U.S. patent application number 11/885356 was filed with the patent office on 2008-06-12 for polyethylene molding composition for producing blown films having improved processability.
This patent application is currently assigned to Basell Polyolefine GmbH. Invention is credited to Joachim Berthold, Lutz-Gerd Heinicke, Gerhardus Meier.
Application Number | 20080139750 11/885356 |
Document ID | / |
Family ID | 36218811 |
Filed Date | 2008-06-12 |
United States Patent
Application |
20080139750 |
Kind Code |
A1 |
Berthold; Joachim ; et
al. |
June 12, 2008 |
Polyethylene Molding Composition for Producing Blown Films Having
Improved Processability
Abstract
The invention relates to a polyethylene molding composition
having a multimodal molar mass distribution particularly suitable
for blow molding films having a thickness in the range from 8 to
200 .mu.m. The molding composition has a density at a temperature
of 23.degree. C. in the range from 0.953 to 0.960 g/cm.sup.3 and an
MFR.sub.190/5 of the final product after extrusion in the range
from 0.10 to 0.50 dg/min. The composition comprises from 30 to 60%
by weight of a first ethylene polymer fraction made of a
homopolymer A having a first molecular weight, from 22 to 40% by
weight of a second ethylene polymer fraction made of a further
homopolymer or first copolymer B of ethylene and at least one first
comonomer from the group of olefins having from 4 to 8 carbon
atoms, the first copolymer B having a second molecular weight
higher than the first molecular weight, and from 10 to 30% by
weight of a third ethylene polymer fraction made of a second
copolymer C having a third molecular weight higher than the second
molecular weight. The molding composition of the invention allows
to produce thin films having improved processability without
impairing the mechanical properties.
Inventors: |
Berthold; Joachim;
(Kelkheim, DE) ; Heinicke; Lutz-Gerd; (Eschborn,
DE) ; Meier; Gerhardus; (Frankfurt, DE) |
Correspondence
Address: |
Basell USA Inc.
Delaware Corporate Center II, 2 Righter Parkway, Suite #300
Wilmington
DE
19803
US
|
Assignee: |
Basell Polyolefine GmbH
Wesseling
DE
|
Family ID: |
36218811 |
Appl. No.: |
11/885356 |
Filed: |
February 23, 2006 |
PCT Filed: |
February 23, 2006 |
PCT NO: |
PCT/EP06/60223 |
371 Date: |
August 30, 2007 |
Current U.S.
Class: |
525/240 |
Current CPC
Class: |
C08J 2323/06 20130101;
C08L 23/04 20130101; C08J 5/18 20130101; C08L 23/08 20130101; C08J
2423/08 20130101; C08L 2205/03 20130101; C08L 23/06 20130101; C08J
2323/04 20130101; C08L 2666/06 20130101; C08L 2666/06 20130101;
C08L 2666/06 20130101; C08L 2666/06 20130101; C08L 23/0807
20130101; C08L 23/04 20130101; C08L 23/0807 20130101; C08L 23/06
20130101; C08L 23/0815 20130101; C08L 2205/025 20130101; C08L
23/0815 20130101; C08L 2203/16 20130101 |
Class at
Publication: |
525/240 |
International
Class: |
C08L 23/04 20060101
C08L023/04; C08J 5/18 20060101 C08J005/18 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 1, 2005 |
DE |
102005009896.7 |
Claims
1. A polyethylene molding composition having a multimodal molar
mass distribution; a density at a temperature of 23.degree. C.
measured in accordance with ISO 1183, in the range from 0.953 to
0.960 g/cm.sup.3; and an MFR.sub.190/5, measured in accordance with
ISO 1133, of the final product after extrusion in the range from
0.10 to 0.50 dg/min, said polyethylene molding composition
comprising: from 30 to 60% by weight of a first ethylene polymer
fraction made of an ethylene homopolymer A having a first molecular
weight; from 22 to 40% by weight of a second ethylene polymer
fraction made of a further homopolymer or first copolymer B of
ethylene and at least one first comonomer selected from the group
of olefins having from 4 to 8 carbon atoms, said first copolymer B
having a second molecular weight higher than said first molecular
weight of the homopolymer A; and from 10 to 30% by weight of a
third ethylene polymer fraction made of a second copolymer C of
ethylene and at least one second comonomer, said second copolymer C
having a third molecular weight higher than said second molecular
weight of the copolymer B, all percentages being based on the total
weight of the molding composition.
