U.S. patent application number 12/857341 was filed with the patent office on 2010-12-02 for propylene polymers with improved properties.
This patent application is currently assigned to BOREALIS TECHNOLOGY OY. Invention is credited to Siegfried LIEDAUER, James MCGOLDRICK, Franz RUEMER, Stefan SCHIESSER.
Application Number | 20100305246 12/857341 |
Document ID | / |
Family ID | 8177494 |
Filed Date | 2010-12-02 |
United States Patent
Application |
20100305246 |
Kind Code |
A1 |
MCGOLDRICK; James ; et
al. |
December 2, 2010 |
PROPYLENE POLYMERS WITH IMPROVED PROPERTIES
Abstract
The invention relates to novel propylene polymers with improved
properties especially with improved stiffness and impact strength
comprising propylene homopolymers or propylene block copolymers
with 90.0 to 99.9 wt % propylene and 0.1 to 10 wt % .alpha.-olefins
with 2 or 4 to 18 carbon atoms, or mixtures thereof, wherein the
propylene homopolymers or propylene block copolymers are
.beta.-nucleated propylene polymers, whereby the .beta.-nucleated
propylene homopolymers have an IR.tau..gtoreq.0.98, a tensile
modulus .gtoreq.1500 MPa at +23.degree. C. and a Charpy impact
strength, .gtoreq.3 kJ/m.sup.2 at -20.degree. C. using notched test
specimens, and the .beta.-nucleated propylene block copolymers are
polymers having an IR.tau. of the propylene homopolymer block of
.gtoreq.0.98, a tensile modulus .gtoreq.1100 Mpa at +23.degree. C.
and a Charpy impact strength of .gtoreq.6 kJ/m.sup.2 at -20.degree.
C. using notched test specimens. The propylene polymers with an
improved property spectrum are suitable for producing molded parts
in a pipe system, such as pipes and fittings, inspection chambers,
pipe ducting systems, extrusion or compression molded sheets and
the like.
Inventors: |
MCGOLDRICK; James;
(Marchtrenk, AU) ; RUEMER; Franz; (St.
Georgen/Gusen, AU) ; SCHIESSER; Stefan; (Leonding,
AU) ; LIEDAUER; Siegfried; (Wilhering, AU) |
Correspondence
Address: |
JORDAN AND HAMBURG LLP
122 EAST 42ND STREET, SUITE 4000
NEW YORK
NY
10168
US
|
Assignee: |
BOREALIS TECHNOLOGY OY
Porvoo
FI
|
Family ID: |
8177494 |
Appl. No.: |
12/857341 |
Filed: |
August 16, 2010 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10478549 |
Feb 25, 2004 |
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PCT/EP02/05548 |
May 21, 2002 |
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12857341 |
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Current U.S.
Class: |
524/90 ; 524/186;
524/229; 524/400; 524/528; 524/582 |
Current CPC
Class: |
C08F 110/06 20130101;
C08K 5/0083 20130101; C08F 297/083 20130101; C08F 10/06 20130101;
C08K 5/0083 20130101; C08F 2500/12 20130101; C08F 210/06 20130101;
C08F 4/6465 20130101; C08F 2500/12 20130101; C08F 2500/15 20130101;
C08L 53/00 20130101; C08F 210/16 20130101; C08F 2500/15 20130101;
C08L 23/12 20130101; C08K 5/0083 20130101; C08F 10/06 20130101;
C08F 210/06 20130101; C08F 110/06 20130101 |
Class at
Publication: |
524/90 ; 524/582;
524/528; 524/229; 524/186; 524/400 |
International
Class: |
C08L 23/12 20060101
C08L023/12; C08L 53/00 20060101 C08L053/00; C08K 5/20 20060101
C08K005/20; C08K 5/17 20060101 C08K005/17; C08K 5/3437 20060101
C08K005/3437; C08K 5/09 20060101 C08K005/09 |
Foreign Application Data
Date |
Code |
Application Number |
May 21, 2001 |
EP |
01112367.6 |
Claims
1. Propylene polymers comprising propylene homopolymers having melt
indices of 0.05 to 15 g/10 min at 230.degree. C./2.6 kg or
propylene block copolymers of 90.0 to 99.9 wt % propylene and 0.1
to 10 wt % .alpha.-olefins of 2 or 4 to 18 carbon atoms having melt
indices of 0.05 to 20 g/10 min at 230.degree. C./2.16 kg, or
mixtures thereof, wherein the propylene homopolymers or propylene
block copolymers are .beta.-nucleated, the .beta.-nucleated
propylene homopolymers having an IR.tau..gtoreq.0.98, a tensile
modulus of .gtoreq.1500 MPa at +23.degree. C. and a Charpy impact
strength of kJ/m.sup.2 at -20.degree. C. using notched test
specimens, and the .beta.-nucleated propylene block copolymers are
polymers having an IR.tau. of the propylene homopolymer block of
.gtoreq.0.98, a tensile modulus of .gtoreq.1100 MPa at +23.degree.
