence of a catalyst which comprises a
metallocene compound (to be referred to as "component (I)"
hereinafter) and an aluminoxane compound or non-coordination
ionized compound (to be referred to as "component (II)"
hereinafter).
[0041] The above component (I) is a known compound which is used
for the polymerization of an olefin. A chiral compound represented
by the following formula (1) is advantageously used as the
component (I):
Q(C.sub.5H.sub.4-mR.sup.1.sub.m)
(C.sub.5H.sub.4-nR.sup.2.sub.n)MX.sup.1X.- sup.2 (1)
[0042] wherein M is the transition metal atom of the group IV of
the periodic table, (C.sub.5H.sub.4-mR.sup.1.sub.m) and
(C.sub.5H.sub.4-nR.sup.2.sub.n) are each a substituted
cyclopentadienyl group, m and n are each an integer of 1 to 3,
R.sup.1 and R.sup.2 may be the same or different and each a
hydrocarbon group having 1 to 20 carbon atoms, silicon-containing
hydrocarbon group or hydrocarbon group forming at least one
hydrocarbon ring which may be bonded to two carbon atoms on a
cyclopentadienyl ring to be substituted by a hydrocarbon, Q is a
divalent hydrocarbon group, non-substituted silylene group or
hydrocarbon-substituted silylene group which can crosslink
(C.sub.5H.sub.4-mR.sup.1.sub.m) and
(C.sub.5H.sub.4-nR.sup.2.sub.n), and X.sup.1 and X.sup.2 may be the
same or different and each hydrogen, halogen or hydrocarbon
group.
[0043] The component (I) is preferably a chiral metallocene
compound of the above formula (1) in which M is a zirconium or
hafnium atom, R.sup.1 and R.sup.2 are the same or different
hydrocarbon groups having 1 to 20 carbon atoms, X.sup.1 and X.sup.2
are the same or different halogen atoms, and the hydrocarbon group
Q is a hydrocarbon-substituted silylene group.
[0044] Illustrative examples of the component (I) include
rac-dimethylsilylene(2,4-dimethylcyclopentadienyl)(3',
5'-dimethylcyclopentadienyl)zirconium dichloride,
rac-dimethylsilylene(2,- 4-dimethylcyclopentadienyl)(3',
5'-dimethylcyclopentadienyl)zirconium dimethyl,
rac-dimethylsilylene(2,3,5-trimethylcyclopentadienyl)(2', 4',
5'-trimethylcyclopentadienyl)zirconium dichloride,
rac-dimethylsilylene(2,3,5-trimethylcyclopentadienyl)(2', 4', 5',
5'-trimethylcyclopentadienyl)zirconium dimethyl,
rac-dimethylsilylenebis(- 2-methyl-indenyl)zirconium dichloride,
rac-diphenylsilylenebis(2-methyl-in- denyl)zirconium dichloride,
rac-dimethylsilylenebis(2-methyl-indenyl)zirco- nium dimethyl,
rac-diphenylsilylenebis(2-methyl-indenyl)zirconium dimethyl,
rac-dimethylsilylenebis(2-methyl-4,5,6,7-tetrahydroindenyl)zirc-
onium dichloride,
rac-diphenylsilylenebis(2-methyl-4,5,6,7-tetrahydroinden-
yl)zirconium dichloride,
rac-dimethylsilylenebis(2-methyl-4,5,6,7-tetrahyd-
roindenyl)zirconium dimethyl,
rac-diphenylsilylenebis(2-methyl-4,5,6,7-tet-
rahydroindenyl)zirconium dimethyl,
rac-dimethylsilylenebis(2,4-dimethyl-in- denyl)zirconium
dichloride, rac-diphenylsilylenebis(2,4-dimethyl-indenyl)z-
irconium dichloride,
rac-dimethylsilylenebis(2,4-dimethyl-indenyl)zirconiu- m dimethyl,
rac-diphenylsilylenebis(2,4-dimethyl-indenyl)zirconium dimethyl,
rac-dimethylsilylenebis(2-methyl-4-isopropylindenyl)zirconium
dichloride,
rac-diphenylsilylenebis(2-methyl-4-isopropylindenyl)zirconium
dichloride,
rac-dimethylsilylenebis(2-methyl-4-isopropylindenyl)zirconium
dimethyl,
rac-diphenylsilylenebis(2-methyl-4-isopropylindenyl)zirconium
dimethyl,
rac-dimethylsilylenebis(2-methyl-4,6-diisopropylindenyl)zirconi- um
dichloride,
rac-diphenylsilylenebis(2-methyl-4,6-diisopropylindenyl)zir- conium
dichloride,
rac-dimethylsilylenebis(2-methyl-4,6-diisopropylindenyl- )zirconium
dimethyl, rac-diphenylsilylenebis(2-methyl-4,6-diisopropylinden-
yl)zirconium dimethyl,
rac-dimethylsilylenebis(2-methyl-4-t-butylindenyl)z- irconium
dichloride, rac-diphenylsilylenebis(2-methyl-4-t-butylindenyl)zir-
conium dichloride,
rac-dimethylsilylenebis(2-methyl-4-t-butylindenyl)zirco- nium
dimethyl,
rac-diphenylsilylenebis(2-methyl-4-t-butylindenyl)zirconium
dimethyl,
rac-dimethylsilylenebis(2-methyl-4-phenylindenyl)zirconium
dichloride,
rac-diphenylsilylenebis(2-methyl-4-phenylindenyl)zirconium
dichloride,
rac-dimethylsilylenebis(2-methyl-4-phenylindenyl)zirconium
dimethyl,
rac-diphenylsilylenebis(2-methyl-4-phenylindenyl)zirconium
dimethyl,
rac-dimethylsilylenebis(2-methyl-4-naphthylindenyl)zirconium
dichloride,
rac-diphenylsilylenebis(2-methyl-4-naphthylindenyl)zirconium
dichloride,
rac-dimethylsilylenebis(2-methyl-4-naphthylindenyl)zirconium
dimethyl,
rac-diphenylsilylenebis(2-methyl-4-naphthylindenyl)zirconium
dimethyl, rac-dimethylsilylenebis(2-methyl-benzindenyl)zirconium
dichloride, rac-diphenylsilylenebis(2-methylbenzindenyl)zirconium
dichloride, rac-dimethylsilylenebis(2-methyl-benzindenyl)zirconium
dimethyl, rac-diphenylsilylenebis(2-methylbenzindenyl)zirconium
dimethyl and the like.
[0045] Compounds obtained by replacing the zirconium of the above
compounds by hafnium may be advantageously used. The above
metallocene compounds may be used in combination.
[0046] Out of the above components (II), aluminum compounds
represented by the following formulas (2) or (3) are preferred as
the aluminoxane compound. 1
[0047] In the above formulas (2) and (3), R is an alkyl group
having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms.
Examples of the alkyl group include methyl group, ethyl group,
propyl group, butyl group and isobutyl group, out of which methyl
group is preferred. Part of R's may be an alkyl group having 2 to 6
carbon atoms. m is an integer of 4 to 100, preferably 6 to 80,
particularly preferably 10 to 60.
[0048] To produce the above aluminoxane compound, various known
methods may be employed. They include one in which a
trialkylaluminum is directly reacted with water in a hydrocarbon
solvent and one in which a trialkylaluminum is reacted with water
adsorbed in a hydrocarbon solvent using copper sulfate hydrate
having crystallization water, aluminum sulfate hydrate, hydrated
silica gel or the like.
[0049] Out of the above components (II), known non-coordination
ionized compounds other than the above aluminoxane compounds are
used as the non-coordination ionized compound. Ionized compounds
containing a boron atom are particularly preferred.
[0050] Out of the ionized compounds containing a boron atom, Lewis
acid containing a boron atom and ionic compounds containing a boron
atom are preferred. The Lewis acid containing a boron atom is a
compound represented by the following formula (4).
BR.sub.3 (4)
[0051] In the above formula, R is a phenyl group having a
substituent such as a fluorine atom, methyl group or
trifluoromethyl group, or fluorine atom.
[0052] Illustrative examples of the compound represented by the
above formula (4) include trifluoroborane, triphenylborane,
tris(4-fluorophenyl)borane, tris(3,5-diflurophenyl)borane,
tris(4-fluoromethylphenyl)borane, tris(pentafluorophenyl)borane,
tris(p-tolyl)borane, tris(o-tolyl)borane,
tris(3,5-dimethylphenyl)borane and the like. Out of these,
tris(pentafluoro)borane is preferred.
[0053] The ionic compound containing boron is a
trialkyl-substituted ammonium salt, N,N-dialkylanilinium salt,
dialkylammonium salt, triaryl phosphonium salt or the like.
Specific examples of the trialkyl-substituted ammonium salt include
triethylammonium tetra(phenyl)boron, tripropylammonium
tetra(phenyl)boron, tri(n-butyl) ammonium tetra(phenyl)boron,
trimethylammonium (p-tolyl)boron, trimethylammonium
tetra(o-tolyl)boron, tributylammonium
tetra(pentafluorophenyl)boron, tripropylammonium
tetra(o,p-dimethylphenyl- )boron, tributylammonium
tetra(m,m-dimethylphenyl)boron, tributylammonium
tetra(p-trifluoromethylphenyl)boron, tri(n-butyl)ammonium
tetra(o-tolyl)boron and the like. Examples of the
N,N-dialkylanilinium salt include N,N-dimethylanilinium
tetra(phenyl)boron, N,N-diethylanilinium tetra(phenyl)boron,
N,N-2,4,6-pentamethylanilinium tetra(phenyl)boron and the like.