2. The polyethylene molding composition according to claim 1,
comprising: from 42 to 52% by weight of the first ethylene polymer
fraction; from 27 to 38% by weight of the second ethylene polymer
fraction, the first copolymer B containing from 0.1 to 1.0% by
weight, based on the weight of copolymer B, of said at least one
first comonomer; and from 15 to 25% by weight of the third ethylene
polymer fraction, the second copolymer C containing from 1 to 15%
by weight, based on the weight of the second copolymer C, of said
at least one second comonomer.
3. The polyethylene molding composition according to claim 1,
wherein said first comonomer and said second comonomer are
independently selected from 1-butene, 1-pentene, 1-hexene,
1-octene, 4-methyl-1-pentene and mixtures thereof.
4. The polyethylene molding composition according to claim 1,
wherein the density is from 0.955 to 0.959 g/cm.sup.3 and the
MFR.sub.190/5 of the final product after extrusion is in the range
from 0.32 to 0.42 g/10 min.
5. The polyethylene molding composition according to claim 4,
further comprising a viscosity number VN.sub.3, measured in
accordance with ISO/R 1191 in decalin at a temperature of
135.degree. C., in the range from 270 to 400 cm.sup.3/g.
6. A process for preparing a polyethylene molding composition
comprising from 30 to 60% by weight of a first ethylene polymer
fraction made of an ethylene homopolymer A having a first molecular
weight; from 22 to 40% by weight of a second ethylene polymer
fraction made of a further homopolymer or first copolymer B of
ethylene and at least one first comonomer selected from the group
of olefins having from 4 to 8 carbon atoms, said first copolymer B
having a second molecular weight higher than said first molecular
weight of the homopolymer A; and from 10 to 30% by weight of a
third ethylene polymer fraction made of a second copolymer C of
ethylene and at least one second comonomer, said second copolymer C
having a third molecular weight higher than said second molecular
weight of the copolymer B. all percentages being based on the total
weight of the molding composition, wherein the polyethylene molding
composition has a multimodal molar mass distribution; a density at
a temperature of 23.degree. C., measured in accordance with ISO
1183, in the range from 0.953 to 0.960 g/cm.sup.3; and an
MFR.sub.190/5, measured in accordance with ISO 1133, of the final
product after extrusion in the range from 0.10 to 0.50 dg/min, the
process comprising the step of polymerizing ethylene, said at least
one first comonomer and said at least one second comonomer in
suspension at temperatures in the range from 20 to 120.degree. C.,
at a pressure in the range from 2 to 10 bar and in the presence of
a Ziegler catalyst comprising a transition metal compound and an
organo-aluminum compound.
7. The process according to claim 6, wherein said polymerization
step is carried out in multiple successive polymerization stages
comprising a first stage, a second stage, and a third stage
performed in corresponding multiple reactors comprising a first
reactor, a second reactor and a third reactor arranged in series,
wherein the first, second and third stages each comprise a molar
mass of a polyethylene composition and a hydrogen concentration,
wherein the molar mass of the polyethylene composition prepared in
each stage is adjusted in each case by means of hydrogen.
8. The process according to claim 7, wherein the hydrogen
concentration in the first polymerization stage is adjusted to
obtain in the homopolymer A a viscosity number VN.sub.1, measured
in accordance with ISO/R 1191 in the range from 70 to 110
cm.sup.3/g.
9. The process according to claim 7, wherein the hydrogen
concentration in the second polymerization stage is adjusted to
obtain in a mixture of homopolymer A plus homopolymer or copolymer
B a viscosity number VN.sub.2, measured in accordance with ISO/R
1191, in the range from 250 to 400 cm.sup.3/g.
