Heterophasic polypropylene with improved impact strength/stiffness balance, improved powder flowability, reduced emissions and low shrinkage

Patent metadata

Field	Value
Publication number	US-9890274-B2
Application number	US-201515519790-A
Country	US
Kind code	B2
Filing date	Oct 16, 2015
Priority date	Oct 27, 2014
Publication date	Feb 13, 2018
Grant date	Feb 13, 2018

Abstract

Heterophasic polypropylene composition with improved impact strength/stiffness balance and with high flowability, reduced emissions and low shrinkage, and its use.

First claim

The invention claimed is:

1. A heterophasic polypropylene composition comprising:
(A) 48 to 78 wt % of a crystalline isotactic propylene homopolymer matrix having a pentad concentration as determined by 13 C-NMR spectroscopy of more than 96 mol % and a matrix melt flow rate (MFR M ) as determined at 230° C. and 2.16 kg load according ISO 1133 in the range of 15 to 200 g/10 min,
(B) 22 to 52 wt % of a predominantly amorphous propylene copolymer with 25 to 48 wt % of ethylene and/or an α-olefin with 4-10 carbon atoms being present in the composition as dispersed particles, and
(C) 0.0 to 5.0 wt % of a crystalline ethylene copolymer with an α-olefin with 3-10 carbon atoms being present in the composition as inclusions of the dispersed particles of (B) and
(D) 0 to 1.0 wt % of an alpha nucleating agent for the α- and/or γ-phase of isotactic polypropylene,
said composition being further characterized by
(i) a total melt flow rate (MFR T ) as determined at 230° C. and 2.16 kg load according ISO 1133 in the range of 2.0 to 50 g/10 min,
(ii) a fraction soluble in xylene (XCS) determined at 25° C. according ISO 16152 in the range of 22 to 52 wt %,
(iii) an intrinsic viscosity of the XCS fraction as measured according to DIN ISO 1628/1 in decalin at 135° C. is in the range of 2.5 to 9.0 dl/g and
(iv) a relative content of isolated to block ethylene sequences (I(E)) of the XCS fraction fulfilling the inequation (I):
I ( E )<78−1.97× C+ 0.015×( C ) 2

wherein C is the comonomer content [wt %] of the XCS fraction and
wherein the I(E) content is defined by equation (II)

I
⁡

(
E
)

=

fPEP

(

fEEE
+
fPEE
+
fPEP

)

×
100

(
II
)

wherein
I(E) is the relative content of isolated to block ethylene sequences [in %];
fPEP is the mol fraction of propylene/ethylene/propylene sequences (PEP) in the sample;
fPEE is the mol fraction of propylene/ethylene/ethylene sequences (PEE) and of ethylene/ethylene/propylene sequences (EEP) in the sample;
fEEE is the mol fraction of ethylene/ethylene/ethylene sequences (EEE) in the sample;
wherein all sequence concentrations being based on a statistical triad analysis of 13 C-NMR data.

2. A heterophasic polypropylene composition according to claim 1 , wherein the ratio of MFR T /MFR M is ≦0.5.

3. A heterophasic polypropylene composition according to claim 1 , having a crystalline polypropylene content with a melting point (T m ) from DSC analysis according ISO 11357 in the range of 160 to 170° C. and optionally a crystalline polyethylene content with a melting point from DSC analysis according ISO 11357 in the range of 105 to 130° C.

4. A heterophasic polypropylene composition according to claim 1 , comprising either a flexural modulus determined according to ISO 178 (FM) on an injection moulded specimen of 80×10×4 mm 3 in the range of 500 to 1100 MPa or a tensile modulus (TM) measured at 23° C. according to ISO 527-1 (cross head speed 1 mm/min) in the range of 500 to 1100 MPa and furthermore by a Charpy notched impact strength (NIS) determined according to ISO 179 1 eA at 23° C. on an injection moulded specimen of 80×10×4 mm 3 of at least 10.0 kJ/m 2 .

5. A heterophasic polypropylene composition according to claim 1 , having a total comonomer content defined as the sum of contents of ethylene and α-olefins with 4-10 carbon atoms in the range of 6.0 to 26.0 wt %.

6. A heterophasic polypropylene composition according to claim 1 , comprising at least two glass transition points (T g ) as determined by dynamic-mechanical thermal analysis according ISO 6721-7, with one T g (T g (1)) associated to the crystalline isotactic propylene homopolymer matrix being in the range of −4 to 4° C. and another T g (T g (2)) associated to the predominantly amorphous propylene copolymer being in the range of −60 to −35° C.

7. A heterophasic polypropylene composition according to claim 1 , comprising a Charpy notched impact strength determined according to ISO 179 1 eA at −20° C. on an injection moulded specimen of 80×10×4 mm 3 in the range of 4.5 to 35 kJ/m 2 .

8. A heterophasic polypropylene composition according to claim 1 , comprising a powder flowability determined according to ISO 6186:1998, Method A, of below 20 seconds, a total emission of volatiles determined according to VDA 277:1995 of below 25 ppm and a shrinkage in the longitudinal direction determined according to the method described in “Description of measuring methods” of less than 1.2%.

9. A heterophasic polypropylene composition according to claim 1 , comprising fillers or reinforcements in amount of less than 30 wt % based on the composition.

10. A heterophasic polypropylene composition according to claim 1 , wherein the composition has been polymerized 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) a co-catalyst (Co), and
c) optionally an external donor (ED).

11. A heterophasic polypropylene composition according to claim 10 , wherein said internal donor (ID) is selected from the group comprising malonates, maleates, succinates, citraconates, glutarates, cyclohexene-1,2-dicarboxylates and benzoates, and any derivatives and/or mixtures thereof.

12. A heterophasic polypropylene composition according to claim 10 , wherein the molar ratio of co-catalyst (Co) to external donor (ED) [Co/ED] is in the range of 5 to 45, and the molar ratio of co-catalyst (Co) to titanium compound (TC) [Co/TC] is in the range of above 80 to 500.

13. A process for obtaining a heterophasic polypropylene composition according to claim 1 , the process comprising:
polymerizing propylene in combination with ethylene and/or an α-olefin with 4-10 carbon atoms in three or more reactors 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) a co-catalyst (Co), and
c) optionally an external donor (ED).

14. A process according to claim 13 , wherein the internal donor (ID) is selected from optionally substituted malonates, maleates, succinates, glutarates, cyclohexene-1,2-dicarboxylates, benzoates and derivatives and/or mixtures thereof.

15. A process for preparing a heterophasic polypropylene composition according to claim 1 , using a pre-polymerization reactor (I), one liquid bulk

Assignees

• Borealis Ag

Inventors

• Wang Jingbo
• Leskinen Pauli
• Horrill Thomas
• Gahleitner Markus
• Tranninger Cornelia
• Friedrich Karlheinz
• Shutov Pavel

Classifications

• C08L23/12 Primary

  Polypropene · CPC title

• C08F10/02

  Ethene · CPC title

• C08L2314/02

  Ziegler natta catalyst · CPC title

• C08L2205/24

  Crystallisation aids · CPC title

• C08L23/16

  Ethylene-propylene or ethylene-propylene-diene copolymers · CPC title