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Title:
SOFT AND FLEXIBLE POLYOLEFIN COMPOSITION
Document Type and Number:
WIPO Patent Application WO/2022/028785
Kind Code:
A1
Abstract:
Disclosed is a polyolefin composition comprising: (A) 10-40% by weight of a copolymer of propylene with hexene-1 comprising 1.0-6.0% by weight, based on the weight of (A), of units deriving from hexene-1 and having melt flow rate (MFRA) measured according to ISO 1133, 230°C, 2.16 kg ranging from 20 to 60 g/10 min.; and (B) 60-90% by weight of a copolymer of propylene with at least one alpha-olefin of formula CH2=CHR, and optionally a diene, where R is H or a linear or branched C2-C8 alkyl and wherein the copolymer comprises 20-35% by weight, based on the total weight of (B), of alpha-olefin, wherein the polyolefin composition comprises an amount of fraction soluble in xylene (XS(tot)) at 25°C equal to or higher than 65% by weight, the amounts of (A), (B) and XS(tot) being based on the total weight of (A)+(B). The polyolefin composition finds use in roofing application and in the productions of geomembranes.

Inventors:
GRAZZI MICHELE (IT)
CAVALIERI CLAUDIO (IT)
Application Number:
PCT/EP2021/068180
Publication Date:
February 10, 2022
Filing Date:
July 01, 2021
Export Citation:
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Assignee:
BASELL POLIOLEFINE ITALIA SRL (IT)
International Classes:
B32B27/32; B32B5/02; C08F210/06; C08L23/16
Domestic Patent References:
WO2009080485A12009-07-02
WO2011076664A12011-06-30
WO2003076509A12003-09-18
WO2009077481A12009-06-25
WO2012072426A12012-06-07
WO2009080485A12009-07-02
WO1998056830A21998-12-17
WO1998056833A11998-12-17
WO1998056834A11998-12-17
WO2000055215A12000-09-21
WO2000063261A12000-10-26
WO2010078494A22010-07-08
WO2002100904A12002-12-19
WO2007057160A22007-05-24
WO2011061134A12011-05-26
WO1998044009A11998-10-08
WO2003011962A12003-02-13
Foreign References:
EP0045977A21982-02-17
EP0395083A21990-10-31
US7388061B22008-06-17
EP0361493A11990-04-04
EP0728769A11996-08-28
US4399054A1983-08-16
US4469648A1984-09-04
EP0472946A21992-03-04
EP0395083A21990-10-31
Other References:
HUGGINS, M.L., J. AM. CHEM. SOC., vol. 64, no. 11, 1942, pages 2716 - 2718
Attorney, Agent or Firm:
LYONDELLBASELL (IT)
Download PDF:
Claims:
CLAIMS

What is claimed is:

1. A polyolefin composition comprising:

(A) 10-40% by weight of a copolymer of propylene with hexene- 1 comprising 1.0-6.0% by weight, based on the weight of (A), of units deriving from hexene- 1 and having melt flow rate (MFRA) measured according to ISO 1133, 230°C, 2.16 kg ranging from 20 to 60 g/10 min.; and

(B) 60-90% by weight of a copolymer of propylene with at least one alpha-olefin of formula CH2=CHR, and optionally a diene, where R is H or a linear or branched C2- C8 alkyl and wherein the copolymer comprises 20-35% by weight, based on the total weight of (B), of alpha-olefin, wherein the polyolefin composition comprises an amount of fraction soluble in xylene (XS(tot)) at 25°C equal to or higher than 65% by weight, the amounts of (A), (B) and XS(tot) being based on the total weight of (A)+(B).

2. The polyolefin composition of claim 1 , wherein the propylene copolymer (A) comprises 2.0- 5.0% by weight, based on the weight of component (A), preferably 2.8-4.8% by weight, more preferably 3.0-4.0% by weight, of hexene- 1.

3. The polyolefin composition of claim 1 or 2, wherein the propylene copolymer (A) has melt flow rate (MFRA) measured according to ISO 1133, 230°C, 2.16 kg ranging from 25 to 55 g/10 min., preferably from 30 to 50 g/10 min.