10. The process according to claim 7, wherein the hydrogen
concentration in the third polymerization stage is adjusted to
obtain in a mixture of homopolymer A plus first homopolymer or
copolymer B plus second copolymer C a viscosity number VN.sub.3,
measured in accordance with ISO/R 1191, in the range from 280 to
400 cm.sup.3/g.
11. A process comprising forming a blown film having a thickness in
the range from 8 to 200 .mu.m, the film comprising a polyethylene
molding composition having a multimodal molar mass distribution; a
density at a temperature of 23.degree. C., measured in accordance
with ISO 1183, in the range from 0.953 to 0.960 g/cm.sup.3; and an
MFR.sub.190/5, measured in accordance with ISO 1133, of the final
product after extrusion in the range from 0.10 to 0.50 dg/min said
polyethylene molding composition comprising: from 30 to 60% by
weight of a first ethylene polymer fraction made of an ethylene
homopolymer A having a first molecular weight; from 22 to 40% by
weight of a second ethylene polymer fraction made of a further
homopolymer or first copolymer B of ethylene and at least one first
comonomer selected from the group of olefins having from 4 to 8
carbon atoms, said first copolymer B having a second molecular
weight higher than said first molecular weight of the homopolymer
A; and from 10 to 30% by weight of a third ethylene polymer
fraction made of a second copolymer C of ethylene and at least one
second comonomer, said second copolymer C having a third molecular
weight higher than said second molecular weight of the copolymer B,
all percentages being based on the total weight of the molding
composition.
12. The process according to claim 11, wherein the blown film is
formed via a blown film process comprising the step of melting the
polyethylene molding composition to obtain a polyethylene melt,
extruding the polyethylene melt by forcing the polyethylene melt
through an annular die to form a bubble having a frost line
oscillating at a maximum of .+-.2 cm in axial direction during the
shock test at a maximal take-off speed.
13. A blown film having a thickness in the range from 8 to 200
.mu.m; a dart drop impact DDI, measured in accordance with ASTM D
1709 method A, of more than 280 g, measured on a film having a
thickness of 20 .mu.m, comprising a polyethylene molding
composition having a multimodal molar mass distribution; a density
at a temperature of 23.degree. C. measured in accordance with ISO
1183, in the range from 0.953 to 0.960 g/cm.sup.3; and an
MFR.sub.190/5, measured in accordance with ISO 1133, of the final
product after extrusion in the range from 0.10 to 0.50 dg/min, said
polyethylene molding composition comprising: from 30 to 60% by
weight of a first ethylene polymer fraction made of an ethylene
homopolymer A having a first molecular weight; from 22 to 40% by
weight of a second ethylene polymer fraction made of a further
homopolymer or first copolymer B of ethylene and at least one first
comonomer selected from the group of olefins having from 4 to 8
carbon atoms, said first copolymer B having a second molecular
weight higher than said first molecular weight of the homopolymer
A; and from 10 to 30% by weight of a third ethylene polymer
fraction made of a second copolymer C of ethylene and at least one
second comonomer, said second copolymer C having a third molecular
weight higher than said second molecular weight of the copolymer B,
all percentages being based on the total weight of the molding
composition.
Description
[0001] This application is the U.S. national phase of International
Application PCT/EP2006/060223, filed Feb. 23, 2006, claiming
priority to German Patent Application 102005009896.7 filed Mar. 1,
2005; the disclosures of International Application
PCT/EP2006/060223, and German Patent Application 102005009896.7,
each as filed, are incorporated herein by reference.
FIELD OF THE INVENTION
[0002] The present invention relates to a polyethylene (PE) molding
composition having a multimodal molar mass distribution, i.e. a
molding composition comprising a plurality of ethylene polymer
fractions having distinct molar masses.