C. and a Charpy impact strength of .gtoreq.6 kJ/m.sup.2 at
-20.degree. C. using notched test specimens.
2. Propylene polymers according to claim 1 wherein the melt indices
at 230.degree. C./2.6 kg of the propylene homopolymers and the
propylene block copolymers are 0.1 to 8 g/10 min, the
.beta.-nucleated propylene homopolymers have a tensile modulus of
.gtoreq.1600 MPa at +23.degree. C. and a Charpy impact strength of
4 to 10 kJ/m.sup.2 at -20.degree. C. using notched test specimens,
and the .beta.-nucleated propylene block copolymers have a tensile
modulus of .gtoreq.1300 MPa at +23.degree. C. and a Charpy impact
strength of .gtoreq.9 kJ/m.sup.2 at -20.degree. C. using notched
test specimens.
3. Propylene polymers according to one of the claim 1 or 2, wherein
the .beta.-nucleated propylene homopolymers and propylene block
copolymers are obtained by polymerization with a Ziegler-Natta
catalyst system comprising titanium-containing solid components, an
organoalumina, magnesium or titanium compound as cocatalyst and an
external donor according to the formula
R.sub.xR'.sub.ySi(MeO).sub.4-x-y' wherein R and R' are identical or
different and are branched or cyclic aliphatic or aromatic
hydrocarbon residues, and y and x independently from each other are
0 or 1, provided that x+y are 1 or 2.
4. Propylene polymers according to claim 3, wherein the external
donor is dicyclopentyldimethoxysilane.
5. Propylene polymers according to claim 1 or 2, wherein the
.beta.-nucleated propylene polymers contain 0.01 to 2.0 wt %, in
each case based on the propylene polymers, dicarboxylic acid
derivative diamide compounds from C.sub.5-C.sub.8-cycloalkyl
monoamines or C.sub.6-C.sub.12-aromatic monoamines and
C.sub.5-C.sub.8-aliphatic, C.sub.5-C.sub.8-cycloaliphatic or
C.sub.6-C.sub.12-aromatic dicarboxylic acids; and/or diamine
derivative diamide compounds from C.sub.5-C.sub.8-cyeloalkyl
monocarboxylic acids or C.sub.6-C.sub.12-aromatic monocarboxylic
acids and C.sub.5-C.sub.8-cycloaliphatic or
C.sub.6-C.sub.12-aromatic diamines; and/or amino acid derivative
diamide compounds from amidation reaction of
C.sub.5-C.sub.8-alkyl-, C.sub.5-C.sub.8-cycloalkyl- or
C.sub.8-C.sub.12-arylamino acids, C.sub.5-C.sub.8-alkyl-,
C.sub.5-C.sub.8-cycloalkyl- or C.sub.6-C.sub.12-aromatic
monocarboxylic acid chlorides and C.sub.5-C.sub.8-alkyl-,
C.sub.5-C.sub.8-cycloalkyl- or C.sub.6-C.sub.12-aromatic
mono-amines, as .beta.-nucleating agent.
6. Propylene polymers according to claim 1 or 2, wherein the
.beta.-nucleated propylene polymers contain 0.0001 to 2.0 wt %
quinacridone compounds, quinacridonequinone compounds, and/or
dihydroquinacridone compounds, as .beta.-nucleating agent.
7. Propylene polymers according to claim 1 or 2, wherein the
.beta.-nucleated propylene polymers contain 0.01 to 2.0 wt %
dicarboxylic acid salts of metals from group IIa of periodic
system, and/or mixtures of dicarboxylic acids and metals from group
IIa of the periodic system, as .beta.-nucleating agent.
8. Propylene polymers according to claim 1 or 2, wherein the
.beta.-nucleated propylene polymers contain 0.01 to 2.0 wt % of
salts of metals from group IIa of the periodic system and imido
acids of the formula ##STR00002## wherein x=1 to 4; R.dbd.H,
--COOH, C.sub.1-C.sub.12-alkyl, C.sub.5-C.sub.8-cycloalkyl or
C.sub.6-C.sub.12-aryl, and Y.dbd.C.sub.1-C.sub.12-alkyl,
C.sub.5-C.sub.8-cycloalkyl or C.sub.6-C.sub.12-aryl-substituted
bivalent C.sub.6-C.sub.12-aromatic residues, as .beta.-nucleating
agent.
9. A process for producing the propylene polymers according to
claim 1 comprising melt mixing said propylene homopolymers having
an IR.tau..gtoreq.0.98, or said propylene block copolymers having
an IR.tau. of the propylene homopolymer block of .gtoreq.0.98, with
0.0001 to 2.0 wt %, based on the propylene polymers, of
.beta.-nucleating agents, said melt mixing occurring at
temperatures from 175 to 250.degree. C.