4. The polyolefin composition according to any one of claims 1-3, wherein the propylene copolymer (A) comprises an amount of fraction soluble in xylene at 25°C (XSA) lower than 12.0% by weight, based on the weight of component (A), preferably lower than 9.0% by weight, more preferably XSA is comprised in the range 5.0-12.0% by weight, preferably 6.0- 9.0% by weight, more preferably 6.0-8.0% by weight.

26 The polyolefin composition according to any one of claims 1-4, comprising an amount of fraction soluble in xylene (XS(tot)) at 25°C higher than 70% by weight, based on the total weight of (A)+(B), preferably ranging from 71 to 90% by weight, more preferably from 72 to 80% by weight. The polyolefin composition according to any one of claims 1 -5, having melt flow rate (MFR) measured according to ISO 1133, 230°C, 2.16 kg, ranging from 0.2 to 6.0 g/10 min., preferably from 0.2 to 2.0 g/10 min., preferably from 0.2 to 1.5 g/10 min., more preferably from 0.25 to 1.00 g/10 min. The polyolefin composition according to any one of claims 1 -6, wherein the fraction soluble in xylene at 25°C (XS(tot)) has intrinsic viscosity ranging from 2.0 to 5.5 dl/g, preferably 2.5 to 4.5 dl/g, more preferably from 3.1 to 3.9 dl/g. The polyolefin composition according to any one of claims 1-7, wherein the at least one alpha-olefin comprised in copolymer (B) is selected from the group consisting of ethylene, butene- 1, hexene- 1, 4-methy-pentene-l, octene- 1 and combinations thereof, the alpha-olefin is preferably ethylene. The polyolefin composition according to claim 1, comprising:

(A) 10-40% by weight, 15-35% by weight, preferably 20-30% by weight of a copolymer of propylene with hexene- 1 comprising 1.0-6.0% by weight, based on the weight of component (A), preferably 2.0-5.0% by weight, preferably 2.8-4.8% by weight, more preferably 3.0-4.0% by weight, of hexene- 1 and having melt flow rate (MFRA) measured according to ISO 1133, 230°C, 2.16 kg ranging from 20 to 60 g/10 min., preferably from 25 to 55 g/10 min., more preferably from 30 to 50 g/10 min.; and

(B) 60-90% by weight, 65-85% by weight, preferably 70-80% by weight, of a copolymer of propylene with ethylene comprising 20-35% by weight of ethylene, based on the total weight of component (B), wherein i) the polyolefin composition comprises an amount of fraction soluble in xylene at 25°C (XS(tot)) higher than 65% by weight, preferably higher than 70% by weight, more preferably ranging from 71 to 90% by weight, preferably from 72 to 80% by weight ii) the amounts of (A), (B) and XS(tot) are based on the total weight of (A)+(B); and iii) the melt flow rate (MFR) measured according to ISO 1133, 230°C, 2.16 kg of the polyolefin composition ranges from 0.2 to 6.0 g/10 min., preferably from 0.2 to 2.0 g/10 min., preferably from 0.2 to 1.5 g/10 min., preferably from 0.25 to 1.00 g/10 min. The polyolefin composition according to any one of claims 1-9, having at least one of the following properties:

- Flexural Modulus ranging from 50 to 90 MPa, preferably from 60 to 85 MPa, more preferably from 65 to 80 MPa, measured according to ISO 178:2019 on injection molded specimens; and/or

- Charpy resistance at -40°C equal to or higher than 6.0 KJ/m2, measured according to ISO 179/1 eA 2010; and/or

- tensile modulus lower than 70.0 MPa, preferably lower than 60.0 MPa, more preferably lower than 50 MPa in MD and/or TD, preferably in MD and TD, determined on Imm-thick extruded sheets according to the method ISO 527-3 (specimens type 2, Crosshead speed: 1 mm/min); and/or

- Strength at break greater than 14.0 MPa, preferably greater than 15.0 MPa, in MD and/or TD, preferably in MD and TD, determined on Imm-thick extruded sheets according to the method ISO527-3 (Specimens type: 5, Crosshead speed: 500 mm/min); and/or

- puncture resistance greater than 170 N, preferably greater than 200 N, measured on a Imm- thick extruded sheet according to method ASTMD 4833 (punch diameter: 8 mm, crosshead speed: 300 mm/min); and/or

- Shore A value lower than 90, measured on Imm-thick extruded sheets according to method ISO 868 (15 sec); and/or

