Polypropylene composition combining low sealing initiation temperature, low haze, low hexane solubles and improved tear resistance and melting temperature

Patent metadata

Field	Value
Publication number	US-9988523-B2
Application number	US-201615551464-A
Country	US
Kind code	B2
Filing date	Feb 29, 2016
Priority date	Mar 2, 2015
Publication date	Jun 5, 2018
Grant date	Jun 5, 2018

Abstract

Polypropylene composition which combines low sealing initiation temperature (SIT) and high melting point (T m ), furthermore showing a broad sealing window, low hexane solubles and good optical properties, like low haze.

First claim

The invention claimed is:

1. A polypropylene composition being a binary blend comprising 2 polypropylene polymer fractions P1 and P2 in specific amounts:
35 to 60 wt % of (P1) being a propylene copolymer comprising hexene-derived comonomer units in an amount of 0.5 to 2.5 wt % and
65 to 40 wt % of (P2) being a propylene terpolymer comprising hexene-derived comonomer units in an amount of 4.0 to 10.0 wt % and ethylene-derived comonomer units in an amount of 0.1 to 1.0 wt %, and
whereby the composition is characterized by
(i) a ratio of the hexene content of polymer fraction P2 to polymer faction P1 between 2.5 and 8.0,
(ii) a ratio of the total hexene amount of the composition to the hexene amount of polymer fraction P1 between 1.5 and 4.0,
(ii) a melt flow rate MFR2 (230° C.) measured according to ISO 1133 in the range of 2.0 to 15.0 g/10 min,
(iii) a melting temperature Tm as determined by DSC according to ISO 11357 of from 128° C. to 145° C.,
(iv) a crystallization temperature T c as determined by DSC according to ISO 11357 of from 82° C. to 110° C.,
(v) a hexane solubles content determined in accordance with FDA section 177.1520 of at most 1.0 wt % and
(vi) an amount of xylene cold soluble (XCS) in the range of 10 to 40 wt % determined at 25° C. according ISO 16152; first edition; 2005-07-01.

2. The polypropylene composition according to claim 1 , whereby the composition is obtained in the presence of a metallocene catalyst.

3. A process for producing a polypropylene composition according to claim 1 by a sequential polymerization process comprising at least two reactors connected in series, wherein the process comprises the steps of
a) polymerizing in a first reactor (R-1) being a slurry reactor (SR), propylene and hexene, obtaining a C 3 C 6 random copolymer fraction (P1),
b) transferring said C 3 C 6 random copolymer fraction (P1) and unreacted comonomers of the first reactor in a second reactor (R-2) being a first gas phase reactor (GPR-1),
c) feeding to said second reactor (R-2) propylene, hexene and ethylene,
d) polymerizing in said second reactor (R-2) and in the presence of said first C 3 C 6 random copolymer fraction (P1) propylene, hexene and ethylene obtaining a C 3 C 6 C 2 terpolymer fraction (P2),
said C 3 C 6 random copolymer (P1) and C 3 C 6 C 2 terpolymer fraction (P2) form the polypropylene composition as defined above,
whereby the polymerization takes place in the presence of single site solid particulate catalyst free from an external carrier comprising (i) a complex of formula (I):

wherein
M is zirconium or hafnium;
each X is a sigma ligand;
L is a divalent bridge selected from —R′ 2 C—, —R′ 2 C—CR′ 2 —, —R′ 2 Si—, —R′ 2 Si—SiR′ 2 —, —R′ 2 Ge—, wherein each R′ is independently a hydrogen atom, C 1 -C 20 -hydrocarbyl, tri(C 1 -C 20 -alkyl)silyl, C 6 -C 20 -aryl, C 7 -C 20 -arylalkyl or C 7 -C 20 -alkylaryl;
R 2 and R 2′ are each independently a C 1 -C 20 hydrocarbyl radical optionally containing one or more heteroatoms from groups 14-16;
R 5 ′ is a C 1-20 hydrocarbyl group containing one or more heteroatoms from groups 14-16 optionally substituted by one or more halo atoms;
R 6 and R 6 ′ are each independently hydrogen or a C 1-20 hydrocarbyl group optionally containing one or more heteroatoms from groups 14-16;
R 7 and R 7 ′ are each independently hydrogen or C 1-20 hydrocarbyl group optionally containing one or more heteroatoms from groups 14-16;
Ar is independently an aryl or heteroaryl group having up to 20 carbon atoms optionally substituted by one or more groups R 1 ;
Ar′ is independently an aryl or heteroaryl group having up to 20 carbon atoms optionally substituted by one or more groups R 1 ;
each R 1 is a C 1-20 hydrocarbyl group or two R 1 groups on adjacent carbon atoms taken together can form a fused 5 or 6 membered non aromatic ring with the Ar group, said ring being itself optionally substituted with one or more groups R 4 ;
each R 4 is a C 1-20 hydrocarbyl group;

and (ii) a cocatalyst comprising a compound of a group 13 metal.