Examples of the dialkylammonium salt include di(1-propyl)ammonium
tetra(pentafluorophenyl)boron, dicyclohexylammonium
tetra(phenyl)boron and the like. Examples of the triarylphosphonium
salt include triphenylphosphonium tetra(phenyl)boron,
tri(methylphenyl)phosphonium tetra(phenyl)boron,
tri(dimethylphenyl)phosp- honium tetra(phenyl)boron and the
like.
[0054] Out of the Lewis acids containing a boron atom and the ionic
compounds containing a boron atom listed above, triphenylcarbonium
tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium
tetrakis(pentafluorophenyl)borate and ferrocenium
tetra(pentafluorophenyl- )borate are preferred. Triphenylcarbonium
tetrakis(pentafluorophenyl)borat- e and N,N-dimethylanilinium
tetrakis(pentafluorophenyl)borate are more preferred.
[0055] The components (I) and (II) may be used in any amounts. When
an aluminoxane compound is used as the component (II), the amount
of the component (II) (the molar amount of an A1 atom in the
component (II)) is preferably 0.1 to 100,000 mols, more preferably
1 to 50,000 mols, particularly preferably 10 to 30,000 mols based
on 1 mol of a transition metal atom contained in the component (I).
When a non-coordination ionized compound is used as the component
(II), the amount of the component (II) (the molar amount of the 3B
group atom in the component (II)) is preferably 0.01 to 10,000
mols, more preferably 0.1 to 5,000 mols, particularly preferably 1
to 3,000 mols based on 1 mol of a transition metal contained in the
component (I).
[0056] An organic aluminum compound (to be referred to as
"component (III)" hereinafter) may be used as required in the
method of producing the polypropylene component (a) and the
propylene-ethylene copolymer component (b) stepwise in the presence
of a catalyst which comprises the component (I) and the component
(II). The component (III) is preferably a compound represented by
the following formula (5):
AlR.sub.mX.sub.3- (5)
[0057] wherein R is an alkyl group having 1 to 10 carbon atoms,
hydrocarbon group such as an aryl group or alkoxy group, X is a
halogen atom, and m is an integer of 1 to 3 indicating the valence
of Al.
[0058] Illustrative examples of the compound represented by the
above formula (5) include trialkylaluminums such as
trimethylaluminum, triethylaluminum, tri-n-propylaluminum,
triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum,
tri-n-hexylaluminum, tri-n-octylaluminum and tri-n-decylaluminum;
dialkylaluminum monohalides such as diethylaluminum monochloride,
diethylaluminum monobromide and diethylaluminum monofluoride;
alkylaluminum halides such as methylaluminum sesquichloride,
ethylaluminum sesquichloride and ethylaluminum dichloride; and
alkoxyaluminums such as diethylaluminum monoethoxide and
ethylaluminum diethoxide. Out of these, trialkylaluminums such as
trimethylaluminum, triethylaluminum and triisobutylaluminum are
preferred.
[0059] The amount of the component (III) is preferably 1 to 50,000
mols, more preferably 5 to 10,000 mols, particularly preferably 10
to 5,000 mols based on 1 mol of a transition metal atom contained
in the component (I).
[0060] The component (I) and/or the component (II) may be carried
on a particulate carrier (to be referred to as "component (IV)"
hereinafter). When the above catalyst component(s) is(are) carried
on the carrier, the particle properties of the obtained polymer are
improved, thereby making it possible to prevent the adhesion of
polymer scales to a reactor and greatly improve process
applicability to the production of a resin.
[0061] The particulate carrier is what has a function as a carrier,
particularly preferably an inorganic oxide.
[0062] Illustrative examples of the inorganic oxide include
SiO.sub.2, Al.sub.2O.sub.3, MgO, ZrO.sub.2, TiO.sub.2,
B.sub.2O.sub.31, CaO, ZnO, BaO, ThO.sub.2, and mixtures thereof
such as SiO.sub.2--Al.sub.2O.sub.3, SiO.sub.2--MgO,
SiO.sub.2--TiO.sub.2, SiO.sub.2--V.sub.2O.sub.5,
SiO.sub.2--Cr.sub.2O.sub.3 and SiO.sub.2--TiO.sub.2--MgO. Out of
these, carriers containing at least one component selected from the
group consisting of SiO.sub.2 and Al.sub.2O.sub.3 as the main
ingredient are preferred.
[0063] The carrier preferably used in the present invention, whose
properties differ according to its type and production method, has
a particle diameter of 10 to 300 .mu.m, preferably 20 to 200 .mu.m,
a specific surface area of 50 to 1,000 m.sup.3/g, preferably 100 to
700 m.sup.3/g and a pore volume of 0.3 to 3.0 cm.sup.3/g,
preferably 0.5 to 2.5 cm.sup.3/g.
[0064] The inorganic particulate carrier is baked at preferably 150
to 1,000.degree. C., more preferably 200 to 800.degree. C.
[0065] The particle diameter of the carrier is preferably 0.1 to
500 .mu.m, more preferably 1 to 200 .mu.m, particularly preferably
10 to 100 .mu.m. When the particle diameter is too small, a fine
powder polymer is formed and when the particle diameter is too
large, coarse particles are formed, thereby making it difficult to
handle powders.
[0066] The pore volume of the carrier is preferably 0.1 to 5
cm.sup.3/g, more preferably 0.3 to 3 cm.sup.3/g. The pore volume
can be measured by a BET method or mercury intrusion porosity
method.
[0067] The amount of the metallocene compound (I) based on 1 g of
the above particulate carrier (IV) is 0.005 to 1 mmol, preferably
0.05 to 0.5 mmol in terms of transition metal atoms. When an
aluminoxane compound is used as the component (II), the amount of
the aluminoxane compound is preferably 1 to 200 mols, more
preferably 15 to 150 mols in terms of the molar amount of an Al
atom based on 1 mol of a transition metal atom contained in the
component (I).
[0068] When a non-coordination ionized compound is used as the
component (II), the amount of the non-coordination ionized compound
is preferably 0.1 to 20 mols, more preferably 1 to 15 mols in terms
of the molar amount of the group XIII atom contained in the
non-coordination ionized compound based on 1 mol of a transition
metal atom in the component (I).
[0069] To obtain a polymer having more excellent particle
properties, the following methods may be employed. That is, an
olefin is prepolymerized in the presence of the above components
(I), (II) and (IV) and the component (III) as required. The amount
of the component (III) to be prepolymerized is preferably 1 to
50,000 mols, more preferably 5 to 10,000 mols, particularly
preferably 10 to 5,000 mols based on 1 mol of a transition metal
atom contained in the component (I). The above components used for
prepolymerization may be added sequentially or simultaneously in
the form of a mixture. Preferably, the components (I) and (II) are
contacted to the catalyst component (IV) in advance. More
preferably, the component (II) is carried on the catalyst component
(IV) and then the component (I) is carried on the catalyst
component (IV). This method is effective in obtaining a random
copolymer having a more excellent bulk specific gravity.
[0070] Examples of the olefin prepared for the preparation of a
prepolymerization catalyst component include .alpha.-olefins such
as ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene,
1-hexene, 4-methyl-1-pentene, 4,4-dimethyl-1-pentene, 1-heptene,
4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 3-ethyl-1-hexene,
4-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene,
1-hexadecene, 1-octadecene and 1-eicosene; and cyclic olefins such
as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene,
tetracyclododecene and
2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene.
In addition to these, styrene, dimethylstyrenes, allylnorbornene,
allylbenzene, allylnaphthalene, allyltoluenes, vinylcyclopentane,
vinylcyclohexane, vinylcycloheptane and dienes may also be used.
Out of these, ethylene, propylene, 1-butene, 1-pentene,
3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene,
4,4-dimethyl-1-pentene, 1-heptene, 4-methyl-1-hexene,
4,4-dimethyl-1-hexene, 3-ethyl-1-hexene, 4-ethyl-1-hexene,
1-octene, 1-decene, cyclopentene and vinylcyclohexane are
preferred, and ethylene, propylene, 1-butene, 1-heptene,
3-methyl-1-butene, 1-hexene and 4-methyl-1-pentene are particularly
preferred.
[0071] Prepolymerization is preferably the homopolymerization of 95
mol % or more of an olefin.
[0072] The amount of an olefin to be prepolymerized firstly in the
present invention is preferably 0.1 to 1,000 g, more preferably 1
to 50 g based on 1 g of a catalyst formed from the catalyst
components (I), (II) and (IV).
[0073] Particularly preferably, prepolymerization is carried out
stepwise in such a manner that propylene is prepolymerized in the
presence of the components (I), (II) and (IV) and the component
(III) as required to obtain a first prepolymerization catalyst and
then 1-butene is prepolymerized in the presence of the first
prepolymerization catalyst and the above component (III).
[0074] The amount of the component (III) used for the
prepolymerization is preferably 1 to 50,000 mols, more preferably 5
to 10,000 mols, particularly preferably 10 to 5,000 mols based on 1
mol of a transition metal atom contained in the component (I).