- Shore D value equal to or lower than 30, measured on Imm-thick extruded sheets according to method ISO 868 (15 sec). A sheet or membrane comprising the polyolefin composition according to any one of claims 1-10. The sheet or membrane according to claim 11, wherein the sheet or membrane has layers structure X/Z/Y, wherein the layer X and the layer Y comprise a polyolefin composition as described in any one of claims 1-10, and the layer Z is a reinforcing layer comprising a plastic material selected from the group consisting of propylene homopolymers, propylene copolymers, polyethylene, polyethylene terephthalate and combinations thereof. The sheet or membrane according to claim 12, wherein the layer Z is a woven or a nonwoven fabric The sheet or membrane according to any one of claims 11-13 for use as single-ply roofing sheet or membrane. The sheet or membrane according to any one of claim 11 -13 for use as geomembrane.

29

Description:
TITLE

SOFT AND FLEXIBLE POLYOLEFIN COMPOSITION

FIELD OF THE INVENTION

[0001] The present disclosure relates to thermoplastic polyolefin compositions that can be used for the preparation of sheets or membranes having high resistance to perforation and deformation, while retaining softness and good mechanical properties. The sheets or membranes are particularly suitable for roofing applications.

BACKGROUND OF THE INVENTION

[0002] Both elastomers and thermoplastic polyolefins are largely used in the art to produce sheets and membranes for single ply roofing.

[0003] Traditionally, polyvinyl chloride (PVC) and other chlorinated TPOs were used to prepare heat-weldable thermoplastic roofing sheets. However, PVC requires plasticizers to have the flexibility needed for roofing applications. The aging of membranes through plasticizers loss and the presence of chlorine in the polymer chains were the drivers for the substitution of PVC with chlorine-free thermoplastic polyolefins having the required mechanical properties in absence of plasticizers.

[0004] Heterophasic polyolefin compositions are used to prepare sheets or membranes for roofing applications, the compositions being heat-weldable, flexible and easily recyclable.

[0005] W003/076509 discloses a polyolefin composition for roofing applications having good tenacity, the composition comprising: (A) 15-40 wt.% of a crystalline copolymer of propylene and (B) 60-85 wt.% of an elastomeric fraction comprising a copolymer of propylene with ethylene and a copolymer of ethylene with alpha-olefins.

[0006] W02009/077481 discloses a membrane comprising a base layer (A) and a top layer

(B). The base layer (A) is made of a heterophasic composition comprising: (a) 10-40 wt.% of a propylene homo- or copolymer; and (b) 60-90 wt.% of one or more copolymers of ethylene with a C3-C10 alpha-olefin. The top layer (B) comprises a propylene polymer selected among propylene homopolymers, propylene copolymers with ethylene or a C4-C10 alpha-olefin and combinations thereof. The membrane has good tensile properties and good tear resistance.

[0007] Highly inert multilayer membranes having good tear and puncture resistance are disclosed in WO2012/072426. The membrane comprises: a base layer (A) and a top layer (B).The base layer (A) comprises: (a) 10-40 wt.% of a propylene homo- or copolymer and (b) 60-90 wt.% of one or more copolymers of ethylene with a C3-C10 alpha-olefin. The top layer (B) comprises an ethylene homopolymer or copolymer having density from 0.915 to 0.980 g/cm 3 .

[0008] Soft and flexible polyolefin compositions for roofing and for producing geomembranes are known from W02009/080485 disclosing a composition comprising: (A) 10-40 wt.% of a propylene/hexene-1 copolymer containing 2.5-10 wt.% of hexene- 1 and having melt flow rate of 0.5-100 g/lOmin, and (B) 60-85 wt.% of an ethylene copolymer containing 40 wt.% or less of ethylene and having solubility in xylene higher than 70 wt.%.

[0009] In this context, there is still the need of polyolefin compositions with an appropriate balance of physical-mechanical properties and good processability, which are particularly suited for preparing sheets or membranes retaining softness and having good puncture and tear resistance.