[0003] In the present description and in the following claims,
unless otherwise indicated, the term "polymer" is used to indicate
both a homopolymer, i.e. a polymer comprising repeating monomeric
units derived from equal species of monomers, and a copolymer, i.e.
a polymer comprising repeating monomeric units derived from at
least two different species of monomers, in which case reference
will be made to a binary copolymer, to a terpolymer, etc. depending
on the number of different species of monomers used.
[0004] The multimodal PE molding composition of the invention is
particularly useful for producing blown films.
[0005] The invention also relates to a process for preparing this
PE molding composition.
[0006] The invention further relates to a blown film produced from
the above-mentioned molding composition by a blown film
process.
PRIOR ART
[0007] Polyethylene is used on a large scale for producing films by
a blown film extrusion process thanks to the mechanical strength,
processability, good chemical resistance and low intrinsic weight
of polyethylene.
[0008] So, for example, EP-A-0 603 935 describes a molding
composition based on polyethylene which has a bimodal molar mass
distribution and is suitable for producing films and moldings
having good mechanical properties.
[0009] However, the prior art films made of bimodal polyethylene
have an inadequate processability, in particular in terms of bubble
stability during processing, and an insufficient drawing
capability. Attempts to attain an improved bubble stability
inevitably resulted in an unacceptable worsening of the mechanical
properties, particularly in terms of Dart Drop Impact strength
(DDI), which is determined in accordance with ASTM D 1709, method
A.
SUMMARY OF THE INVENTION
[0010] The technical problem underlying the present invention is
therefore that of providing a novel PE molding composition having
an improved processability in the blown film extrusion process
without impairing the mechanical strength, particularly in terms of
DDI. More in particular, the mechanical strength of films produced
from the novel PE molding composition of the invention, expressed
as DDI, should not be lower than 280 g for a film having a
thickness of 20 .mu.m.
[0011] For the purpose of the present description and of the claims
which follow, except where otherwise indicated, all numbers
expressing amounts, quantities, percentages, and so forth, are to
be understood as being modified in all instances by the term
"about". Also, all ranges include any combination of the maximum
and minimum points disclosed and include any intermediate ranges
therein, which may or may not be specifically enumerated
herein.
[0012] The above-mentioned technical problem is solved by a PE
molding composition having a multimodal molar mass distribution, a
density at a temperature of 23.degree. C. in the range from 0.953
to 0.960 g/cm.sup.3 and a MFR.sub.190/5 of the final product after
extrusion in the range from 0.10 to 0.50 dg/min, the polyethylene
molding composition comprising: [0013] from 30 to 60% by weight of
a first ethylene polymer fraction made of an ethylene homopolymer A
having a first molecular weight, [0014] from 22 to 40% by weight of
a second ethylene polymer fraction made of a further homopolymer or
first copolymer B of ethylene and at least one first comonomer from
the group of olefins having from 4 to 8 carbon atoms, said first
copolymer B having a second molecular weight higher than said first
molecular weight, and [0015] from 10 to 30% by weight of a third
ethylene polymer fraction made of a second copolymer C of ethylene
and at least one second comonomer, said second copolymer C having a
third molecular weight higher than said second molecular weight,
[0016] all percentages being based on the total weight of the
molding composition.
[0017] In the present description and in the following claims, the
melt flow rate MFR.sub.190/5 is the melt flow rate measured in
accordance with ISO 1133 at 190.degree. C. and under a load of 5
kg. The density is determined in accordance with ISO1183.
[0018] Advantageously, the films produced from the novel PE molding
composition of the invention have a better bubble stability, a
reduced melt pressure and adequate mechanical properties when
compared to the prior art films, in the sense that the DDI is above
280 g for a film having a thickness of 20 .mu.m.
[0019] The polyethylene molding composition of the invention has a
density at a temperature of 23.degree. C. in the range from 0.953
to 0.960 g/cm.sup.3, preferably from 0.955 to 0.959 g/cm.sup.3, and
a broad trimodal molar mass distribution.