10. Molded articles comprising the propylene polymers according to
claim 1 or 2.
11. Molded articles comprising the propylene homopolymers according
to claim 1.
12. Molded articles comprising propylene block copolymers of 90.0
to 99.9 wt % propylene and 0.1 to 10 wt % .alpha.-olefins of 2 or 4
to 18 carbon atoms having melt indices of 0.05 to 20 g/10 min at
230.degree. C./2.16 kg which propylene block copolymers are
.beta.-nucleated, where the .beta.-nucleated propylene block
copolymers have an IR.tau. of the propylene homopolymer block of
.gtoreq.0.98, the molded articles having a tensile modulus of
.gtoreq.1100 MPa at +23.degree. C. and a Charpy impact strength of
.gtoreq.kJ/m.sup.2 at -20.degree. C. using notched test
specimens.
13. Propylene polymers according to claim 5, wherein the
dicarboxylic acid derivative diamide compounds are
N,N'-di-C.sub.5-C.sub.8-cycloalkyl-2,6-naphthalene dicarboxamide
compounds,
N,N'-di-C.sub.5-C.sub.8-cycloalkyl-4,4-biphenyldicarboxamide
compounds, N,N'-di-C.sub.5-C.sub.8-cycloalkylterephthalamide
compounds,
N,N-di-C.sub.5-C.sub.8-cycloalkyl-1,4-cyclohexanedicarboxamide
compounds and/or
N,N'-di-C.sub.6-C.sub.12-aryl-C.sub.5-C.sub.8-diamide compounds,
the diamine derivative diamide compounds are
N,N'-C.sub.6-C.sub.12-arylene-bis-benzamide compounds,
N,N-p-C.sub.6-C.sub.12-arylene-bis-C.sub.5-C.sub.8-cycloalkyl-bis-benzami-
de compounds,
N,N'-p-C.sub.6-C.sub.12-arylene-bis-C.sub.5-C.sub.8-cycloalkylcarboxamide
compounds and/or
N,N-C.sub.5-C.sub.8-cycloalkyl-bis-cyclohexanecarboxamide
compounds, and the amino acid derivative diamide compounds are
N-phenyl-5-(N-benzoylamino) pentaneamide and/or
N-cyclohexyl-4-(N-cyclohexylcarbonylamino) benzamide.
14. Propylene polymers according to claim 6, wherein the
quinacridone compounds are quinacridone, dimethylquinacridone
and/or dimethoxyquinacridone, the quinacridonequinone compounds are
quinacridonequinone, a mixed crystal of
5,12-dihydro(2,3b)acridine-7,14-dione with
quino(2,3b)acridine-6,7,13,14-(5H,12H)-tetrone and/or
dimethoxyquinacridonequinone, and the dihydroquinacridone compounds
are dihydroquinacridone, dimethoxydihydroquinacridone and/or
dibenzodihydroquinacridone.
15. Propylene polymers according to claim 7, wherein the
dicarboxylic acid salts of metals from group IIa of the periodic
system are pimelic acid calcium salt and/or suberic acid calcium
salt.
16. Propylene polymers according to claim 8, wherein the salts of
metals from group Ha of the periodic system and said amido acids
are calcium salts of phthaloylglycine, hexahydrophthaloylglycine,
N-phthaloylalanine and/or N-4-methylphthaloylglycine.
Description
REFERENCE TO RELATED APPLICATION
[0001] This is a continuation application of Ser. No. 10/478,549,
filed Feb. 25, 2004, which is currently pending. The subject matter
of the aforementioned prior application is hereby incorporated
herein by reference.
FIELD OF THE INVENTION
[0002] The invention relates to propylene polymers with improved
properties as well as to a process for producing them.
BACKGROUND OF THE INVENTION
[0003] Propylene polymer compositions from common propylene
polymers and .beta.-nucleating agents are known. .beta.-Nucleating
agents are useful in compositions for forming unstretched films
which can be made porous by extraction of .beta.-spherulites and
stretching the films (disclosed for example in U.S. Pat. No.
4,386,129; U.S. Pat. No. 4,975,469).
[0004] Another effect of .beta.-nucleating agents in propylene
compositions is the improved thermoformability. As the melting
point of the .beta.-form of the spherulites of polypropylene based
resins is generally about 144 to 148.degree. C., contrasted with
the typical melting point range of .alpha.-form spherulites of
about 159 to 163.degree. C., melt forming from these compositions
is possible at lower temperatures and higher production rates (WO
93/12 262).
[0005] The disadvantage of these compositions having good impact
properties is that they show unsatisfactory strength.
[0006] Conventional polypropylene homopolymers usually show high
stiffness, but poor impact strength. Conventional .beta.-nucleated
polypropylenes usually have improved impact strength but also
exhibit reduced stiffness.