SUMMARY OF THE INVENTION

[0010] The present disclosure provides a polyolefin composition comprising:

(A) 10-40% by weight of a copolymer of propylene with hexene- 1 comprising 1.0-6.0% by weight, based on the weight of (A), of units deriving from hexene- 1 and having melt flow rate (MFRA) measured according to ISO 1133, 230°C, 2.16 kg ranging from 20 to 60 g/10 min. ; and

(B) 60-90% by weight of a copolymer of propylene with at least one alpha-olefin of formula CH2=CHR, and optionally a diene, where R is H or a linear or branched C2-C8 alkyl and wherein the copolymer comprises 20-35% by weight, based on the total weight of (B), of alpha-olefin, wherein the polyolefin composition comprises an amount of fraction soluble in xylene (XS(tot)) at 25°C equal to or higher than 65% by weight, the amounts of (A), (B) and XS(tot) being based on the total weight of (A)+(B).

[0011] The present disclosure also provides a sheet or membrane comprising a polyolefin composition comprising: (A) 10-40% by weight of a copolymer of propylene with hexene- 1 comprising 1.0-6.0% by weight, based on the weight of (A), of units deriving from hexene- 1 and having melt flow rate (MFRA) measured according to ISO 1133, 230°C, 2.16 kg ranging from 20 to 60 g/10 min.; and

(B) 60-90% by weight of a copolymer of propylene with at least one alpha-olefin of formula CH2=CHR, and optionally a diene, where R is H or a linear or branched C2-C8 alkyl and wherein the copolymer comprises 20-35% by weight, based on the total weight of (B) of alpha-olefin, wherein the polyolefin composition comprises an amount of fraction soluble in xylene (XS(tot)) at 25°C equal to or higher than 65% by weight, the amounts of (A), (B) and XS(tot) being based on the total weight of (A)+(B).

[0012] The polyolefin composition of the present disclosure shows a good balance of mechanical properties, in particular of flexibility and softness, at the same time retaining good elastic properties and having remarkable puncture and tear resistance.

[0013] The polyolefin composition has reduced stickiness and it is therefore easily processable into sheets or membranes, particularly into sheets or membranes suited for roofing applications and for producing geomembranes.

[0014] The sheets or membranes comprising the polyolefin composition of the present disclosure are soft, flexible and easy to install.

[0015] While multiple embodiments are disclosed, still other embodiments will become apparent to those skilled in the art from the following detailed description. As will be apparent, certain embodiments, as disclosed herein, are capable of modifications in various obvious aspects, all without departing from the spirit and scope of the claims as presented herein. Accordingly, the following detailed description is to be regarded as illustrative in nature and not restrictive.

DETAILED DESCRIPTION OF THE INVENTION

[0016] In one embodiment, the propylene copolymer (A) comprises 2.0-5.0% by weight, preferably 2.8-4.8% by weight, more preferably 3.0-4.0% by weight of hexene- 1, the amount of hexene- 1 being based on the weight of component (A). [0017] In one embodiment, the propylene copolymer (A) also comprises 0.1-3.0% by weight, based on the weight of component (A), of at least one further alpha-olefin selected from the group consisting of ethylene, butene- 1, 4-methyl-l -pentene, octene- 1 and combinations thereof.

[0018] In some embodiments, the propylene copolymer (A) has melt flow rate (MFRA) measured according to ISO 1133, 230°C, 2.16 kg ranging from 25 to 55 g/10 min., preferably from 30 to 50 g/10 min.

[0019] In some embodiments, the propylene copolymer (A) comprises an amount of fraction soluble in xylene at 25 °C (XS A) lower than 12.0% by weight, based on the weight of component (A), preferably lower than 9.0% by weight, more preferably XS A is comprised in the range 5.0- 12.0% by weight, preferably 6.0-9.0% by weight, more preferably 6.0-8.0% by weight.

[0020] In some embodiments, the propylene copolymer (B) comprises an amount of fraction soluble in xylene at 25°C (XSB) higher than 80% by weight, based on the total weight of component (B), preferably higher than 85% by weight, more preferably higher than 90% by weight.

[0021] In one embodiment, the upper limit of the amount of the fraction of component (B) soluble in xylene at 25 °C (XSB) is 97% by weight, based on the total weight of component (B), for each lower limit.

[0022] In some embodiments, the component (B) comprises a first copolymer (Bl) and a second copolymer (B2) of propylene with at least one alpha-olefin of formula CH2=CHR, and optionally a diene, where R is H or a linear or branched C2-C8 alkyl, provided that the total amount of alpha-olefin comprised in the propylene copolymer (B) is 20-35% by weight, based on the total weight of component (B).

