Propylene copolymer composition with improved long-term mechanical properties
View Patent ↗Propylene-ethylene random copolymers with improved long-term mechanical properties, especially improved impact strength retention, their manufacture as well as their use, e.g. for the production of moulded articles, particularly injection moulded articles, such as thin-walled plastic containers for packaging.
1. A propylene-ethylene random copolymer having:
(i) a melt flow rate MFR 2 (according to ISO 1133, 230° C., 2.16 kg) in the range of 50 to 120 g/10 min,
(ii) a total ethylene comonomer content of 3.0 to 9.0 mol %
(iii) a content of an orthorhombic gamma-crystal phase 100.Kγ of less than 45% as determined by wide-angle X-ray diffraction (WAXS) on a 60×60×2 mm 3 injection moulded test specimen and comprising:
0.0001 to 1.0 wt %, based on the total weight of the propylene-ethylene random copolymer, of a polymeric α-nucleating agent (pNA).
2. The propylene-ethylene random copolymer according to claim 1 , comprising two propylene copolymer fractions:
a) a first propylene copolymer fraction (PP-COPO-1) having an ethylene comonomer content of at most 3.5 mol %, and
b) a second propylene copolymer fraction (PP-COPO-2),
said first propylene copolymer fraction (PP-COPO-1) having a higher MFR 2 and/or a lower ethylene comonomer content than said second propylene copolymer fraction (PP-COPO-2).
3. The propylene-ethylene copolymer according to claim 2 , wherein the first propylene copolymer fraction (PP-COPO-1) has an ethylene comonomer content of at least 1.0 mol % and at most 3.5 mol % and the second propylene copolymer fraction (PP-COPO-2) has an ethylene comonomer content in the range of 2.0 mol % to at most 11.0 mol %, whereby the first propylene copolymer fraction (PP-COPO-1) has an ethylene comonomer content below that of the second propylene copolymer fraction (PP-COPO-2).
4. The propylene-ethylene copolymer according to claim 2 , wherein the first propylene copolymer fraction (PP-COPO-1) has a melt flow rate MFR 2 (230° C.) in the range of 50.0 to 150 g/10 min and the second propylene copolymer fraction (PP-COPO-2) has a melt flow rate MFR 2 (230° C.) in the range of 40.0 to 120 g/10 min, whereby the MFR 2 of the second propylene copolymer fraction (PP-COPO-2) is lower than the MFR 2 of the first propylene copolymer fraction (PP-COPO-1).
5. The propylene-ethylene copolymer according to- claim 2 , wherein the second propylene copolymer fraction (PP-COPO-2) has an ethylene comonomer content which is higher than the ethylene comonomer content of the first propylene copolymer fraction (PP-COPO-1) and has an MFR 2 which is lower than the MFR 2 of the first propylene copolymer fraction (PP-COPO-1).
6. The propylene-ethylene copolymer according to- claim 1 , wherein the polymeric α-nucleating agent is a polymerized vinyl compound of formula (I):
wherein R 1 and R 2 together form a 5 or 6 membered saturated or unsaturated or aromatic ring or they stand independently for a lower alkyl comprising 1 to 4 carbon atoms.
7. The propylene-ethylene copolymer according to claim 6 , whereby the polymerized vinyl compound is selected from the group consisting of vinyl cycloalkanes.
8. The propylene-ethylene copolymer according to- claim 1 , wherein the propylene-ethylene copolymers is prepared in the presence of:
a) a Ziegler-Natta catalyst (ZN-C) comprising compounds (TC) of a transition metal of Group 4 to 6 of IUPAC, a Group 2 metal compound (MC) and an internal donor (ID), wherein said internal donor (ID) is a non-phthalic compound;
b) optionally a co-catalyst (Co), and
c) optionally an external donor (ED).
9. The propylene-ethylene copolymer according to claim 8 , wherein:
a) the internal donor (ID) is selected from optionally substituted malonates, maleates, succinates, glutarates, cyclohexene-1,2-dicarboxylates, benzoates and derivatives or mixtures thereof; and
b) a molar-ratio of co-catalyst (Co) to external donor (ED) [Co/ED] is 5 to 45.
10. The propylene-ethylene copolymer according to claim 1 , wherein the propylene-ethylene copolymer is produced in a sequential polymerization process, comprising a prepolymerization reactor (PPR) and at least one reactor (R1) or at least two reactors (R1) and (R2), whereby in the prepolymerization reactor a vinyl compound is first polymerized with a catalyst system, comprising a Ziegler-Natta catalyst component, a cocatalyst and optional external donor, a reaction mixture of a polymer of the vinyl compound and the catalyst system is then introduced in a first polymerization reactor (R1), whereby in the first polymerization reactor (R1) a first propylene copolymer fraction (PP-COPO-1) is produced and subsequently transferred into a second polymerization reactor (R2), in the second polymerization reactor (R2) a second propylene copolymer fraction (PP-COPO-2) is produced in the presence of the first propylene copolymer fraction (PP-COPO-1).
11. A molded article, comprising a propylene-ethylene copolymer according to claim 1 .
12. A thin wall packaging made by injection molding, comprising a propylene-ethylene copolymer according to claim 1 .
13. A molded article according to claim 11 , having:
a tensile modulus (measured according to ISO 527) measured after 96 hours of storage at +23±1° C. and 50% relative humidity (standard conditions) of at least 1050 MPa and tensile modulus (measured according to ISO 527) measured after 1440 hours of storage under standard conditions of at least 1100 MPa and
simultaneously having a puncture energy (measured according to ISO 6603-2; 60×60×2 mm 3 specimens) measured after 96 hours of storage under standard conditions of at least 23 J, and measured after 1440 hours of storage under standard conditions of at least 19 J.