OBJECT OF THE INVENTION
[0007] Therefore it is the object of the present invention to
provide propylene polymers with improved properties characterized
in having high stiffness and good impact properties
simultaneously.
BRIEF DESCRIPTION OF THE INVENTION
[0008] According to the present invention, this object is achieved
by propylene polymers with improved properties comprising propylene
homopolymers with melt indices of 0.05 to 15 g/10 min at
230.degree. C./2.16 kg or propylene block copolymers with 90.0 to
99.9 wt % propylene and 0.1 to 10 wt % .alpha.-olefins with 2 or 4
to 18 carbon atoms with melt indices of 0.05 to 20 9/10 min at
230.degree. C./2.16 kg, or mixtures thereof, wherein the propylene
homopolymers or propylene block copolymers are .beta.-nucleated
propylene polymers, whereby the .beta.-nucleated propylene
homopolymers have an IR.tau..gtoreq.0.98, a tensile modulus of
.gtoreq.1500 MPa at +23.degree. C. and a Charpy impact strength of
.gtoreq.3 kJ/m.sup.2 at -20.degree. C. using notched test
specimens, and the .beta.-nucleated propylene block copolymers are
polymers having an IR.tau. of the propylene homopolymer block of
.gtoreq.0.98, a tensile modulus of 1100 MPa at +23.degree. C. and a
Charpy impact strength, of 6 kJ/m.sup.2 at -20.degree. C., using
notched test specimens.
DETAILED DESCRIPTION OF THE INVENTION
[0009] .beta.-nucleated propylene polymers are isotactic propylene
polymers composed of chains in a 3.sub.1 helical conformation
having an internal microstructure of .beta.-form spherulites being
composed of radial arrays of parallel stacked lamellae. This
microstructure can be realized by the addition of .beta.-nucleating
agents to the melt and subsequent crystallization. The presence of
the .beta.-form can be detected through the use of wide angle X-ray
diffraction (Moore, J., Polypropylene Handbook, p. 134-135, Hanser
Publishers Munich 1996).
[0010] The IR.tau. of the propylene polymers is measured and
calculated as described in EP 0 277 514 A2 on page 5 (column 7,
line 53 to column 8, line 11).
[0011] According to a preferred embodiment the .beta.-nucleated
propylene homopolymers or the propylene homopolymer block of the
.beta.-nucleated propylene block copolymers have an IR.tau. of
.gtoreq.20.985. The difference of 0.005 in IR.tau., IR.tau. being a
measure for isotacticity, encompasses a significant increase in
mechanical polymer properties, especially in stiffness.
[0012] The propylene homopolymers according to the present
invention have melt indices of 0.05 to 15 g/10 min at 230.degree.
C./2.16 kg, preferably 0.1 to 8 g/10 min at 230.degree. C./2.16 kg,
most preferably 0.2 to 5 g/10 min at 230.degree. M. 16 kg. The
propylene copolymers according to the present invention have melt
indices of 0.05 to 20 g/10 min at 230.degree. C./2.16 kg,
preferably 0.1 to 8 g/10 min at 230.degree. C./2.16 kg, most
preferably 0.2 to 5 g/10 min at 230.degree. C./2.16 kg.
[0013] According to the present invention the propylene
homopolymers show a tensile modulus .gtoreq.1500 MPa, preferably
.gtoreq.1600 MPa and the propylene copolymers show a tensile
modulus .gtoreq.1100 MPa, preferably .gtoreq.1300 MPa and most
preferably .gtoreq.1500 MPa.
[0014] The propylene homopolymers according to the present
invention have a Charpy impact strength of .gtoreq.3 kJ/m.sup.2 at
-20.degree. C., preferably 4 to 10 kJ/m.sup.2 at -20.degree. C.,
most preferably 5 to 10 kJ/m.sup.2 at -20.degree. C.
[0015] The propylene copolymers according to the present invention
have a Charpy impact strength of .gtoreq.6 kJ/m.sup.2 at
-20.degree. C., preferably .gtoreq.9 kJ/m.sup.2 at -20.degree. C.,
most preferably .gtoreq.10 kJ/m.sup.2 at -20.degree. C. Charpy
impact strength of up to at least 60 kJ/m.sup.2 is possible for
copolymers according to the invention.
[0016] According to an advantageous feature of the present
invention the .beta.-nucleated propylene polymers with an
IR.tau..gtoreq.0.98 being propylene polymers obtained by
polymerization with a Ziegler-Natta catalyst system comprising
titanium-containing solid components, an organo alumina, magnesium
or titanium compound as cocatalyst and an external donor according
to the formula
R.sub.xR'.sub.ySi(MeO).sub.4-x-y'
wherein R and R' are identical or different and are branched or
cyclic aliphatic or aromatic hydrocarbon residues, and y and x
independently from each other are O or 1, provided that x+y are 1
or 2.