After the first prepolymerization catalyst is obtained by the
prepolymerization of propylene, unreacted propylene and the
component (III) used as required are desirably removed by washing
and then used for the subsequent prepolymerization.
[0075] Substantial homopolymerizations of 95 mol% or more,
preferably 98 mol% or more each of propylene and 1-butene are
carried out in the above prepolymerization stages.
[0076] The amount of propylene first prepolymerized is preferably
0.1 to 1,000 g, more preferably 1 to 10 g based on 1 g of a
catalyst formed from the catalyst components (I), (II) and (IV).
The amount of 1-butene prepolymerized subsequently is preferably
0.1 to 1,000 g, more preferably 1 to 500 g based on 1 g of a
catalyst formed from the components (I), (II) and (III). The weight
ratio of propylene to 1-butene is preferably 0.001 to 100, more
preferably 0.005 to 10.
[0077] Slurry polymerization is preferably applied in
prepolymerization. The solvent used for the slurry polymerization
is a saturated aliphatic hydrocarbon such as hexane, heptane,
cyclohexane, benzene or toluene, aromatic hydrocarbon or mixture
thereof. The prepolymerization temperature is preferably -20 to
100.degree. C., more preferably 0 to 60.degree. C. The
prepolymerization stages may be carried out at different
temperatures. The prepolymerization time is suitably determined
according to the prepolymerization temperature and the amount of
prepolymerization. The prepolymerization pressure is, for example,
atmospheric pressure to 5 kg/cm.sup.2 in the case of slurry
polymerization.
[0078] Prepolymerization of each stage may be carried out in either
batch, semi-batch or continuous system.
[0079] After the end of prepolymerization, the obtained polymer is
preferably washed with a saturated aliphatic hydrocarbon such as
hexane, heptane, cyclohexane, benzene or toluene, aromatic
hydrocarbon or mixed solvent thereof. The number of times of
washing is preferably 5 to 6.
[0080] The modifier (A1) is produced by polymerizing a
polypropylene component and a propylene-ethylene copolymer
component stepwise in the presence of the above catalyst
components. As for polymerization order, the polypropylene
component (a) is preferably formed in the first stage and the
propylene-ethylene copolymer component (b) in the second stage.
Thereby, a polymer having excellent particle properties can be
produced.
[0081] The polymerization of the polypropylene component (a) is
carried out by supplying propylene alone or a mixture of propylene
and other .alpha.-olefin including ethylene. The temperature for
the polymerization of propylene is preferably 0 to 100.degree. C.,
more preferably 20 to 80.degree. C.
[0082] Hydrogen may be existent as a molecular weight modifier
during the polymerization. Polymerization may be slurry
polymerization using a monomer for use in polymerization as a
solvent, vapor-phase polymerization or solution polymerization.
Slurry polymerization using propylene itself as a solvent is
preferred when process simplicity, reaction rate and the particle
properties of the formed copolymer are taken into
consideration.
[0083] Polymerization system may be either batch, semi-batch or
continuous. Further, polymerization may be carried out in two or
more stages under different conditions such as hydrogen
concentration and polymerization temperature.
[0084] Thereafter, the random copolymerization of propylene and
ethylene is carried out. The random copolymer component (b) of
propylene and ethylene can be obtained by supplying ethylene gas
continuously even after the polymerization of propylene in the case
of slurry polymerization-using propylene itself as a solvent or
supplying mixed gas of propylene and ethylene in the case of
vapor-phase polymerization.
[0085] The random copolymerization of propylene and ethylene is
preferably carried out in a single stage after the polymerization
of propylene but may be carried out in multiple stages by changing
the concentration of ethylene. The temperature for the random
copolymerization of propylene and ethylene is preferably 0 to
100.degree. C., more preferably 20 to 80.degree. C. Hydrogen may be
used as a molecular weight modifier as required. Polymerization may
be carried out by changing the concentration of hydrogen stepwise
or continuously.
[0086] The random copolymerization system of propylene and ethylene
may be either batch, semi-batch or continuous. Polymerization may
be carried out in multiple stages. Polymerization may be slurry
polymerization, vapor-phase polymerization or solution
polymerization.
[0087] After the end of the polymerization, the monomers are
evaporated from a polymerization system to obtain the
propylene-based resin (modifier (A1)) of the present invention.
This propylene-based resin may be subjected to conventional washing
with a hydrocarbon having 7 or less carbon atoms or countercurrent
washing.
[0088] Production of Crystalline Polyolefin Resin Composition
[0089] The method of producing the crystalline polyolefin resin
composition of the present invention by mixing the above modifier
(A1) with the crystalline polyolefin resin is not particularly
limited. For instance, a powder blending method using a tumbler,
Henschel mixer or the like, or pellet blending method may be
used.
[0090] The crystalline polyolefin resin composition of the present
invention may also be produced by forming the effective components
of the modifier (A1) and the crystalline polyolefin in the same
polymerization system and mixing the both components formed in the
polymerization system. For example, several different
polymerization catalyst components capable of forming polypropylene
resins which differ from each other in isotacticity are mixed
together to polymerize propylene. A method of polymerizing
propylene by mixing a solid titanium catalyst component, organic
aluminum compound and two or more electron donors which give
polypropylene resins different from each other in isotacticity is
particularly preferably employed. In this method, known electron
donors which are generally used in the polymerization of propylene
may be used without restriction. When an organic silicon compound
represented by the following formula (V) or (VI) is used out of
these, a composition containing a component having an elution
temperature of 36 to 104.degree. C. and a molecular weight of
100,000 to 1,000,000 measured by TREF/SEC in amount of 4 to 20 wt %
is obtained with ease. 2
[0091] wherein R.sup.1, R.sup.2 and R.sup.3 are the same or
different hydrocarbon groups, and n is 0 or 1.
[0092] Known compounds which are used for the polymerization of
propylene may be used as the above solid titanium catalyst
component. Solid titanium catalyst components containing titanium,
magnesium or halogen and having high catalytic activity are
particularly preferred. The catalyst components are titanium
halides, particularly titanium tetrachloride carried on various
magnesium compounds, particularly magnesium chloride.
[0093] Known compounds which are used for the polymerization of
propylene may be used as the organic aluminum compound, as
exemplified by trialkylaluminums such as trimethylaluminum,
triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum,
tri-isobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum and
tri-n-decylaluminum; diethylaluminum monohalides such as
diethylaluminum monochloride; and alkylaluminum halides such as
methylaluminum dichloride and ethylaluminum dichloride.
Alkoxyaluminums such as monoethoxy diethylaluminum and diethoxy
monoethylaluminum may also be used. Out of these, triethylaluminum
is the most preferred. As for the amount of the organic aluminum
compound, the molar ratio of aluminum atoms to titanium atoms
contained in the solid titanium catalyst component is preferably 10
to 1,000, more preferably 50 to 500.
[0094] In the organic silicon compounds represented by the above
formulas (V) and (VI), the hydrocarbon groups represented by
R.sup.1, R.sup.2 and R.sup.3 may be chain, branched or cyclic
aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The
number of carbon atoms of the hydrocarbon groups is not
particularly limited. The hydrocarbon groups preferably used in the
present invention include alkyl groups having 1 to 6 carbon atoms
such as methyl group, ethyl group, n-propyl group, i-propyl group,
n-butyl group, i-butyl group, s-butyl group, t-butyl group, pentyl
group and hexyl group; alkenyl groups having 2 to 6 carbon atoms
such as vinyl group, propenyl group and allyl group; alkinyl groups
having 2 to 6 carbon atoms such as ethynyl group and propynyl
group; cycloalkyl groups having 5 to 7 carbon atoms such as
cyclopentyl group, cyclohexyl group and cycloheptyl group; and aryl
groups having 6 to 12 carbon atoms such as phenyl group, tolyl
group, xylyl group and naphthyl group. Out of these, R.sup.3 is
preferably a linear alkyl group, alkenyl group or aryl group. n is
0 or 1.
[0095] Illustrative examples of the organic silicon compound
represented by the formula (V) preferably used in the present
invention include dimethyldimethoxysilane, diethyldimethoxysilane,
dipropyldimethoxysilane, divinyldimethoxysilane,
diallyldimethoxysilane, di-1-propenyldimethoxysil- ane,
diethynyldimethoxysilane, diphenyldimethoxysilane,
methylphenyldimethoxysilane, cyclohexylmethyldimethoxysilane,
tertiary-butylethyldimethoxysilane, ethylmethyldimethoxysilane,
propylmethyldimethoxysilane, cyclohexyltrimethoxysilane,
diisopropyldimethoxysilane, dicyclopentyldimethoxysilane,
vinyltrimethoxysilane, phenyltrimethoxysilane,
allyltrimethoxysilane and the like.
[0096] Illustrative examples of the organic silicon compound
represented by the above formula (VI) include tetraethoxysilane,
methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane,
butyltriethoxysilane, pentyltriethoxysilane,
isopropyltriethoxysilane, 1-propenyltriethoxysilane,
isopropenyltriethoxysilane, ethynyltriethoxysilane,
octyltriethoxysilane, dodecyltriethoxysilane,
phenyltriethoxysilane, allyltriethoxysilane and the like.
[0097] As for the amount of the organic silicon compound
represented by the above formula (V) or (VI), the molar ratio of
silicon atoms to titanium atoms contained in the solid titanium
catalyst component is preferably 0.1 to 500, more preferably 1 to
100. The molar ratio (V/VI) of the two different organic silicon
compounds is preferably 1: 5 to 1:25, more preferably 1:10 to 1:20.