[0020] According to a preferred embodiment of the invention, the
polyethylene molding composition comprises: [0021] from 42 to 52%
by weight of the first ethylene polymer fraction, i.e. of the
homopolymer A, [0022] from 27 to 38% by weight of the second
ethylene polymer fraction, i.e. of a further homopolymer or of the
first copolymer B, and [0023] from 15 to 25% by weight of the third
ethylene polymer fraction, i.e. of the second copolymer C.
[0024] The second copolymer B preferably contains, in addition to
ethylene, predetermined proportions, preferably from 0.1 to 1.0% by
weight based on the weight of the second copolymer B, of at least
one first olefin comonomer having from 4 to 8 carbon atoms.
[0025] Examples of such comonomer(s) are 1-butene, 1-pentene,
1-hexene, 1-octene and 4-methyl-1-pentene and mixture thereof.
[0026] In an analogous manner, the second copolymer C is preferably
a copolymer of ethylene and of at least one second comonomer
preferably selected from the group of olefins having from 4 to 8
carbon atoms, more preferably from the above-mentioned list of
comonomers.
[0027] Preferably, the at least one second comonomer is present in
an amount of from 1 to 15% by weight, based on the weight of the
second copolymer C.
[0028] Furthermore, the PE molding composition of the invention has
a melt flow rate MFR.sub.190/5 of the final product after extrusion
in accordance with ISO 1133, in the range from 0.10 to 0.50 g/10
min, preferably from 0.32 to 0.42 g/10 min.
[0029] Preferably, the PE molding composition of the invention has
a viscosity number VN.sub.3, measured in accordance with ISO/R 1191
in decalin at a temperature of 135.degree. C., in the range from
270 to 400 cm.sup.3/g, in particular from 320 to 400
cm.sup.3/g.
[0030] If, as provided by a preferred embodiment of the invention
described more in detail in the following, the PE molding
composition is prepared by means of a cascaded polymerization
process comprising at least three successive polymerization stages
comprising a first stage, a second stage and a third stage, the
trimodality of the composition of the invention can be described in
terms of viscosity numbers VN, measured in accordance with ISO/R
1191, of the ethylene polymer fractions formed in the different
subsequent polymerization stages.
[0031] Here, the different viscosity numbers will be indicated as
explained in the following.
[0032] The viscosity number VN.sub.1 shall be used to indicate the
viscosity number measured on the polymer after the first
polymerization stage. The viscosity number VN.sub.1 is identical to
the viscosity number VN.sub.A of the homopolymer A.
[0033] According to a preferred embodiment of the invention, the
viscosity number VN.sub.1 is in the range from 60 to 110
cm.sup.3/g, more preferably from 60 to 110 cm.sup.3/g.
[0034] The viscosity number VN.sub.2 shall be used to indicate the
viscosity number measured on the polymer after the second
polymerization stage. The viscosity number VN.sub.2 is therefore
the viscosity number of the mixture of homopolymer A plus further
homopolymer or first copolymer B. The viscosity number of the
further homopolymer or of the first copolymer B formed in the
second polymerization stage can be instead determined only
mathematically.
[0035] According to a preferred embodiment of the invention, the
viscosity number VN.sub.2 is in the range from 250 to 400
cm.sup.3/g, preferably from 300 to 370 cm.sup.3/g.
[0036] The viscosity number VN.sub.3 shall be used to indicate the
viscosity number measured on the polymer after the third
polymerization stage. The viscosity number VN.sub.3 is therefore
the viscosity number of the mixture of homopolymer A plus further
homopolymer or first copolymer B plus second copolymer C. The
viscosity number of the second copolymer C formed in the third
polymerization stage can be instead determined only
mathematically.
[0037] According to a preferred embodiment of the invention, the
viscosity number VN.sub.3 is in the range from 270 to 400
cm.sup.3/g, in particular from 320 to 440 cm.sup.3/g.