[0023] In one embodiment, the component (B) comprises:

(Bl) 30-60% by weight, preferably 40-55% by weight, of a first copolymer of propylene with at least one alpha-olefin of formula CH2=CHR, and optionally a diene, where R is H or a linear or branched C2-C8 alkyl, and wherein the first propylene copolymer comprises 20-40% by weight, preferably 25-35% by weight of alpha-olefin and a fraction soluble in xylene at 25°C (XSBI) higher than 80% by weight, preferably higher than 85% by weight, more preferably higher than 90% by weigh, the amount of alpha-olefin and of XSBI are based on the weight of component (Bl); and (B2) 40-70% by weight, preferably 45-60% by weight, of a second copolymer of propylene with at least one alpha-olefin of formula CH2=CHR, and optionally a diene, where R is H or a linear or branched C2-C8 alkyl, and wherein the second propylene copolymer comprises 25- 45% by weight, preferably 30-43% by weight of alpha-olefin and a fraction soluble in xylene at 25°C (XS B2 ) higher than 80% by weight, preferably higher than 85% by weight, more preferably higher than 90% by weigh, the amount of alpha-olefin and of XSB2 are based on the weight of component (B2), wherein the amounts of (Bl) and (B2) are based on the total weight of the component (B).

[0024] In one embodiment, the upper limit of the amount of the fraction of component (Bl) and/or of the component (B2) soluble in xylene at 25°C (XSBI and/or XSB2) is 97% by weight for each lower limit, the amounts of XSBI and XSB2 being based on the weight of component (Bl) and (B2) respectively.

[0025] In one embodiment, the upper limit of XSBI and of XSB2 is 97% by weight for each lower limit, the amounts of XSBI and XSB2 being based on the weight of component (Bl) and (B2) respectively.

[0026] In some embodiments, the at least one alpha-olefin comprised in components (B), (Bl) and (B2) is independently selected from the group consisting of ethylene, butene- 1, hexene- 1, 4- methy-pentene-1, octene- 1 and combinations thereof. In a preferred embodiment, the alpha-olefin is ethylene.

[0027] Optionally, the propylene copolymers (B), (Bl) and/or (B2) comprise recurring units derived from a diene, the diene being preferably independently selected from the group consisting of butadiene, 1,4-hexadiene, 1,5-hexadiene, ethylidene-l-norbonene and combinations thereof.

[0028] In some embodiments, the total amount of recurring units deriving from a diene comprised in the propylene copolymer (B), (Bl) and/or (B2) ranges from 1 to 10% by weight, based on the weight of the relevant component.

[0029] In some embodiments of the present disclosure, the polyolefin composition comprises an amount of fraction soluble in xylene (XS(tot)) at 25°C higher than 70% by weight, based on the total weight of (A)+(B), preferably ranging from 71 to 90% by weight, preferably from 72 to 80% by weight.

[0030] In some embodiments of the present disclosure, the polyolefin composition has melt flow rate (MFR) measured according to ISO 1133, 230°C, 2.16 kg ranging from 0.2 to 6.0 g/10 min., preferably from 0.2 to 2.0 g/10 min., preferably from 0.2 to 1.5 g/10 min., more preferably from 0.25 to 1.00 g/10 min.

[0031] In some embodiments, the melt flow rate (MFR) of the polyolefin composition measured according to ISO 1133, 230°C, 2.16 kg ranging from 0.2 to 6.0 g/10 min., preferably from 0.2 to 2.0 g/10 min., preferably from 0.2 to 1.5 g/10 min., preferably from 0.25 to 1.00 g/10 min. , is obtained directly from polymerization.

[0032] In some embodiments, the melt flow rate (MFR) of the polyolefin composition measured according to ISO 1133, 230°C, 2.16 kg ranging from 0.2 to 6.0 g/10 min., preferably from 0.2 to 2.0 g/10 min., preferably from 0.2 to 1.5 g/10 min., preferably from 0.25 to 1.00 g/10 min. is not obtained by degrading (visbreaking) the polyolefin composition obtained from the polymerization reaction.