When the molar ratio of the organic silicon compounds (V) and (VI)
is smaller than 1:5, the elution peak width measured by TREF of the
obtained polypropylene resin becomes narrow, that is, the amount of
a component having an elution temperature of 36 to 104.degree. C.
decreases, thereby reducing stretchability at the time of film
formation, increasing a metal load and causing the breakage of a
film by stretching very often.
[0098] The addition order of the above components is not
particularly limited. The organic silicon compounds represented by
the above formulas (V) and (VI) may be supplied at the same time or
separately. They may be contacted to or mixed with the organic
aluminum compound and then supplied.
[0099] Other preferred polymerization conditions are as follows.
The polymerization temperature is preferably 20 to 200.degree. C.,
more preferably 50 to 150.degree. C. Hydrogen may be existent in
polymerization as a molecular weight modifier. Polymerization may
be slurry polymerization, solvent-free polymerization or
vapor-phase polymerization and may be carried out in batch,
semi-batch or continuous system. Polymerization may be carried out
in two stages under different conditions. Before the polymerization
of propylene, the prepolymerization of propylene or other monomer
may be carried out. The above polymerization may be carried out in
multiple stages.
[0100] In the present invention, the polypropylene resin
composition obtained by the above method may be used alone or
blended with other polypropylene resin. Polypropylene resin
compositions obtained by the above method may be blended together
as a matter of course.
[0101] In the present invention, a polyolefin resin composition
containing a component having an elution temperature of 36 to 10420
C. and a molecular weight of 100,000 to 1,000,000 measured by
TREF/SEC in an amount of 4 to 20 wt % can be obtained directly from
the polyolefin resin composition obtained as described above or by
selecting an appropriate polyolefin resin composition obtained as
described above. Alternatively, the crystalline polyolefin resin
composition of the present invention having desired composition can
be obtained by mixing the modifier (A1) or crystalline polyolefin
resin with the above resin composition.
[0102] The crystalline polyolefin resin composition of the present
invention which comprises a modifier (A1) and a modifier (A2)
containing a component having an elution temperature of more than
116.degree. C. and a molecular weight of 10,000 to 100,000 measured
by TREF/SEC in an amount of 20 to 100 wt % can be obtained in the
same manner as described above. Alternatively, the crystalline
polyolefin resin composition of the present invention may be
obtained by mixing the modifier (A1) and the modifier (A2) which
contains a component having an elution temperature of more than
116.degree. C. and a molecular weight of 10,000 to 100,000 measured
by TREF/SEC in an amount of 20 to 100 wt % with the crystalline
polyolefin resin.
[0103] Modifier (A2)
[0104] The above modifier (A2) is a highly crystalline
polypropylene resin. The melt flow rate of the modifier (A2) is
preferably 5 to 100 g/10 min, more preferably in the range of 30 to
80 g/10 min in consideration of moldability into a film. The weight
average molecular weight (Mw) of the modifier (A2) is preferably in
the range of 50,000 to 800,000, more preferably 100,000 to
300,000.
[0105] The molecular weight distribution (Mw/Mn) of the modifier
(A2) is preferably 1.5 to 40, more preferably 2 to 10 in
consideration of film forming ease and the improvement of
workability caused by an increase in melt tension.
[0106] The melting point of the above modifier (A2) is preferably
150.degree. C. or more, more preferably 155 to 170.degree. C.
[0107] The peak top temperature of an elution curve measured by
TREF of the modifier (A2) is preferably 110.degree. C. or more,
more preferably 115 to 130.degree. C. in consideration of the
rigidity and heat resistance of the formed oriented film.
[0108] The component having an elution temperature of 0.degree. C.
or less measured by TREF/SEC of the modifier (A2) is preferably
contained in an amount of 5 wt % or less, more preferably 3 wt % or
less in consideration of the surface properties such as
anti-blocking properties, scratch resistance and slipperiness of
the formed polyolefin film.
[0109] When the modifier (A2) is a propylene homopolymer or
propylene-.alpha.-olefin copolymer and contains an .alpha.-olefin
other than propylene in an amount of less than 1 mol%, the fraction
of isotactic pentad sequence measured by .sup.13C-NMR and
indicating the crystallizability of the modifier is preferably 0.80
to 1, more preferably 0.93 to 0.99.
[0110] Alternatively, a modifier (to be referred to as "modifier
(A1/A2)") may be obtained by mixing the modifier (A1) and the
modifier (A2) in a ratio of 20/80 or 80/20 and mixed with the
crystalline resin.
[0111] The weight ratio (A2/A1) of the effective component of the
modifier (A1) to the effective component of the modifier (A2) to be
mixed with the crystalline polyolefin resin is preferably in the
range of 0.5 to 2, more preferably 0.8 to 1.5. Within the above
range, the effect of improving stretchability at the time of film
formation, that is, the expansion of the width of film processable
temperature, a reduction in mechanical load, a reduction in film
breakage and the improvement of thickness accuracy for stretching
can be made possible.
[0112] Other Components
[0113] The polyolefin resin composition of the present invention
may contain additives such as an antioxidant, chlorine trapping
agent, heat stabilizer, antistatic agent, anti-fogging agent,
ultraviolet light absorber, lubricant, nucleating agent,
anti-blocking agent, pigment, other resin and filler as required in
limits that do not prevent the effect of the present invention.
[0114] Molding of Polyolefin Resin Composition
[0115] The polyolefin resin composition of the present invention
may be used in the production of all kinds of moldings and exhibits
excellent extrudability and stretchability. Particularly, it shows
a marked effect when it is stretched to obtain an oriented
film.
[0116] The polyolefin oriented film of the present invention may be
either a biaxially oriented or uniaxially oriented film. The
thickness of the oriented film is preferably 3 to 150 .mu.m in the
case of a biaxially oriented film and 10 to 254 .mu.m in the case
of a uniaxially oriented film. The draw ratio is 4 to 10 times in a
uniaxial direction and further 4 to 15 times in a direction
perpendicular to the above uniaxial direction in the case of
biaxial orientation.
[0117] One side or both sides of the polyolefin oriented film of
the present invention may be surface treated by corona discharge or
the like as required. Further, a layer of other resin having a
lower melting point than the polyolefin resin used in the present
invention may be formed on one side or both sides of the polyolefin
oriented film to provide such a function as heat sealability. The
method of forming the other resin layer on the polyolefin oriented
film is not particularly limited but it is preferably coextrusion
or lamination.
[0118] To produce the polyolefin oriented film of the present
invention, known methods may be employed. For example, when an
oriented film is formed by sequential biaxial orientation using a
tenter, the above polypropylene resin composition is formed into a
sheet or film by a T-die method or inflation method, the sheet or
film is supplied to a vertical stretching machine to be stretched
to 3 to 10 times in a longitudinal direction at a heating roll
temperature of 120 to 170.degree. C. and then stretched to 4 to 15
times in a transverse direction at a tenter temperature of 130 to
180.degree. C. using a tenter. The above molding conditions are not
particularly limited. However, to obtain an oriented film having
excellent thickness accuracy and fusing sealability, the sheet or
film is preferably stretched to 3 to 5 times in a longitudinal
direction at 145 to 170.degree. C. and to 4 to 12 times in a
transverse direction at 155 to 180.degree. C. Further, it is heat
set at 80 to 180.degree. C. while it is relaxed by 0 to 25% in a
transverse direction as required. As a matter of course, it may be
stretched again after this and multi-stage stretching and rolling
may be combined for stretching in a longitudinal direction. An
oriented film may be obtained by stretching in only a uniaxial
direction.
[0119] The polyolefin resin composition of the present invention is
characterized in that it has a wider range of film processable
temperature than conventionally known polyolefin resins, the
mechanical load at the time of stretching is small, the thickness
accuracy of the formed film is high, stretchability is satisfactory
and film breakage by stretching hardly occurs. Therefore, the
polyolefin resin composition of the present invention is a
polyolefin resin composition which allows for stable and continuous
operation and is suitable for the production of an oriented film.
Further, the formed oriented film has excellent heat resistance
such as thermal shrinkage. These effects show that the polyolefin
resin composition of the present invention is excellent as a
polyolefin resin composition for an oriented film and of great
industrial value.
EXAMPLES
[0120] The following examples and comparative examples are provided
for the purpose of further illustrating the present invention but
are in no way to be taken as limiting.
[0121] (1) TREF/SEC
[0122] The molecular weight distribution curve, the weight average
molecular weight and the amount of elution measured at an elution
temperature range by TREF/SEC were obtained using the multi-purpose
liquid chromatograph of Uniflows Co., Ltd. in a TREF/SEC mode under
the following conditions.
[0123] solvent: orthodichlorobenzene
[0124] TREF column: 4.6 mm in diameter.times.150 mm
[0125] filler: chromosolve P
[0126] flow rate: 1.0 ml/min
[0127] crystallization condition: 140 to 0.degree. C. (cooling
rate: 2.0.degree. C./hr)
[0128] temperature elevation condition: 4.degree. C. in each step,
36 fractions in total (0, 4, 8, 12, 16, 20, 24, 28, 32, 36, 40, 44,
48, 52, 56, 60, 64, 68, 72, 76, 80, 84, 88, 92, 96, 100, 104, 108,
112, 116, 120, 124, 128, 132, 136, 140)
[0129] SEC column: SHODEX UT 807+806M.times.2
[0130] SEC constant temperature bath: 145.degree. C.