[0017] Examples of propylene polymers with high IRE obtained by
polymerization with a Ziegler-Natta catalyst system, for example by
slurry, bulk or gas phase polymerization, are propylene polymers as
described in EP-A-0,790, 262, WO 99/24,478 and WO 99/16,797.
[0018] A preferred external donor of the Ziegler-Natta catalyst
system is dicyclopentyldimethoxysilane.
[0019] According to a preferred embodiment the, B-nucleated
propylene polymer contains 0.01 to 2.0 wt %, in each case based on
the propylene polymers used, of [0020] dicarboxylic acid derivative
type diamide compounds from C.sub.5-C.sub.8-cycloalkyl monoamines
or C.sub.6-C.sub.12-aromatic monoamines and
C.sub.5-C.sub.8-aliphatic, C.sub.5-C.sub.8-cycloaliphatic or
C.sub.6-C.sub.12-aromatic dicarboxylic acids, preferably
N,N'-di-C.sub.5-C.sub.8-cycloalkyl-2,6-naphthalene dicarboxamide
compounds,
N,N'-di-C.sub.5-C.sub.8-cycloalkyl-4,4-biphenyidicarboxamide
compounds, N,N'-di-C.sub.5-C.sub.8-cycloalkylterephthalamide
compounds, N.
N'-di-C.sub.5-C.sub.8-cycloalkyl-1,4-cyclohexanedicarbox-amide
compounds and/or
N,N'-di-C.sub.6-C.sub.12-aryl-C.sub.5-C.sub.8-diamide compounds;
and/or diamine derivative type diamide compounds from
C.sub.5-C.sub.8-cycloalkyl monocarboxylic acids or
C.sub.6-C.sub.12-aromatic monocarboxylic acids and
C.sub.5-C.sub.8-cycloaliphatic or C.sub.6-C.sub.12-aromatic
diamines, preferably N,N'-C.sub.6-C.sub.12-arylene-bis-benzamide
compounds, N,N'-C.sub.5-C.sub.8-cycloalkyl-bis-benzamide compounds,
N,N'-p-C.sub.6-C.sub.12-arylene-bis-C.sub.5-C.sub.8-cycloalkylcarboxamide
compounds and/or
N,N'-C.sub.5-C.sub.8-cycloalkyl-bis-cyclohexanecarboxamide
compounds; and/or [0021] amino acid derivative type diamide
compounds from amidation reaction of C.sub.5-C.sub.8-alkyl-,
C.sub.5-C.sub.8-cycloalkyl- or C.sub.6-C.sub.12-arylamino acids,
C.sub.5-C.sub.8-alkyl-, C.sub.5-C.sub.8-cycloalkyl- or
C.sub.6-C.sub.12-aromatic monocarboxylic acid chlorides and
C.sub.5-C.sub.8-alkyl-, C.sub.5-C.sub.8-cycloalkyl- or
C.sub.6-C.sub.12-aromatic mono-amines, preferably
N-phenyl-5-(N-benzoylamino)pentaneamide and/or
N-cyclohexyl-4-N-cyclohexylcarbonylamino) benzamide, as
p-nucleating agent.
[0022] Examples of N,N'-di-C.sub.5-C.sub.8-cyclo
alkyl-2,6-naphthalene dicarboxamide compounds are
N,N'-dicyclohexyl-2,6-naphthalene dicarboxamide and
N,N'-dicyclooctyl-2,6-naphthalene dicarboxamide.
[0023] Examples of
N,N'-di-C.sub.5-C.sub.8-cycloalkyl-4,4-biphenyldicarboxamide
compounds are N,N'-dicyclohexyl-4,4-biphenyldicarboxamide and N.
N'-dicyclopentyl-4,4-biphenyldicarboxamide.
[0024] Examples of
N,N'-di-C.sub.5-C.sub.8-cycloalkylterephthalamide compounds are
N,N'-dicyclohexylterephthalamide and
N,N'-dicyclopentylterephthalamide.
[0025] Examples of
N,N'-di-C.sub.5-C.sub.8-cycloalkyl-1,4-cyclohexanedicarboxamide
compounds are N,N'-dicyclohexyl-1,4-cyclohexanedicarboxamide and
N,N'-dicyclohexyl-1,4-cyclopentanedicarboxanaide.
[0026] Examples of N,N'-di-C.sub.6-C.sub.12-aryl-Cs-C-diamide
compounds are N,N'-bis(p-methylphenyl)-hexanediamide,
N,N'-bis(4-cyclohexylphenyl)hexanediamide,
N,N'-diphenylhexanediamide, N,N'-diphenyloctanediamide and
N,N'-bis(p-ethylphenyl)hexanediamide.
[0027] Examples of N,N'-C.sub.6-C.sub.12-arylene-bis-benzamide
compounds are N,N'-p-phenylene-bis-benzamide and
N,N'-1,5-naphthalene-bis-benzamide.