[0033] In some embodiments of the present disclosure, the fraction soluble in xylene at 25 °C of the polyolefin composition (XS(tot)) has intrinsic viscosity ranging from 2.0 to 5.5 dl/g, preferably 2.5 to 4.5 dl/g, more preferably from 3.1 to 3.9 dl/g.

[0034] In some embodiments of the present disclosure, the polyolefin composition comprises 15-35% by weight, preferably 20-30% by weight of component (A) and 65-85% by weight, preferably 70-80% by weight of component (B), wherein the amounts of (A) and (B) are based on the total weight of (A)+(B).

[0035] In a preferred embodiment of the present disclosure, the polyolefin composition comprises:

(A) 10-40% by weight, 15-35% by weight, preferably 20-30% by weight of a copolymer of propylene with hexene- 1 comprising 1.0-6.0% by weight, based on the weight of component (A), preferably 2.0-5.0% by weight, preferably 2.8-4.8% by weight, more preferably 3.0- 4.0% by weight, of hexene- 1 and having melt flow rate (MFRA) measured according to ISO 1133, 230°C, 2.16 kg ranging from 20 to 60 g/10 min., preferably from 25 to 55 g/10 min., more preferably from 30 to 50 g/10 min.; and

(B) 60-90% by weight, 65-85% by weight, preferably 70-80% by weight, of a copolymer of propylene with ethylene comprising 20-35% by weight of ethylene, based on the total weight of component (B), wherein i) the polyolefin composition comprises an amount of fraction soluble in xylene at 25°C (XS(tot)) higher than 65% by weight, preferably higher than 70% by weight, more preferably ranging from 71 to 90% by weight, preferably from 72 to 80% by weight; ii) the amounts of (A) and (B) and XS(tot) are based on the total weight of (A)+(B); and iii) the melt flow rate (MFR) measured according to ISO 1133, 230°C, 2.16 kg of the polyolefin composition ranges from 0.2 to 6.0 g/10 min., preferably from 0.2 to 2.0 g/10 min., preferably from 0.2 to 1.5 g/10 min., preferably from 0.25 to 1.00 g/10 min..

[0036] In some embodiments, the polyolefin composition has at least one of the following properties:

[0037] - Flexural Modulus ranging from 50 to 90 MPa, preferably from 60 to 85 MPa, more preferably from 65 to 80 MPa, measured according to ISO 178:2019 on injection molded specimens obtained as disclosed in the experimental section; and/or

[0038] - Charpy resistance at -40°C equal to or higher than 6.0 KJ/m 2 , measured according to

ISO 179/leA 2010. In one embodiment, the Charpy resistance at -40°C is comprised in the range 6.0 - 10.0 KJ/m 2 ; and/or

[0039] - tensile modulus lower than 70.0 MPa, preferably lower than 60.0 MPa, more preferably lower than 50 MPa in MD and/or TD, preferably in MD and TD, determined on 1mm- thick extruded sheets according to the method ISO 527-3 (specimens type 2, Crosshead speed: 1 mm/min). In one embodiment, the tensile modulus in MD and/or TD, preferably in MD and TD, is comprised in the range 30.0-70.0 MPa, preferably 30.0-60.0 MPa; and/or

[0040] - Strength at break greater than 14.0 MPa, preferably greater than 15.0 MPa, in MD and/or TD, preferably in MD and TD, determined on Imm-thick extruded sheets according to the method ISO527-3 (Specimens type: 5, Crosshead speed: 500 mm/min). In one embodiment, the strength at break in MD and/or TD, preferably in MD and TD, is comprised in the range 14.0-20.0, preferably 15.0-18.0; and/or

[0041] - puncture resistance greater than 170 N, preferably greater than 200 N, measured on a

Imm-thick extruded sheet according to method ASTM D 4833 (punch diameter: 8 mm, crosshead speed: 300 mm/min). In one embodiment, the puncture resistance is comprised in the range 170- 250 N, preferably 200-250 N; and/or [0042] - Shore A value lower than 90, measured on Imm-thick extruded sheets according to method ISO 868 (15 sec). In one embodiment, the Shore A value is comprised in the range 70-90; and/or

[0043] - Shore D value equal to or lower than 30, measured on Imm-thick extruded sheets according to method ISO 868 (15 sec). In one embodiment, the Shore D value is comprised in the range 23-30.