[0131] detector: infrared detector for high-temperature liquid
chromatography
[0132] measurement wavelength: 3.41 .mu.m
[0133] sample concentration: 0.4 wt %
[0134] amount of injection: 500 .mu.l
[0135] In this case, a sample solution is introduced into the TREF
column at 140.degree. C. and stopped, and the temperature of the
TREF column is lowered from 140.degree. C. to 0.degree. C. at a
rate of 2.degree. C./hour to crystallize the sample polymer on the
surface of a filler. After the sample polymer is maintained at
0.degree. C. for 30 minutes, a component dissolved at 0.degree. C.
is introduced into the SEC column at a rate of 1.0 ml/min to carry
out SEC measurement. Meanwhile, the temperature of the TREF
constant temperature bath is raised to the next measurement
temperature (4.degree. C.) rapidly and maintained at that
temperature until the SEC measurement is over. Similarly, a
component dissolved at 4.degree. C. is introduced into the SEC
column to carry out SEC measurement. The SEC measurement is carried
out repeatedly until the set temperature is reached.
[0136] (2) TREF
[0137] The amount of elution at each temperature measured by TREF
is obtained using the multi-purpose liquid chromatograph of
Uniflows Co., Ltd. in a TREF mode under the following
conditions.
[0138] solvent: orthodichlorobenzene
[0139] TREF column: 4.6 mm in diameter.times.150 mm
[0140] filler: chromosolve P
[0141] flow rate: 1.0 ml/min
[0142] crystallization condition: 140 to 0.degree. C. (cooling
rate: 2.0.degree. C./hr)
[0143] temperature elevation condition: continuous elevation of
temperature, 40.degree. C./hr (temperature range of 0 to
140.degree. C.)
[0144] detector: infrared detector for high-temperature liquid
chromatography
[0145] measurement wavelength: 3.41 .mu.m
[0146] sample concentration: 0.4 wt %
[0147] amount of injection: 500 .mu.l
[0148] Like TREF/SEC, after the sample is crystallized, it is
maintained at 0.degree. C. for 30 minutes and the concentration of
a component dissolved at 0.degree. C. is detected. Thereafter, the
temperature of the TREF column is elevated linearly at a
predetermined rate, a solvent is caused to flow to detect the
concentration of the component, and the amount of elution is
obtained at each elution temperature.
[0149] (3) Melt Flow Rate (MFR)
[0150] This is measured in accordance with JIS K 7210.
[0151] (4) Molecular Weight Distribution
[0152] This is calculated from values of weight average molecular
weight and number average molecular weight obtained from an elution
profile which is measured using the SSC-7100 high-temperature GPC
apparatus of Senshu Kagaku Co., Ltd. under the following
conditions.
[0153] solvent: orthodichlorobenzene
[0154] flow rate: 1.0 ml/min
[0155] column temperature: 145.degree. C.
[0156] detector: high-temperature differential refractive index
detector
[0157] column: SHODEX UT 807 (1), 806M (2), 802.5 (1)
[0158] sample concentration: 0.1 wt %
[0159] amount of injection: 0.50 ml
[0160] (5) Fraction of Isotactic Pentad Sequence
[0161] This is measured using the JNM-GSX-270 (.sup.13C-NMR having
a nuclear resonance frequency of 67.8 MHz) of JEOL Ltd. under the
following conditions.
[0162] measurement mode: 1H-complete decoupling
[0163] pulse width: 7.0 .mu.sec (C45.degree.)
[0164] pulse repetition time: 3 sec
[0165] total number of times: 50,000
[0166] solvent: mixed solvent of orthodichlorobenzene/heavy benzene
(90/10 vol %)
[0167] sample concentration: 120 mg/2.5 ml of solvent
[0168] measurement temperature: 120.degree. C.
[0169] In this case, the fraction of isotactic pentad sequence is
obtained by measuring the cleavage peak in the methyl group region
of the .sup.13C-NMR spectrum. The assignment of the peak of the
methyl group region is based on A. Zambelli et al (Macromolecules
13, 267 (1980)).
[0170] (6) DSC Measurement
[0171] The melting point is measured using the DSC6200R apparatus
of Seiko Instruments Co., Ltd. under the following conditions.
[0172] temperature ascending rate: 10.degree. C./min (temperature
range of 230 to -30.degree. C.)
[0173] temperature descending rate: 10.degree. C./min (temperature
range of -30 to 230.degree. C.)
Example 1
[0174] (Preparation of Solid Titanium Catalyst)
[0175] A solid titanium catalyst was prepared in accordance with
themethod described in Example 1 of JP-A 58-83006. That is, 9.5 g
(100 mmol) of anhydrous magnesium chloride, 100 ml of decane and 47
ml (300 mmol) of 2-ethylhexyl alcohol were heated at 125.degree. C.
and stirred for 2 hours, and 5.5 g (37.5 mmol) of anhydrous
phthalic acid was added to this solvent and stirred and mixed at
125.degree. C. for 1 hour to prepare a uniform solution. After the
solution was cooled to room temperature, the total amount of the
solution was added dropwise to 400 ml (3.6 mmol) of titanium
tetrachloride maintained at -20.degree. C. over 1 hour. Thereafter,
the temperature of this mixed solution was raised to 110.degree. C.
over 2 hours and 5.4 ml (25 mmol) of diisobutyl phthalate was added
when 110.degree. C. was reached and maintained at 110.degree. C.
for 2 hours under agitation. After the end of 2 hours of a
reaction, a solid portion was collected by filtration under heating
and suspended in 2,000 ml of titanium tetrachloride again and a
heating reaction was carried out at 110.degree. C. for 2 hours
again. After the end of the reaction, a solid portion was collected
by filtration under heating again and fully washed with decane and
hexane until a free titanium compound in the wash liquid was not
detected. The solid titanium catalyst prepared by the above
production method was kept as a heptane slurry. As for the
composition of the solid titanium catalyst, it contained 2.1 wt %
of titanium, 57.0 wt % of chlorine, 18.0 wt % of magnesium and 21.9
wt % of diisobutyl phthalate.
[0176] (Prepolymerization)
[0177] 2,000 ml of purified n-hexane, 500 mmol of triethylaluminum,
25 mmol of cyclohexylmethyldimethoxysilane and 50 mmol in terms of
titanium atoms of a solid titanium compound component which was
subjected to a contact treatment were charged into a 10 liter
polymerizer the inside of which was substituted with nitrogen, and
propylene was introduced into the polymerizer continuously for 1
hour in an amount of 2 g based on 1 g of the solid titanium
catalyst component. The temperature was maintained at 15.degree. C.
during this period. The reaction was stopped after 1 hour and the
inside of the reactor was fully substituted by nitrogen. The solid
portion of the obtained slurry was washed with purified n-hexane 5
times to obtain a prepolymerization catalyst (titanium-containing
polypropylene). As the result of analysis, 1.7 g of propylene was
polymerized based on 1 g of the solid titanium catalyst.
[0178] (Polymerization)
[0179] 500 kg of propylene was charged into a 2,000-liter
polymerizer the inside of which was substituted by nitrogen, 1,752
mmol of triethylaluminum, 17.5 mmol of
cyclohexylmethyldimethoxysilane and 350 mmol of tetraethoxysilane
as organic silicon compounds, and 10 of hydrogen were charged into
the polymerizer, and then the temperature inside the polymerizer
was elevated to 65.degree. C. 4.38 mmol in terms of titanium atoms
of the prepolymerization catalyst obtained in the above
prepolymerization was charged and then the inside of the
polymerizer was elevated to 70.degree. C. to carry out the
copolymerization of propylene and ethylene for 2 hours. After the
end of the polymerization, unreacted propylene was purged, and the
obtained white granular polymer was vacuum dried at 70.degree. C.
for 1 hour. The structural characteristics of the obtained
polyolefin resin a are shown in Table 1 and Table 2.
[0180] (Granulation)
[0181] 0.1 part by weight of 2,6-di-t-butylhydroxytoluene as an
antioxidant, 0.1 part by weight of calcium stearate as a chlorine
trapping agent, 0.2 part by weight of stearyl diethanolamide as an
antistatic agent and 0.1 part by weight of spherical polymethyl
methacrylate particles having an average particle diameter of 1.5
.mu.m as an anti-blocking agent were added to 100 parts by weight
of the polyolefin resin a powders obtained in the above
polymerization of propylene, mixed with a Henschel mixer for 5
minutes, extruded with an extrusion granulating machine having a
screw diameter of 65 mm at 230.degree. C. and granulated to obtain
raw material pellets.
[0182] (Formation of Biaxially Oriented Film)
[0183] Experiments on the formation of a biaxially oriented film
were conducted using the obtained raw material pellets by the
following method. The raw material pellets were extruded from a
T-die sheet extruder having a screw diameter of 90 mm at
280.degree. C. to form a sheet having a thickness of 1 mm with a
30.degree. C. cooling roll. Thereafter, this raw sheet was
stretched between rolls to 5.6 times in a longitudinal direction
(machine direction:MD) using a tenter system sequential biaxial
stretching machine and then to 10 times in a transverse direction
(TD) in the tenter at 165.degree. C., relaxed by 4 % and heat set
to form a 20 .mu.m-thick biaxially oriented polyolefin film at a
rate of 50 m/min.