[0038] The PE molding composition of the invention may further
comprise additional additives. Such additives may be, for example,
heat stabilizers, anti-oxidants, UV stabilizers, light stabilizers,
metal deactivators, peroxide-destroying compounds, basic
co-stabilizers in amounts of from 0 to 10% by weight, preferably
from 0 to 5% by weight, but also fillers, reinforcing materials,
plasticizers, lubricants, emulsifiers, pigments, optical
brighteners, flame retardants, antistatics, blowing agents or
combinations of these in total amounts of from 0 to 50% by weight,
based on the total weight of the composition.
[0039] The present invention also relates to a process for
preparing a polyethylene molding composition as described above,
comprising the step of polymerizing ethylene, said at least one
first comonomer and said at least one second comonomer in
suspension at a temperature preferably in the range from 20 to
120.degree. C., more preferably from 70 to 90.degree. C. and, still
more preferably, from 80 to 90.degree. C., and at a pressure
preferably in the range from 2 to 10 bar and, preferably, in the
presence of a Ziegler catalyst.
[0040] The process for preparing the PE molding composition is
preferably carried out in the presence of a catalytic system
comprising a highly active Ziegler catalyst comprising a transition
metal compound and a co-catalyst, preferably an organo-aluminum
compound, by means of a multistage reaction sequence comprising at
least three successive polymerizations.
[0041] Preferably, the polymerization is carried out in multiple
successive polymerization stages comprising a first stage, a second
stage, and a third stage performed in corresponding multiple
reactors comprising a first reactor, a second reactor and a third
reactor arranged in series.
[0042] The polymerization is preferably carried out in a cascaded
suspension polymerization as described in EP-A-1 228 101.
[0043] The molar mass in each polymerization stage is preferably
adjusted by means of a chain transfer agent, preferably hydrogen,
and preferably in such a manner that the above-mentioned preferred
values of viscosity numbers are obtained after each polymerization
stage.
[0044] The PE molding composition of the invention is particularly
suitable for the production of blown films by the blown film
extrusion process. A possible way to carry out such process is
detailed in the following.
[0045] The polyethylene molding composition is preferably firstly
plasticized at temperatures in the range from 200 to 250.degree. C.
in an extruder. Subsequently, the plasticized polyethylene is
extruded in the molten state through an annular die so as to form a
bubble having a substantially tubular form. The bubble is cooled,
preferably by means of compressed air, and subsequently collapsed
by means of rollers and rolled up into a film.
[0046] The molding composition of the invention can be processed
particularly well by the film blowing process because this
composition ensures an improved drawing capability and an adequate
film bubble stability even under the typical processing conditions
of large scale industrial plants. In other words, thanks to the
drawing capability, particularly thin films having a regular and
constant thickness may be produced.
[0047] Thanks to the bubble stability, the film bubble coming out
from the annular die remains stable even at high take-off speeds
and shows no tendency to alter its geometry neither in axial
direction nor in radial direction. Preferably, the bubble has a
frost line delimiting the molten material from the solidified
material oscillating not more than .+-.2 cm in axial direction
during the shock test (performed as detailed in following Example
3) at a maximal take-off speed.
[0048] The invention further relates to a film comprising a PE
molding composition as described above and having a thickness in
the range from 8 to 200 .mu.m, preferably from 10 to 100 .mu.m,
more preferably from 8 to 50 .mu.m and, still more preferably, from
8 to 10 .mu.m. Preferably, the DDI of a film having a thickness of
20 .mu.m is higher than 280 g.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0049] The present invention will be further described by means of
the following preferred embodiments without restricting the scope
of the invention.
EXAMPLE 1
Polymerization (Invention)
[0050] Ethylene was polymerized in a continuous process performed
in a cascaded mode in three reactors reciprocally arranged in
series. A Ziegler catalyst prepared by the method of EP-A 401 776,
Example 1, was used, having an extremely high responsiveness to
hydrogen and an activity sufficient to carry out the cascaded
polymerization, since this catalyst was able to maintain the
activity over a long period, from 1 to 8 hours.
[0051] The catalyst had in particular the following analytical
composition:
TABLE-US-00001 Ti 6.2% by weight Mg 70.8% by weight Cl 23.0% by
weight.