[0044] In a preferred embodiment of the present disclosure, the polyolefin composition has Flexural Modulus, Charpy resistance at -40°C, Strength at Break, Tensile Modulus, Puncture Resistance, Shore A and Shore D values comprised in the ranges indicated above.

[0045] In some embodiments, the polyolefin composition is also endowed with at least one of the following properties measured on injection molded specimens:

[0046] - Strength at break greater than or equal to 9.0 MPa, measured according to the method

ISO 527. In one embodiment, the strength at break is comprised in the range 9.0-15.0 MPa; and/or [0047] - Elongation at break, determined according to the method ISO 527, comprised in the range 350-550%; and/or

[0048] - Vicat softening temperature, determined according to the method ISO 306 (A50), comprised in the range 40°-60°C; and/or

[0049] - Shore A value, determined according to the method ISO 868 (15 sec), comprised in the range 70-90; and/or

[0050] - Shore D value, determined according to the method ISO 868 (15 sec), comprised in the range 23-30.

[0051] In some embodiments, the polyolefin composition is also endowed with at least one of the following properties, measured on Imm-thick extruded sheets:

[0052] - Elongation at break in MD and/or TD, preferably in MD and TD, determined according to the method ISO527-3 (Specimens type: 5, Crosshead speed: 500 mm/min), comprised in the range 600-800%; and/or

[0053] - Tear resistance in MD and/or TD, preferably in MD and TD, determined according to the method ASTM D 1004 (Crosshead speed: 51 mm/min; V-shaped die cut specimen), comprised in the range 40-70 g, preferably 50-65 g; and/or

[0054] - puncture deformation greater than or equal to 40 mm, preferably greater than or equal to 45 mm, measured according to method ASTM D 4833 (punch diameter: 8 mm, crosshead speed: 300 mm/min). In one embodiment, the puncture deformation is comprised in the range 40-60 mm, preferably 45-60 mm.

[0055] In one embodiment, the polyolefin composition is endowed with all the properties described above.

[0056] The properties disclosed above are measured on injection molded and extruded specimens obtained as described in the experimental part of the disclosure.

[0057] In some preferred embodiments, the polyolefin composition is prepared by sequential polymerization in at least two stages, wherein the second and each subsequent polymerization stage is carried out in the presence of the polymer produced in the immediately preceding polymerization stage.

[0058] In some embodiments, the polymerization processes to prepare the single components (A) and (B) or the sequential polymerization process to prepare the polyolefin composition are carried out in the presence of a catalyst selected from metallocene compounds, highly stereospecific Ziegler-Natta catalyst systems and combinations thereof.

[0059] In some preferred embodiments, the polymerization processes to prepare the single components (A) and (B) or the sequential polymerization process to prepare the polyolefin composition are carried out in the presence of a highly stereospecific Ziegler-Natta catalyst system comprising:

[0060] (1) a solid catalyst component comprising a magnesium halide support on which a Ti compound having at least a Ti-alogen bond is present, and a stereoregulating internal donor;

[0061] (2) optionally, but preferably, an Al-containing cocatalyst; and

[0062] (3) optionally, but preferably, a further electron-donor compound (external donor).

[0063] In some preferred embodiments, the solid catalyst component (1) comprises a titanium compound of formula Ti(OR)nX y-n , wherein n is comprised between 0 and y; y is the valence of titanium; X is halogen and R is a hydrocarbon group having 1-10 carbon atoms or a -COR group. Among them, particularly preferred are titanium compounds having at least one Ti-halogen bond such as titanium tetrahalides or titanium halogenalcoholates. Preferred specific titanium compounds are T1CI3, TIC1 4 , TI(OBU) 4 , TI(OBU)C1 3 , TI(OBU) 2 C1 2 , TI(OBU) 3 C1. TIC1 4 is particularly preferred. [0064] In one embodiment, the solid catalyst component (1) comprises a titanium compound in an amount securing the presence of from 0.5 to 10% by weight of Ti with respect to the total weight of the solid catalyst component (1).

[0065] The solid catalyst component (1) comprises at least one stereoregulating internal electron donor compound selected from mono or bidentate organic Lewis bases, preferably selected from esters, ketones, amines, amides, carbamates, carbonates, ethers, nitriles, alkoxysilanes and combinations thereof.