[0184] At the time of film formation, the preheating temperature of
a roll for stretching in a longitudinal direction was changed to
evaluate the range of film processable temperature (from lower
limit temperature to upper limit temperature). By lowering the
preheating temperature of the roll, the lower limit temperature at
which 10 minutes of stable film formation was possible without
causing film whitening, thickness nonuniformity and film breakage
was taken as the lower limit of film processable temperature. By
raising the preheating temperature of the roll, the upper limit
temperature at which 10 minutes of stable film formation was
possible without causing film whitening by the melting of the
surface of a longitudinally stretched sheet, thickness
nonuniformity and the like was taken as the upper limit of film
processable temperature. The difference between the upper limit and
the lower limit of film processable temperature was taken as the
width of film processable temperature. The film processability
(stretchability) was evaluated from mechanical loads (current
value, unit ampere) applied to longitudinal-direction stretching
and transverse-direction stretching at a center temperature of the
temperature width. The influence of stretching nonuniformity on
thickness accuracy was evaluated from the thickness pattern of a
film measured with the WEB GAGE infrared thickness measuring
instrument of Yokogawa Electric Corporation installed between the
tenter and the winding machine based on the following criteria.
[0185] .circleincircle.: less than .+-.0.5 .mu.m
[0186] .smallcircle.: .+-.0.5 .mu.m or more and less than 1.0
.mu.m
[0187] .DELTA.: .+-.1.0 .mu.m or more and less than 1.5 .mu.m
[0188] X: .+-.1.5 .mu.m or more
[0189] Further, the number of times of film breakage by stretching
in the tenter was evaluated by carrying out 5 hours of continuous
operation. One side of the formed film was treated with 30 W
min/m.sup.2 of corona discharge by a commonly used method and
wound. After the obtained oriented film was aged at 40.degree. C.
for 3 days, the thermal shrinkage (heat resistance) of the film was
measured by the following method.
[0190] A tape-form sample measuring 600 mm in length and 15 mm in
width was cut out from the film in longitudinal and transverse
directions, marked for a length of 500 mm (50 mm from both ends)
and left in a 120.degree. C. atmosphere for 15 minutes. Then, the
film sample was taken out and cooled at room temperature for 15
minutes to measure the length between marks so as to measure its
thermal shrinkage from the following equation.
thermal shrinkage (%)={(L.sub.0=L.sub.S)/L.sub.0}.times.100
[0191] L.sub.0: length between marks before thermal shrinkage (500
mm)
[0192] L.sub.S: length between marks after thermal shrinkage
(mm)
[0193] The range of film processable temperature, mechanical loads
applied to longitudinal-direction stretching and
transverse-direction stretching, the number of times of film
breakage by stretching during 5 hours of continuous operation,
thickness accuracy and thermal shrinkages in longitudinal and
transverse direction of an oriented film are shown in Table 3.
Example 2
[0194] The procedure of Example 1 was repeated except that 27 mmol
of cyclohexylmethyldimethoxysilane and 285 mmol of
ethyltriethoxysilane were used as organic silicon compounds to
homopolymerize propylene to obtain a polyolefin resin b shown in
Table 1. The results are shown in Tables 1, 2 and 3.
Comparative Example 1
[0195] The procedure of Example 1 was repeated except that 164 mmol
of cyclohexylmethyldimethoxysilane was used alone as an organic
silicon compound to homopolymerize propylene to obtain
polypropylene (polyolefin resin c) shown in Table 1. The results
are shown in Tables 1, 2 and 3.
Comparative Examples 2 and 3
[0196] The procedure of Comparative Example 1 was repeated to
obtain polyolefin resins d and e except that ethylene was
copolymerized. The results are shown in Tables 1, 2 and 3.
Comparative Example 4
[0197] The procedure of Comparative Example 1 was repeated except
that propylene was homopolymerized using
t-butylethyldimethoxysilane as an organic silicone compound in the
polymerization to obtain a polyolefin resin f. The results are
shown in Tables 1, 2 and 3.
Example 3
[0198] The procedure of Comparative Example 1 was repeated except
that copolymerization with ethylene was conducted in polymerization
to obtaine a polyolefin resin g shown in table 1.
[0199] The procedure of Example 1 was repeated except that the
polyolefin resin g and the polyolefin resin c obtained in
Comparative Example 1 were used in amounts shown in Table 2. The
results are shown in Tables 2 and 3.
Examples 4 and 5
[0200] The procedure of Example 3 was repeated except that the
amounts were changed as shown in Table 2. The results are shown in
Tables 2 and 3.
Example 6
[0201] The procedure of Example 1 was repeated except that the
propylene-ethylene copolymer (polyolefin resin h) (Biscole 660 of
Sanyo Chemical Industries, Ltd.) shown in Table 1 and the
polyolefin resin d obtained in Comparative Example 2 were used in
amounts shown in Table 2. The results are shown in Tables 2 and
3.
Example 7
[0202] Method of Producing Polyolefin Resin i (Preparation of
Carried Metallocene Catalyst)
[0203] 100 ml of a toluene solution of
rac-dimethylsilylenebis-1-(2-methyl- benzindenyl)zirconium
dichloride (0.005 mmol/ml of toluene solution) was added to 10 g of
methyl aluminoxane carried on a silica gel (MaO on SiO.sub.2,
manufactured by Whitco Co., Ltd., 25 wt %-Al product) and stirred
at room temperature for 30 minutes. The reaction mixture was then
filtered, and the obtained solid was washed with 50 ml of toluene
two times and vacuum dried to obtain a metallocene catalyst carried
on a silica gel. It was found that 0.045 mmol of metallocene was
carried based on 1 g of the catalyst.
[0204] (Polymerization)
[0205] 600 kg of propylene was injected into a polymerizer having
an inner volume of 2 m.sup.3 and 612 mmol of triisobutylaluminum
was introduced into the polymerizer. Thereafter, the temperature
inside the polymerizer was elevated to 55.degree. C. Subsequently,
ethylene gas was supplied to a vapor-phase concentration of 6.0 mol
% and then 10 g of the above metallocene catalyst carried on a
silica gel was charged. The temperature inside an autoclave was
elevated to 60.degree. C. to carry out polymerization for 2 hours
while ethylene gas was supplied to achieve a constant ethylene
vapor-phase concentration. After the end of polymerization,
unreacted propylene was purged and dried at 50.degree. C. for 1
hour to obtain 175 kg of a white granular polymer. The structural
characteristics of the obtained polyolefin resin i are shown in
Table 1.
[0206] The procedure of Example 1 was repeated except that the
above polyolefin i and the polyolefin resin d obtained in
Comparative Example 2 were used in amounts shown in Table 2. The
results are shown in Tables 2 and 3.
Example 8
[0207] Method of Producing Polyolefin Resin j
[0208] (Polymerization)
[0209] (Former Stage, Polymerization of Propylene)
[0210] 600 kg of propylene was injected into a polymerizer having
an inner volume of 2 m.sup.3 and 612 mmol of triisobutylaluminum
was introduced into the polymerizer. Thereafter, the temperature
inside the polymerizer was elevated to 55.degree. C. Subsequently,
5 g of a metallocene catalyst carried on a silica gel obtained in
the same manner as in [preparation of carried metallocene catalyst]
of Example 7 was charged. The temperature inside an autoclave was
elevated to 60.degree. C. to carry out polymerization for 70
minutes.
[0211] (Latter Stage, Copolymerization of Propylene and
Ethylene)
[0212] Ethylene gas was supplied to a vapor-phase concentration of
10.1 mol % after the former stage of polymerization.
Copolymerization was carried out for 70 minutes while ethylene gas
was supplied to maintain a constant vapor-phase concentration.
After the end of polymerization, unreacted propylene was purged and
dried at 50.degree. C. for 1 hour to obtain 135 kg of a white
granular polymer. The structural characteristics of the obtained
polyolefin resin j are shown in Table 1.
[0213] The procedure of Example 1 was repeated except that the
above polyolefin resin j and the polyolefin resin d obtained in
Comparative Example 2 were used in amounts shown in Table 2. The
results are shown in Tables 2 and 3.
Example 9
[0214] The procedure of Example 8 was repeated to obtain 175 kg of
a white granular polymer except that the vapor-phase concentration
of ethylene in the latter stage of polymerization in Example 8 was
changed to 17.2 mol %. The structural characteristics of the
obtained polyolefin resin k are shown in Table 1.
[0215] The procedure of Example 1 was repeated except that the
above polyolefin resin k and the polyolefin resin d obtained in
Comparative Example 2 were used in amounts shown in Table 2. The
results are shown in Tables 2 and 3.
Examples 10 to 12
[0216] The procedure of Example 1 was repeated except that the
commercially available propylene-butene copolymer (polyolefin resin
l) shown in Table 1 and the polyolefin resin d obtained in
Comparative Example 2 were used in amounts shown in Table 2. The
results are shown in Tables 2 and 3.
Comparative Example 5
[0217] The procedure of Example 1 was repeated except that the
polyolefin resin l used in Example 10 and the polyolefin resin c
obtained in Comparative Example 1 were used in amounts shown in
Table 2. The results are shown in Tables 2 and 3.