[0028] Examples of N,N'-C.sub.5-C.sub.8-cycloalkyl-bis-benzamide
compounds are N,N'-1,4-cyclopentane-bis-benzamide and
N,N'-1,4-cyclohexane-bis-benzamide.
[0029] Examples of
N,N'-p-C.sub.6-C.sub.12-arylene-bis-C.sub.5-C.sub.8-cycloalkylcarboxamide
compounds are N,N'-1,5-naphthalene-bis-cyclohexanecarboxamide and
N,N'-1,4-phenylene-bis-cyclohexanecarboxamide.
[0030] Examples of
N,N'-C.sub.5-C.sub.8-cycloalkyl-bis-cyclohexanecarboxamide
compounds are N,N'-1,4-cyclopentane-bis-cyclohexanecarboxamide and
N,N'-1,4-cyclohexane-bis-cyclohexanecarboxamide.
[0031] According to a further preferred embodiment the
.beta.-nucleated propylene polymer contains 0.0001 to 2.0 wt % of
quinacridone type compounds, especially quinacridone,
dimethylquinacridone and/or dimethoxyquinacridone;
quinacridonequinone type compounds, especially quinacridonequinone,
a mixed crystal of 5,12-dihydro(2,3b)acridine-7,14-dione with
quino(2,3b)acridine-6,7,1 3,14-(5H, 12H)-tetrone as disclosed in
EP-B 0 177 961 and/or dimethoxyquinacridonequinone; and/or
dihydroquinacridone type compounds, especially dihydroquinacridone,
di-methoxydihydroquinacridone and/or dibenzodihydroquinacridone, as
.beta.-nucleating agent.
[0032] According to a further preferred embodiment the
.beta.-nucleated propylene polymer contains 0.01 to 2.0 wt % of
dicarboxylic acid salts of metals from group Ha of periodic system,
especially pimelic acid calcium salt and/or suberic acid calcium
salt; and/or mixtures of dicarboxylic acids and salts of metals
from group Ha of periodic system, as .beta.-nucleating agent.
[0033] According to a further preferred embodiment the p-nucleated
propylene polymer contains 0.01 to 2.0 wt % of salts of metals from
group Ha of periodic system and imido acids of the formula
##STR00001##
wherein x=1 to 4; R.dbd.H, --COOH, C.sub.1-C.sub.12-alkyl,
C.sub.5-C.sub.8-cycloalkyl or C.sub.6-C.sub.12-aryl, and
Y.dbd.C.sub.1-C.sub.12-alkyl, C.sub.5-C.sub.8-cycloalkyl or
C.sub.6-C.sub.12-aryl-substituted bivalent
C.sub.6-C.sub.12-aromatic residues, especially calcium salts of
phthaloylglycine, hexahydrophthaloylglycine, N-phthaloylalanine
and/or N-4-methylphthaloylglycine, as .beta.-nucleating agent.
[0034] The inventive propylene polymers with improved properties
may contain usual auxiliary materials such as 0.01 to 2.5 wt %
stabilizers, and/or 0.01 to 1 wt % processing aids, and/or 0.1 to 1
wt % antistatic agents and/or 0.2 to 3 wt % pigments, in each case
based on the propylene polymers used.
[0035] The stabilizers, contained in the inventive propylene
polymers, preferably are mixtures of 0.01 to 0.6 wt % phenolic
antioxidants, 0.01 to 0.6 wt % 3-arylbenzofuranones, 0.01 to 0.6 wt
% processing stabilizers based on phosphites, 0.01 to 0.6 wt % high
temperature stabilizers based on disulfides and thioethers and/or
0.01 to 0.8 wt % statically hindered amines (HALS).
[0036] A further object of the present invention is a process for
producing propylene polymers with an improved property spectrum
from propylene homopolymers with melt indices of 0.05 to 15 9/10
min at 230.degree. C./2.16 kg and/or block copolymers from 90.0 to
99.9 wt % of propylene and 0.1 to 10 wt % of .alpha.-olefins with 2
or 4 to 18 carbon atoms with melt indices of 0.05 to 20 9/10 min at
230.degree. C./2.16 kg, wherein .beta.-nucleated propylene
homopolymers have an IR.tau..gtoreq.20.98, a tensile modulus of
.gtoreq.1500 MPa at +23.degree. C. and a Charpy impact strength of
3 kJ/m.sup.2 at -20.degree. C. using notched test specimens,
respectively, .beta.-nucleated propylene block copolymers having an
IR.tau. of the propylene homopolymer block of 0.98, a tensile
modulus of .gtoreq.1100 MPa at +23.degree. C. and a Charpy impact
strength, .gtoreq.6 kJ/m.sup.2 at -20.degree. C. using notched test
specimens, are produced by melt mixing of propylene homopolymers
having an IR.tau..gtoreq.0.98, respectively propylene block
copolymers having an IR.tau. of the propylene homopolymer block of
.gtoreq.0.98, with 0.0001 to 2.0 wt %, based on the polypropylenes
used, of .beta.-nucleating agents at temperatures from 175 to
250.degree. C.
