C
New C 2 C 3 random copolymer (RACO), which shows improved sealing behaviour due to low sealing initiation temperature (SIT) and high hot tack force. In addition, the inventive C 2 C 3 random copolymer (RACO) shows an excellent sterilization behaviour, i.e. retention of low haze level after sterilization. The present invention is furthermore related to the manufacture of said C 2 C 3 random copolymer (RACO) and to its use.
1 . A C 2 C 3 random copolymer (RACO) having:
a) an ethylene content in a range of from 2.5 to 5.2 wt %;
b) a melt flow rate MFR 2 (230° C./2.16 kg) measured according to ISO 1133 in a range of from 1.0 to 20.0 g/10 min;
c) a melting temperature Tm as determined by DSC according to ISO 11357 of from 115 to 130° C.; and
d) a xylene cold soluble (XCS) fraction of from 0.1 wt % to below 15.0 wt %,
wherein the C2C3 random copolymer (RACO) is bimodal in view of the comonomer content.
2 . The C 2 C 3 random copolymer (RACO) according to claim 1 , further having:
e) a crystallization temperature Tc as determined by DSC according to ISO 11357 in a range of 75° C. to 110° C.; and
f) a flexural modulus as determined according to ISO 178 on injection moulded specimens of 500 to below 1000 MPa.
3 . The C 2 C 3 random copolymer (RACO) according claim 1 , whereby the C 2 C 3 random copolymer (RACO) comprises:
30.0 to 70.0 wt % of polymer fraction (RACO-1) having:
i) an ethylene content in a range of from 1.5 to 5.5 wt % and
ii) a melt flow rate MFR2 (230° C./2.16 kg) measured according to ISO 1133 in a range of from 4.0 to 15.0 g/10 min and
70.0 to 30.0 wt % of polymer fraction (RACO-2) having:
i) an ethylene content in a range of from 3.5 to 7.0 wt % and
ii) a melt flow rate MFR2 (230° C./2.16 kg) measured according to ISO 1133 in a range of from 4.0 to 12.0 g/10 min,
whereby the ethylene content of polymer fraction (RACO-1) is lower than the ethylene content of polymer fraction (RACO-2).
4 . The C 2 C 3 random copolymer (RACO) according to claim 1 , whereby the C 2 C 3 random copolymer (RACO) is obtained in the presence of a metallocene catalyst.
5 . The C 2 C 3 random copolymer (RACO) according to claim 1 , wherein the C 2 C 3 random copolymer (RACO) has a xylene cold soluble (XCS) fraction of from 0.5 wt % to below 15.0 wt %.
6 . A process for producing a C 2 C 3 random copolymer (RACO) according to claim 1 , whereby the C 2 C 3 random copolymer (RACO) is produced by polymerizing propylene and ethylene in a sequential polymerization process comprising at least two reactors connected in series in the presence of a metallocene catalyst.
7 . The process for producing a C 2 C 3 random copolymer (RACO) according to claim 5 , whereby:
the process comprises the following steps:
a) polymerizing in a first reactor (R1) propylene and ethylene, obtaining polymer fraction (RACO-1) of the C 2 C 3 random copolymer (RACO),
b) transferring said polymer fraction (RACO-1) and unreacted comonomers of the first reactor into a second reactor (R2),
c) feeding to said second reactor (R2) propylene and ethylene,
d) polymerizing in said second reactor (R2) and in the presence of said polymer fraction (RACO-1) propylene and ethylene obtaining polymer fraction (RACO-2)
said polymer fraction (RACO-1) and said polymer fraction (RACO-2) forming the C 2 C 3 random copolymer (RACO) as defined in claim 1 ,
whereby the polymerization takes place in the presence of a metallocene catalyst 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 is hydrogen or C 1-20 hydrocarbyl group optionally containing one or more heteroatoms from groups 14-16;
R 7 ′ is hydrogen;
Ar and Ar′ are each 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 R1 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 at least one or two compounds of a group 13 metal, Al and/or boron compound.
8 . The process according to claim 7 , wherein as cocatalyst (ii) a cocatalyst system comprising a boron containing cocatalyst and an aluminoxane cocatalyst is used and the catalyst is supported on a silica support.
9 . A sterilizable or sterilized article comprising a C 2 C 3 random copolymer (RACO) according to claim 1 .
10 . Sterilizable or sterilized articles comprising a C 2 C 3 random copolymer (RACO) having:
a) an ethylene content in a range of from 2.5 to 5.2 wt %;
b) a melt flow rate MFR2 (230° C./2.16 kg) measured according to ISO 1133 in a range of from 1.0 to 20.0 g/10 min;
c) a melting temperature Tm as determined by DSC according to ISO 11357 of from 115 to 135° C.; and
d) a xylene cold soluble (XCS) fraction of from 0.1 wt % to below 14.0 wt %, wherein the articles are films and the films comprise:
i) a sealing initiation temperature (SIT) (determined as described in the experimental part) in a range of from 80° C. to below 120° C.
ii) a hot-tack force (determined as described in the experimental part on 50 μm cast film) of above 1.5 N to 6.0 N
iii) a haze (determined according to ASTM D1003-00 on cast film with a thickness of 50 μm) of from 0.05% to below 2.00% and a haze (determined according to ASTM D 1003-00 measured on a 50 μm cast film) after sterilization (steam sterilization at 121° C. for 30 min) of from 0.30% to below 7.00% and
iv) a clarity (determined according to ASTM D1003-00 on cast films with a thickness of 50 μm) of at least 85.0% up to 100.0% and a clarity (determined according to ASTM D1003-00 on cast films with a thickness of 50 μm) after sterilization (steam sterilization at 121° C. for 30 min) of at least 75.0% up to 98.0%.
11 . The articles according to claim 10 , wherein the films have additionally a tensile modulus determined according to ISO 527-3 at 23° C. on cast films with a thickness of 50 μm in machine direction as well as in transverse direction in a range of 300 to 600 MPa.
12 . The articles according to claim 10 , wherein the films have a resistance factor (R-factor) according to formula:
R
-
factor
=
Tensile
Modulus
(
MD
)
[
MPa
]
*
HTF
[
N
]
Haze
(
b
.
s
.
)
[
%
]
of more than 3 000 up to 6 000, wherein
Tensile Modulus (MD) is determined according to ISO 527-3 at 23° C. on cast films with a thickness of 50 μm in machine direction,
HTF is the hot-tack force measured on 50 μm cast film, and
Haze (b.s.) is determined according to ASTM D1003-00 on cast film with a thickness of 50 μm before sterilization.
13 . The articles according to claim 10 , wherein the films are multi-layer films that comprise the C 2 C 3 random copolymer (RACO) in a sealing layer.
14 . Flexible packaging systems, selected from bags or pouches for food and pharmaceutical packaging comprising a film according claim 10 .