Examples 13 and 14
[0218] The procedure of Example 1 was repeated except that the
polyolefin resin l used in Example 10 and the polyolefin resin c
obtained in Comparative Example 1 were used in amounts shown in
Table 2. The results are shown in Tables 2 and 3.
Comparative Example 6
[0219] The procedure of Example 1 was repeated except that the
polyolefin resin l used in Example 10 and the polyolefin resin c
obtained in Comparative Example 1 were used in amounts shown in
Table 2. The results are shown in Tables 2 and 3.
Examples 15 to 17
[0220] The procedure of Example 1 was repeated except that the
polyolefin resin j obtained in Example 8 and the polyolefin resin c
obtained in Comparative Example 1 were used in amounts shown in
Table 2. The results are shown in Tables 2 and 3.
Example 18
[0221] The procedure of Example 1 was repeated except that the
polyolefin resin k obtained in Example 9 and the polyolefin resin c
obtained in Comparative Example 1 were used in amounts shown in
Table 2. The results are shown in Tables 2 and 3.
Examples 19 and 20
[0222] The procedure of Example 1 was repeated except that the
polyolefin resin k obtained in Example 9 and the polyolefin resin f
obtained in Comparative Example 4 were used in amounts shown in
Table 2. The results are shown in Tables 2 and 3.
Comparative Example 7
[0223] The procedure of Example 1 was repeated except that the
commercially available elastomer polyolefin resin m shown in Table
1 and the polyolefin resin f obtained in Comparative Example 4 were
used in amounts shown in Table 2. The results are shown in Tables 2
and 3.
Examples 21 and 22
[0224] (Preparation of Solid Titanium Catalyst)
[0225] A solid titanium catalyst was prepared in accordance with
the method described in Example 1 of JP-A 58-83006. That is, 0.95 g
(10 mmol) of anhydrous magnesium chloride, 10 ml of decane and 4.7
ml (30 mmol) of 2-ethylhexyl alcohol were heated at 125.degree. C.
and stirred for 2 hours, and 0.55 g (6.75 mmol) of anhydrous
phthalic acid was added to this solvent and stirred and mixed at
125.degree. C. for 1 hour to prepare a uniform solution. After the
solution was cooled to room temperature, the total amount of the
solution was added dropwise to 40 ml (0.36 mmol) of titanium
tetrachloride maintained at -20.degree. C. over 1 hour. Thereafter,
the temperature of this mixed solution was raised to 110.degree. C.
over 2 hours and 0.54 ml (2.5 mmol) of diisobutyl phthalate was
added when 110.degree. C. was reached and maintained at 110.degree.
C. for 2 hours under agitation. After the end of 2 hours of a
reaction, a solid portion was collected by filtration under heating
and suspended in 200 ml of titanium tetrachloride again and a
heating reaction was carried out at 110.degree. C. for 2 hours
again. After the end of the reaction, a solid portion was collected
by filtration under heating again and fully washed with decane and
hexane until a free titanium compound in the wash liquid was not
detected. The solid titanium catalyst prepared by the above
production method was kept as a heptane slurry. As for the
composition of the solid titanium catalyst, it contained 2.1 wt %
of titanium, 57.0 wt % of chlorine, 18.0 wt % of magnesium and 21.9
wt % of diisobutyl phthalate.
[0226] (Prepolymerization)
[0227] 200 ml of purified n-hexane, 50 mmol of triethylaluminum, 10
mmol of dicyclopentyl dimethoxysilane and 5 mmol in terms of
titanium atoms of a solid titanium compound component which was
subjected to a contact treatment were charged into a 1-liter
polymerizer the inside of which was substituted with nitrogen, and
propylene was introduced into the polymerizer continuously for 30
minutes in an amount of 2 g based on 1 g of the solid titanium
catalyst component. The temperature was maintained at 10.degree. C.
during this period. The reaction was stopped after 30 minutes and
the inside of the reactor was fully substituted by nitrogen. The
solid portion of the obtained slurry was washed with purified
n-hexane 5 times to obtain a prepolymerization catalyst
(titanium-containing polypropylene). As the result of analysis, 1.7
g of propylene was polymerized based on 1 g of the solid titanium
catalyst.
[0228] (Polymerization)
[0229] 100 kg of propylene was charged into a 400-liter polymerizer
the inside of which was substituted by nitrogen, 75 mmol of
triethylaluminum, 37.5 mmol of dicyclopentyl dimethoxysilane as an
organic silicon compound and hydrogen gas were further charged into
the polymerizer, and then the temperature inside the polymerizer
was elevated to 65.degree. C. 0.25 mmol in terms of titanium atoms
of the prepolymerization catalyst obtained in the above
prepolymerization was charged and then the temperature inside the
polymerizer was elevated to 70.degree. C. to carry out
polymerization for 6 hours. After the end of the polymerization, 50
ml of methanol was added as a polymerization inhibitor to stop the
reaction, 30 kg of liquid propylene was added to the polymerizer,
stirred for 1 hour and left to stand to precipitate polymer
particles, and a liquid propylene portion was extracted from the
top portion of the polymerizer by an extraction nozzle. The polymer
slurry in the polymerizer was supplied to a flash tank to separate
the polymer from unreacted propylene to obtain a white granular
polymer. The structural characteristics of the obtained polyolefin
resin n are shown in Table 1.
[0230] The procedure of Example 1 was repeated except that the
polyolefin resin l used in Example 10, the polyolefin resin n and
the polyolefin resin d obtained in Comparative Example 2 were used
in amounts shown in Table 2. The results are shown in Tables 2 and
3.
Example 23
[0231] The procedure of Example 1 was repeated except that the
polyolefin resin k obtained in Example 9 shown in Table 1, the
polyolefin resin n obtained in Example 21 and the polyolefin resin
c obtained in Comparative Example 1 were used in amounts shown in
Table 2. The results are shown in Tables 2 and 3.
Examples 24 to 26
[0232] (Preparation of Solid Titanium Catalyst)
[0233] A solid titanium catalyst was prepared in accordance with
the method described in Example 1 of JP-A 7-292029.
[0234] That is, 10 g of diethoxy magnesium and 80 ml of toluene
were charged into a 200 ml flask having a round bottom and equipped
with a stirrer the inside of which was fully substituted by
nitrogen gas to prepare a suspension. Thereafter, 20 ml of titanium
tetrachloride was added to the suspension and heated, and 2.7 ml of
di-n-butyl phthalate was added when the temperature reached
80.degree. C. and further heated at 110.degree. C. Thereafter, the
solution was stirred for 2 hours to carry out a reaction while the
temperature was maintained at 110.degree. C. After the end of the
reaction, the reaction product was washed with 100 ml of toluene
heated at 90.degree. C. two times, and 20 ml of titanium
tetrachloride and 80 ml of toluene were newly added, heated at
100.degree. C. and stirred for 2 hours to carry out a reaction.
After the end of the reaction, the reaction product was washed with
100 ml of n-heptane heated at 40.degree. C. 10 times to obtain a
solid titanium catalyst. When the solid and liquid contained in the
solid titanium catalyst were separated from each other to measure
the titanium content of the solid, it was found to be 2.91 wt
%.
[0235] Prepolymerization and polymerization were carried out in the
same manner as in Example 21 to obtain a white granular polymer.
The structural characteristics of the obtained polyolefin resin o
are shown in Table 1.
[0236] The procedure of Example 1 was repeated except that the
polyolefin resin k obtained in Example 9 shown in Table 1, the
polyolefin resin o and the polyolefin resin d obtained in
Comparative Example 2 were used in amounts shown in Table 2. The
results are shown in Tables 2 and 3.
1 TABLE 1 MFR TREF36-104 TREF>116 TREF40-88 TREF44-68 melting
stereo- molecular g/10 10.sup.5-10.sup.6 10.sup.4-10.sup.5
TREF<0.degree. C. 10.sup.5-10.sup.6 10.sup.5-10.sup.6 point
regularity comonomer weight min wt % wt % wt % wt % wt % .degree.