[0037] For the melt mixing of the propylene polymers and the
.beta.-nucleating agents, conventional compounding extruders are
used.
[0038] In producing the inventive propylene polymers the
.beta.-nucleating agents may be introduced into the propylene
polymers as master batch for example from 0.05 to 25 parts by
weight of .beta.-nucleating agent and 75 to 99.95 parts by weight
of propylene polymer.
[0039] Preferred applications of the propylene polymers with
improved properties as well as of mixtures with conventional
propylene homopolymers and/or propylene copolymers are molded parts
in a pipe system, such as pipes and fittings, inspection chambers,
pipe ducting systems, extrusion or compression molded sheets and
the like.
[0040] A further object of the invention is to provide articles
with an improved balance of stiffness and impact strength at low
temperatures.
[0041] It has been found that this object is achieved by using
propylene homopolymers with melt indices of 0.05 to 15 g/10 min at
230.degree. C./2.16 kg, which propylene homopolymers are
.beta.-nucleated, where the .beta.-nucleated propylene homopolymers
have an IR.tau..gtoreq.20.98, for producing these articles.
Articles with a tensile modulus of .gtoreq.1500 MPa at +23.degree.
C. and a Charpy impact strength of .gtoreq.3 kJ/m.sup.2 at
-20.degree. C., using notched test specimens, can be produced by
using the aforementioned propylene homopolymers.
[0042] It has been found that this object is also achieved by using
propylene block copolymers with 90.0 to 99.9 wt % propylene and 0.1
to 10 wt % .alpha.-olefins with 2 or 4 to 18 carbon atoms with melt
indices of 0.05 to 20 g/10 min at 230.degree. C./2.16 kg, which
propylene block copolymers are .beta.-nucleated, where the
.beta.-nucleated propylene block copolymers have an IR.tau. of the
propylene homopolymer block of .gtoreq.0.98, for producing these
articles. Articles with a tensile modulus of .gtoreq.1100 MPa at
+23.degree. C. and a Charpy impact strength, of .gtoreq.6
kJ/m.sup.2 at -20.degree. C., using notched test specimens, can be
produced by using the aforementioned propylene block
copolymers.
EXAMPLES
[0043] The following tests were made using injection molded samples
prepared according to ISO 1873
[0044] Tensile modulus according to ISO 527 (cross head speed 1
mm/min) at +23.degree. C. Charpy impact strength using notched
specimens, according to ISO 179/1 eA
Example 1
[0045] A mixture of
90 wt % of a propylene block copolymer, obtained by combined bulk
and gas phase polymerization using a Ziegler-Natta catalyst system
with dicyclopentyldimethoxysilane as external donor, having an
ethylene content of 8.3 wt %, an IR.tau. of the propylene
homopolymer block of 0.98, and a melt index of 0.30 g/10 min at
230.degree. C./2.16 kg, 10 wt % of a master batch comprising 99
parts by weight of a propylene block copolymer having an ethylene
content of 8.3 wt %, an IR.tau. of the propylene homopolymer block
of 0.985 and a melt index of 0.30 g/10 min at 230.degree. C./2.16
kg, and 1 part by weight of pimelic acid calcium salt and 0.1 wt %
calcium stearate, 0.1 wt %
tetrakis[methylene(3,5-di-t-butylhydroxyhydrocinnamate)]methane and
0.1 wt % tris-(2,4-di-t-butylphenyl)phosphite, based on the sum of
the propylene polymers used, is melted in a twin screw extruder
with a temperature profile of 100/145/185/210/220/200/185.degree.
C., homogenized, discharged and pelletized.
[0046] The resulting polypropylene polymer has a melt index of 0.32
9/10 min at 230.degree. C./2.16 kg, a tensile modulus of 1290 MPa
and a Charpy impact strength, notched, of 39 kJ/m.sup.2 at
-20.degree. C.
Example 2
[0047] A mixture of
94 wt % of a propylene homopolymer, obtained by bulk polymerization
using a Ziegler-Natta catalyst system with
dicyclopentyldimethoxysilane as external donor, having an IR.tau.
of 0.985 and a melt index of 1.1 g/10 min at 230.degree. C./2.16
kg, 6 wt % of a master batch comprising 98.8 parts by weight of a
propylene block copolymer having an ethylene content of 8.3 wt %,
an IR.tau. of the propylene homopolymer block of 0.985 and a melt
index of 0.30 g/10 min at 230.degree. C./2.16 kg, and 0.2 parts by
weight of a mixed crystal of 5,12-dihydro(2,3b) acridine-7,14-dione
with quino(2,3b)acridine-6,7,13,14-(5H,12H)-tetrone and 0.05 wt %
calcium stearate, 0.1 wt %
tetrakis[methylene(3,5-di-t-butylhydroxyhydrocinnamate)]methane and
0.1 wt % tris-(2,4-di-t-butyl-phenyl)-phosphite, based on the sum
of the propylene polymers used is melted in a twin screw extruder
with a temperature profile of 100/145/190/215/225/205/190.degree.