4. The process according to claim 3 , wherein the catalyst comprises a complex of formula (III) or (III′)

M is zirconium or hafnium;
each X is a sigma ligand;
L is a divalent bridge selected from —R′ 2 C— or —R′ 2 Si— wherein each R′ is independently a hydrogen atom, C 1-20 alkyl or C 3-10 cycloalkyl;
R 6 is hydrogen or a C 1-10 alkyl group;
R 6 ′ is a C 1-10 alkyl group or C 6-10 aryl group;
R 7 is hydrogen, C 1-6 alkyl or OC 1-6 alkyl;
Z′ is O or S;
R 3 ′ is a C 1-10 alkyl group, or C 6-10 aryl group optionally substituted by one or more halo groups;
n is independently 0 to 4; and
each R 1 is independently a C 1-10 alkyl group.

5. A process for producing water or air quench blown films, comprising
i) blowing up a tube of a molten polypropylene composition according to claim 1 with air perpendicularly to an upwards direction from a side-fed blown film die;
ii) cooling the composition down with a water contact cooling ring or air quench; and
iii) folding and guiding the composition over deflector rolls onto a winder.

6. A sterilizable or sterilized article, comprising the polypropylene composition according to claim 1 .

7. A sterilizable or sterilized film comprising the polypropylene composition according to claim 1 .

8. The sterilizable or sterilized film according to claim 7 , whereby the film is characterized by
(i) a seal initiation temperature (SIT) of below 110° C.,
(ii) satisfying the equation T m −SIT≥25, wherein Tm is the melting temperature of the polypropylene composition,
(iii) a haze (determined according to ASTM D1003-00 on cast films with a thickness of 50 μm) of at most 1.5%,
(iv) a transparency (determined according to ASTM D1003-00 on cast films with a thickness of 50 μm) of at least 90.0%,
(v) a relative tear resistance in machine direction [N/mm] according to Elmendorf method (ISO 6383-2) for a cast film thickness of 50 μm of at least 20.0 N/mm and
(vi) a relative tear resistance in transverse direction [N/mm] according to Elmendorf method (ISO 6383-2) for a cast film thickness of 50 μm of at least 170.0 N/mm.

9. The film according to claim 8 prepared by cast film technology.

10. The film according to claim 8 having a haze value (determined according to ASTM D1003-00 on cast films with a thickness of 50 μm) after steam sterilization at 121° C. for 30 min of at most 10% and a transparency (determined according to ASTM D1003-00 on cast films with a thickness of 50 μm) after steam sterilization at 121° C. for 30 min of at least 90.0%.

11. The film according to claim 9 having a haze value (determined according to ASTM D1003-00 on cast films with a thickness of 50 μm) after steam sterilization at 121° C. for 30 min of at most 10% and a transparency (determined according to ASTM D1003-00 on cast films with a thickness of 50 μm) after steam sterilization at 121° C. for 30 min of at least 90.0%.

12. The process according to claim 3 , comprising
a) polymerizing in a first reactor (R-1) being a loop reactor (LR), propylene and hexene, obtaining a C 3 C 6 random copolymer fraction (P1).

13. The process according to claim 4 , wherein each X is independently a hydrogen atom, a halogen atom, C 1-6 a

Assignees

• Borealis Ag

Inventors

• Tranninger Cornelia
• Alastalo Kauno
• Lilja Johanna
• Reichelt Kristin
• Doshev Petar

Classifications

• C08J5/18

  Manufacture of films or sheets · CPC title

• C08J2423/14

  Copolymers of propene (C08J2423/16 takes precedence) · CPC title

• B29K2023/12

  PP, i.e. polypropylene · CPC title

• B29C47/0057

  Operations & Transport · mapped topic

• C08L23/14 Primary

  Copolymers of propene (C08L23/16 takes precedence) · CPC title