[0052] The catalyst was pre-activated by means of a sufficient
amount of triethylaluminum and then fed into a first reactor in an
amount of 4.8 mmol/h.
[0053] Sufficient suspension medium, in particular hexane, ethylene
and hydrogen were additionally fed in the first reactor. The amount
of ethylene (=46 kg/h) and the amount of hydrogen (=55 g/h) were
set in such a manner that a percentage of 16.8% by volume of
ethylene and a percentage of 68% by volume of hydrogen were
measured in the gas space (gas temperature for the analytical
measurement=5.+-.1.degree. C.) of the first reactor. The remainder
was a mixture of nitrogen and vaporized suspension medium.
[0054] The polymerization in the first reactor was carried out at a
temperature of 84.degree. C. and under a pressure of 8.8 bar,
corresponding to 0.88 MPa.
[0055] The suspension from the first reactor was then conveyed into
a second reactor arranged in series with and downstream of the
first reactor. The percentage of hydrogen in the gas space (gas
temperature for the analytical measurement=5.+-.1.degree. C.) in
the second reactor was reduced to 8.6% by volume by means of an
intermediate H.sub.2 depressurization. An amount of 30.7 kg/h of
ethylene together with a very small amount of a first comonomer,
namely 1-butene, were introduced into the second reactor. 62.5% by
volume of ethylene, 8.6% by volume of hydrogen and 0.4% by volume
of 1-butene were measured in the gas space of the second reactor;
the remainder was a mixture of nitrogen and vaporized suspension
medium.
[0056] The polymerization in the second reactor was carried out at
a temperature of 84.degree. C. and under a pressure of 2.7 bar,
corresponding to 0.27 MPa.
[0057] The suspension from the second reactor was conveyed via a
further intermediate depressurization operated without off-gas into
a third reactor arranged in series with and downstream of the
second reactor. The hydrogen concentration was set to 14.6% by
volume in the gas space by introducing hydrogen. Apart from 19.2
kg/h of ethylene, 240 g/h of a second comonomer equal to the first
comonomer introduced in the second stage, namely 1-butene, and 6.9
g/h of hydrogen were additionally introduced into the third
reactor.
[0058] A percentage of ethylene of 66% by volume, a percentage of
hydrogen of 14.6% by volume and a percentage of 1-butene of 1% by
volume were measured in the gas space of the third reactor (gas
temperature for the analytical measurement=5.+-.1.degree. C.); the
remainder was a mixture of nitrogen and vaporized suspension
medium.
[0059] The polymerization in the third reactor was carried out at a
temperature of 84.degree. C. and under a pressure of 3 bar,
corresponding to 0.3 MPa.
[0060] The suspension medium was separated off from the polymer
suspension leaving the third reactor and the powder was dried and
passed to pelletization.
[0061] The polyethylene molding composition prepared as described
above had a density of 0.957 g/cm.sup.3, viscosity numbers
VN.sub.1, VN.sub.2 and VN.sub.3, proportions W.sub.A, W.sub.B and
W.sub.C of the homopolymer A, of the first copolymer B and,
respectively, of the second copolymer C and melt flow rates
MFR.sub.1, MFR.sub.2 and MFR.sub.3 which are reported in Table 1
below.
TABLE-US-00002 TABLE 1 Example 1 w.sub.A [% by weight] 48 w.sub.B
[% by weight] 32 w.sub.C [% by weight] 20 VN.sub.1 [cm.sup.3/g] 81
VN.sub.2 [cm.sup.3/g] 337 VN.sub.3 [cm.sup.3/g] 365
MFR.sub.1(190.degree. C./1.2 kg) [g/10 min] 85
MFR.sub.2(190.degree. C./5 kg)[g/10 min] 1.1 MFR.sub.3(190.degree.