C. mmmm (mol %) distribution a 3.1 4.3 2.5 2.7 4.0 2.8 159 0.932
ethylene 7.0 0.5 b 2.1 4.1 6.3 3.3 3.7 2.3 160 0.937 -- 8.5 c 2.3
2.3 7.8 2.0 1.1 0.9 161 0.962 -- 6.2 d 3.0 3.0 6.2 2.3 2.4 1.3 158
0.960 ethylene 6.5 0.7 e 1.9 44.1 0 5.2 35.2 23.5 145 -- ethylene
4.3 5.3 f 3.5 1.8 11.8 1.2 0.8 0.1 162 0.975 -- 6.1 g 7.5 55.0 0
6.1 39.2 28.8 137 -- ethylene 4.5 8.1 h 60 40.3 0 4.3 35.1 24.1 147
-- ethylene 3.1 5.1 i 8.7 45.2 0 0 12.3 10.2 125 -- ethylene 2.3
5.1 j 10.1 65.1 0 1.3 64.2 63.7 101-146 -- ethylene 2.2 7.0 k 13.2
95.7 0 0.5 92.2 90.3 85-146 -- ethylene 2.3 12.3 l 8 55.3 0 9.2
41.1 28.8 110 -- butene 4.6 25 m 8 4.8 0 95.2 0 0 -- -- ethylene
2.0 18.2 n 40 1.9 22.2 2.1 1.0 0.1 161 0.981 -- 6.0 o 40 0.8 39.8
0.5 0.5 0 163 0.993 -- 5.8
[0237]
2 TABLE 2 raw raw raw material 1 material 2 material 3 TREF36-104
TREF>116 (quantity) (quantity) (quantity) 10.sup.5-10.sup.6
10.sup.4-10.sup.5 TREF<0.degree. C. wt % wt % wt % wt % A1 wt %
A2 wt % Ex.1 a 100 -- -- -- -- 4.3 2.5 2.7 Ex.2 b 100 -- -- -- --
4.1 6.3 3.3 C.Ex.1 c 100 -- -- -- -- 2.3 7.8 2.0 C.Ex.2 d 100 -- --
-- -- 3.0 6.2 2.3 C.Ex.3 e 100 -- -- -- -- 44.1 0 5.2 C.Ex.4 f 100
-- -- -- -- 1.8 11.8 1.2 Ex.3 c 96 g 4 -- -- 4.4 7.5 2.2 Ex.4 c 92
g 8 -- -- 6.5 7.2 2.3 Ex.5 c 85 g 15 -- -- 10.2 6.5 2.6 Ex.6 d 92 h
8 -- -- 6.0 5.7 2.5 Ex.7 d 92 i 8 -- -- 6.4 5.7 2.1 Ex.8 d 92 j 8
-- -- 8.0 5.7 2.2 Ex.9 d 92 k 8 -- -- 10.4 5.7 2.2 Ex.10 d 92 l 8
-- -- 7.2 5.7 2.9 Ex.11 d 96 l 4 -- -- 5.5 6.0 2.3 Ex.12 d 98 l 2
-- -- 4.2 6.0 2.3 C.Ex.5 c 98 l 2 -- -- 2.9 6.0 2.3 peak top
molecular TREF40-88 TREF44-68 weight of TREF at 0.degree. C.
10.sup.5-10.sup.6 10.sup.5-10.sup.6 MFR (.times.10.sup.-4) wt % wt
% A2/A1 g/10 min Ex.1 22.3 4.0 2.8 0.58 3.1 Ex.2 32.4 3.7 2.3 1.54
2.1 C.Ex.1 22.9 1.1 0.9 3.39 2.3 C.Ex.2 21.5 2.4 1.3 2.07 3.0
C.Ex.3 11.5 35.2 23.5 0 1.9 C.Ex.4 19.5 0.8 0.1 6.56 3.5 Ex.3 22.9
2.6 2.0 1.70 2.4 Ex.4 22.9 4.1 3.1 1.10 2.5 Ex.5 16.9 6.8 5.1 0.65
2.8 Ex.6 21.5 5.0 3.1 0.95 3.8 Ex.7 21.5 3.2 2.0 0.89 3.3 Ex.8 21.5
7.3 6.3 0.72 3.3 Ex.9 21.5 9.6 8.4 0.55 3.4 Ex.10 21.5 5.5 3.5 0.79
3.2 Ex.11 21.5 4.9 3.8 1.09 3.1 Ex.12 21.5 3.6 2.5 1.43 3.1 C.Ex.5
22.9 2.4 1.3 2.07 2.4 raw raw raw material 1 material 2 material 3
TREF36-104 TREF>116 (quantity) (quantity) (quantity)
10.sup.5-10.sup.6 10.sup.4-10.sup.5 TREF<0.degree. C. wt % wt %
wt % wt % A1 wt % A2 wt % Ex.13 c 96 l 4 -- -- 4.4 6.0 2.3 Ex.14 c
85 l 15 -- -- 10.3 6.0 3.1 C.Ex.6 c 60 l 40 -- -- 23.5 4.7 4.9
Ex.15 c 95 j 5 -- -- 5.4 7.4 2.0 Ex.16 c 90 j 10 -- -- 8.6 7.0 1.9
Ex.17 c 75 j 25 -- -- 18.0 5.9 1.8 Ex.18 c 95 k 5 -- -- 7.0 7.4 1.9
Ex.19 f 95 k 5 -- -- 6.5 5.4 4.6 Ex.20 f 90 k 10 -- -- 11.8 10.5
1.1 C.Ex.7 f 90 m 10 -- -- 2.1 10.6 10.6 Ex.21 d 92 l 4 n 4 5.0 6.6
2.6 Ex.22 d 84 l 8 n 8 7.1 7.0 2.8 Ex.23 c 68 k 12 n 20 9.8 9.7 1.9
Ex.24 d 94 k 4 o 2 6.7 6.6 2.2 Ex.25 d 97 k 2 o 1 4.8 6.4 2.2 Ex.26
d 70 k 10 o 20 11.8 12.3 1.8 peak top molecular TREF40-88 TREF44-68
weight of TREF at 0.degree. C. 10.sup.5-10.sup.6 10.sup.5-10.sup.6
MFR (.times.10.sup.-4) wt % wt % A2/A1 g/10 min Ex.13 22.9 2.7 2.0
1.69 2.4 Ex.14 22.9 7.1 5.1 0.65 2.8 C.Ex.6 22.9 17.1 12.1 0.20 3.8
Ex.15 22.9 4.3 4 1.36 2.5 Ex.16 22.9 7.4 7.2 0.82 2.7 Ex.17 22.9
16.9 16.6 0.33 3.3 Ex.18 22.9 5.7 5.4 1.06 2.5 Ex.19 24.1 1.2 11.2
1.73 3.7 Ex.20 24.1 10.5 9.7 0.89 4.0 C.Ex.7 9.1 0.7 0.1 5.01 3.8
Ex.21 21.5 3.9 2.4 1.31 3.5 Ex.22 20.8 5.4 3.4 0.98 4.0 Ex.23 18.4
8.7 8.3 1.00 5.0 Ex.24 21.5 6.0 4.8 0.99 3.4 Ex.25 21.5 4.2 3.1
1.33 3.2 Ex.26 16.8 11.0 9.9 1.04 5.8 Ex.: Example C.Ex.:
Comparative Example
[0238]
3 TABLE 3? !film processable? ? mechanical? ? thermal?
!temperature? temperature? load? film breakage? ? shrinkage? !lower
limit? upper limit? width? MD? TD? (number of? thickness? MD? TD?
!.degree. C.? .degree. C.? .degree. C.? A? A? times)? accuracy? %?
% Ex.1 146 157 11 4.4 28.0 0 .smallcircle. 3.8 3.7 Ex.2 147 158 11
4.2 28.0 0 .smallcircle. 4.0 3.8 C.Ex.1 157 160 3 5.3 31.0 13 x 2.9
2.1 C.Ex.2 154 158 4 5.1 29.5 8 .DELTA. 3.4 3.2 C.Ex.3 129 145 16
3.0 22.0 0 .smallcircle. 8.1 17.6 C.Ex.4 158 160 2 5.7 32.5 17 x
2.0 1.7 Ex.3 147 159 12 4.2 27.5 0 .smallcircle. 3.2 2.5 Ex.4 142
158 16 3.6 24.5 0 .circleincircle. 3.8 4.7 Ex.5 137 156 19 3.2 23.0
0 .circleincircle. 5.6 6.1 Ex.6 144 157 14 4.0 26.0 0
.circleincircle. 4.2 5.1 Ex.7 143 158 15 4.0 25.5 0
.circleincircle. 4.3 5.1 Ex.8 141 158 17 3.6 23.5 0
.circleincircle. 4.2 4.6 Ex.9 139 158 19 3.3 24.0 0
.circleincircle. 4.8 5.9 Ex.10 141 157 16 3.5 24.5 0
.circleincircle. 4.8 5.9 Ex.11 145 158 13 4.1 26.0 0 .smallcircle.
4.2 5.3 Ex.12 147 158 11 4.2 27.0 0 .smallcircle. 3.8 3.5 C.Ex.5
156 160 4 5.2 32.5 10 x 3.4 3.0 Ex.13 147 159 12 4.3 27.5 0
.smallcircle. 3.4 2.9 Ex.14 139 158 19 3.7 23.5 0 .circleincircle.
4.8 5.7 C.Ex.6 133 157 24 3.1 22.5 0 .circleincircle. 7.8 14.6
Ex.15 147 160 13 4.3 27.0 0 .smallcircle. 4.0 4.9 Ex.16 142 159 18
3.8 24.0 0 .circleincircle. 3.9 4.1 Ex.17 141 157 26 3.8 23.5 0
.smallcircle. 5.9 12.4 Ex.18 144 160 17 4.0 26.0 0 .circleincircle.
4.6 4.3 Ex.19 145 160 15 4.1 26.0 0 .circleincircle. 5.8 6.8 Ex.20
137 158 21 3.2 23.0 0 .circleincircle. 4.5 4.7 C.Ex.7 156 160 4 5.3
31.0 15 x 3.2 2.0 Ex.21 146 158 12 4.0 26.5 0 .smallcircle. 4.0 4.9
Ex.22 141 157 16 3.7 24.0 0 .circleincircle. 4.5 4.1 Ex.23 141 160
19 3.7 24.0 0 .circleincircle. 4.2 4.4 Ex.24 142 158 16 3.7 24.5 0
.circleincircle. 4.2 4.1 Ex.25 146 158 12 4.1 26.5 0 .smallcircle.
3.9 4.8 Ex.26 136 157 21 3.2 22.5 0 .circleincircle. 4.2 4.5 Ex.:
Example C.Ex.: Comparative Example
* * * * *