C., homogenized, discharged and pelletized.
[0048] The resulting polypropylene polymer has a melt index of 1.0
g/10 min at 230.degree. C./2.16 kg, a tensile modulus of 1500 MPa
and a Charpy impact strength, notched, of 11 kJ/m.sup.2 at
-20.degree. C.
Example 3
[0049] A mixture of
75 wt % of a propylene block copolymer, obtained by combined bulk
and gas phase polymerization using a Ziegler-Natta catalyst system
with dicyclopentyldimethoxysilane as external donor, having an
ethylene content of 8.3 wt %, an IR.tau. of the propylene
homopolymer block of 0.985 and a melt index of 0.30 g/10 min at
230.degree. C./2.16 kg, 25 wt % of a master batch comprising 99.5
parts by weight of a propylene block copolymer having an ethylene
content of 8.3 wt %, an IR.tau. of the propylene homopolymer block
of 0.987 and a melt index of 0.30 g/10 min at 230.degree. C./2.16
kg, and 0.5 parts by weight of hexahydrophthaloylglycine calcium
salt and 0.1 wt % calcium stearate, 0.1 wt %
tetrakis[methylene(3,5-di-t-butylhydroxyhydrocinnamate)]methane and
0.1 wt % tris-(2,4-di-t-butylphenyl)phosphite, based on the sum of
the propylene polymers used, is melted in a twin screw extruder
with a temperature profile of 100/145/185/210/220/200/185.degree.
C., homogenized, discharged and pelletized.
[0050] The resulting polypropylene polymer has a melt index of 0.32
WI 0 min at 230.degree. C./2.16 kg, a tensile modulus of 1310 MPa
and a Charpy impact strength, notched, of 37 kJ/m.sup.2 at
20.degree. C.
Example 4
[0051] A mixture of
95 wt % of a propylene homopolymer, obtained by bulk phase
polymerization using a Ziegler-Natta catalyst system with
dicyclopentyldimethoxysilane as external donor, having an IR.tau.
of 0.987, and a melt index of 1.1 g/10 min at 230.degree. C./2.16
kg, 5 wt % of a master batch comprising 97.5 parts by weight of a
propylene homopolymer having an IR.tau. of 0.987 and a melt index
of 4.2 g/10 min at 230.degree. C./2.16 kg, and 2.5 parts by weight
of N,N'-dicyclohexyl-2,6-naphthalenedicarboxamide and 0.05 wt %
calcium stearate, 0.1 wt %
tetrakis[methylene(3,5-di-t-butylhydroxyhydrocinnamate)]methane and
0.1 wt % tris-(2,4-di-t-butylphenyl)-phosphite, based on the sum of
the propylene polymers used, is melted in a twin screw extruder
with a temperature profile of 100/145/190/215/225/205/190.degree.
C., homogenized, discharged and pelletized.
[0052] The resulting polypropylene polymer has a melt index of 1.2
g/10 min at 230.degree. C./2.16 kg, a tensile modulus of 1765 MPa
and a Charpy impact strength, notched, of 5.5 kJ/m.sup.2 at
-20.degree. C.
Example 5
[0053] A mixture of 95 wt % of a propylene homopolymer, obtained by
bulk phase polymerization using a Ziegler-Natta catalyst system
with dicyclopentyldimethoxysilane as external donor, having i an
IR.tau. of 0.987, and a melt index of 0.3 g/10 min at 230.degree.
C./2.16 kg, 5 wt % of a master batch comprising 97.5 parts by
weight of a propylene homopolymer having an IR.tau. of 0.987 and a
melt index of 0.3 g/10 min at 230.degree. C./2.16 kg, and 2.5 parts
by weight of N,N'-dicyclohexyl-2,6-naphthalenedicarboxamide and
0.05 wt % calcium 3 stearate, 0.1 wt %
tetrakis[methylene(3,5-di-t-butylhydroxyhydrocinnamate)]methane and
0.1 wt % tris-(2,4-di-t-butylphenyl)-phosphite, based on the sum of
the propylene polymers used, is melted in a twin screw extruder
with a temperature profile of 100/145/190/215/225/205/190.degree.
C., homogenized, discharged and pelletized.
[0054] The resulting polypropylene polymer has a melt index of 0.3
9/10 min at 230.degree. C./2.16 kg, a tensile modulus of 1750 MPa
and a Charpy impact strength, notched, of 8.4 kJ/m.sup.2 at
20.degree. C.
* * * * *