C./5 kg) [g/10 min] 0.65 MFR.sub.pellets(190.degree. C./5 kg) [g/10
min] 0.39
[0062] The abbreviations for the physical properties in Table 1
have the following meanings: [0063] W.sub.A, W.sub.B,
W.sub.C=proportion of homopolymer A, first copolymer B and,
respectively, second copolymer C in the total molding
composition=reactor split, determined by the amount of ethylene fed
into the respective reactor; [0064] VN.sub.1, VN.sub.2,
VN.sub.3=viscosity number of the polymer leaving the first, second
and, respectively, third reactor measured in accordance with ISO/R
1191 in decalin at a temperature of 135.degree. C.; [0065]
MFR.sub.1, MFR.sub.2, MFR.sub.3=melt flow rate of the polymer
leaving the first, second and, respectively, third reactor,
measured in accordance with ISO 1133 with indication of the
temperature and the load; [0066] MFR.sub.pellets=melt flow rate of
the final product after extrusion.
EXAMPLE 2
Film Preparation (Invention)
[0067] From the molding composition so prepared, a film was
produced in the following way.
[0068] A film having a thickness of 20 .mu.m was produced on an
Alpine film blowing plant comprising an extruder with a diameter
d.sub.1 of 50 mm and a length of 21.times.d.sub.1(=1.05 m) and an
annular die having a diameter d.sub.2 of 120 mm and a gap width of
1 mm. The film was produced at a blow-up ratio of 4:1 and a neck
length of 7.5.times.d.sub.2(=90 cm). The melt temperature of the
molding composition in the extruder was 205-210.degree. C.
[0069] The film properties are shown in Table 2 below.
EXAMPLE 3
Film Preparation (Comparison)
[0070] A 20 .mu.m film was produced using a commercial film raw
material from Borealis, which is commercially available under the
designation FS 1560, on the same plant and under the same
conditions described in Example 2 with the exception that the melt
temperature of the molding composition in the extruder was
205-215.degree. C.
[0071] The film properties are shown in Table 2 below.
TABLE-US-00003 TABLE 2 Example 2 (invention) Example 3 (comparison)
Take-off: 58 m/min + + Shock test: + + Take-off: 63 m/min + + Shock
test: + - Take-off: 70 m/min + - Shock test: + - Take-off: 77 m/min
+ - Shock test: + - Take-off: 87 m/min + - Shock test: + - DDI [g]
290 310 Specks No specks high specks count Melt pressure [bar] 330
340
[0072] More in particular, the film bubble stability was determined
by the following procedure, including a preliminary test and a
shock test as detailed below.
[0073] In the preliminary test, the take-off speed was set at
predetermined increasing take-off speeds, namely ar 58, 63, 70, 77
and 87 m/min(=maximum rolling-up speed). After the respective
take-off speed had been attained and the neck length had been
adjusted to 90 cm by adjusting the cooling air blower, the axial
oscillation of the film bubble was observed.
[0074] The test was considered finished and passed at a given speed
if the axial oscillation of the bubble being formed was in the
range of .+-.2 cm over a period of observation of one (1)
minute.
[0075] The shock test was subsequently carried out at the same
take-off speed setting as in the preliminary test.
[0076] In the shock test, the bubble was made axially oscillate.
This was performed by fully opening the iris of the cooling air
blower for a period of about 7 s. The iris was then reset to the
initial position. The opening and closing of the iris was monitored
via the pressure of the cooling air. At room temperature greater
than 25.degree. C., however, the opening of the above-mentioned
iris alone is not sufficient to set the film bubble into
oscillation. Accordingly, at temperatures greater than 25.degree.
C., the iris was firstly opened and then shut completely for a
maximum of 3 s, after which it was reset to the initial position,
always monitoring by means of the air pressure. The shock test was
considered passed at a given take-off speed if the oscillations of
the film bubble had abated to .+-.2 cm within 2 minutes.
[0077] This was made for each one of the above-mentioned increasing
take-off speeds. If the shock test or the preliminary test was not
passed at a particular take-off speed, the stability grade
corresponding to the previous lower take-off speed was awarded.
[0078] The dart drop impact strength of the films was determined
according to the standard ASTM D 1709, method A.
[0079] The assessment of specks was carried out visually.
* * * * *