[0066] Particularly preferred are the electron donors belonging to aliphatic or aromatic mono- or dicarboxylic acid esters and diethers.

[0067] Among alkyl and aryl esters of optionally substituted aromatic polycarboxylic acids, preferred donors are the esters of phthalic acids such as those described in EP45977A2 and EP395083A2.

[0068] In some embodiments, the internal electron donor is selected from the group consisting of mono- or di-substituted phthalates, wherein the substituents are independently selected among linear or branched Ci-io alkyl, C3-8 cycloalkyl and aryl radicals.

[0069] In some preferred embodiments, the internal electron donor is selected among diisobutyl phthalate, di-n-butyl phthalate, di-n-octyl phthalate, diphenyl phthalate, benzylbutyl phthalate and combinations thereof.

[0070] In one embodiment, the internal electron donor is di-isobutyl phthalate.

[0071] Esters of aliphatic acids can be selected from malonic acids such as those described in WO98/056830, WO98/056833, WO98/056834, glutaric acids such as those disclosed in WO00/55215, and succinic acids such as those disclosed WOOO/63261.

[0072] Particular type of diesters are those deriving from esterification of aliphatic or aromatic diols such as those described in WO2010/078494 and USP 7,388,061.

[0073] In some embodiments, the internal electron donor is selected from 1,3-diethers of formula [0074] wherein R 1 and R n are independently selected from Ci-18 alkyl, C3-18 ccycloalkyl and C 7 - 18 aryl radicals, R 111 and R IV are independently selected from Ci-4 alkyl radicals; or the carbon atom in position 2 of the 1,3-diether belongs to a cyclic or polycyclic structure made up of from 5 to 7 carbon atoms, or of 5-n or 6-n' carbon atoms, and respectively n nitrogen atoms and n' heteroatoms selected from the group consisting of N, O, S and Si, where n is 1 or 2 and n' is 1, 2, or 3, said structure containing two or three unsaturations (cyclopolyenic structures), and optionally being condensed with other cyclic structures, or substituted with one or more substituents selected from the group consisting of linear or branched alkyl radicals; cycloalkyl, aryl, aralkyl, alkaryl radicals and halogens, or being condensed with other cyclic structures and substituted with one or more of the above mentioned substituents that can also be bonded to the condensed cyclic structures, wherein one or more of the above mentioned alkyl, cycloalkyl, aryl, aralkyl, or alkaryl radicals and the condensed cyclic structures optionally contain one or more heteroatom(s) as substitutes for carbon and/or hydrogen atoms. Ethers of this type are described in EP361493, EP728769 and WO02/100904.

[0075] When 1,3-diethers described above are used, the external electron donor (3) can be absent.

[0076] In some cases, specific mixtures of internal donors, in particular between aliphatic or aromatic mono or dicarboxylic acid esters and 1,3-diethers as disclosed in W007/57160 and WO2011/061134 can be used as internal donor.

[0077] Preferred magnesium halide support is magnesium dihalide.

[0078] In one embodiment, the amount of internal electron donor which remains fixed on the solid catalyst component (1) is 5 to 20% by moles, with respect to the magnesium dihalide.

[0079] Preferred methods for the preparation of the solid catalyst components start from Mg dihalide precursors that upon reaction with titanium chlorides converts the precursor into the Mg dihalide support. The reaction is preferably carried out in the presence of the steroregulating internal donor.

[0080] In a preferred embodiment the magnesium dihalide precursor is a Lewis adduct of formula MgChmR l OH, where n is a number between 0.1 and 6, and R1 is a hydrocarbon radical having 1-18 carbon atoms. Preferably, n ranges from 1 to 5 and more preferably from 1.5 to 4.5. [0081] The adduct can be suitably prepared by mixing alcohol and magnesium chloride, operating under stirring conditions at the melting temperature of the adduct (100-130°C). [0082] Then, the adduct is mixed with an inert hydrocarbon immiscible with the adduct thereby creating an emulsion which is quickly quenched causing the solidification of the adduct in the form of spherical particles.

[0083] The so obtained adduct can be directly reacted with the Ti compound or it can be previously subjected to thermal controlled dealcoholation (80-130°C) so as to obtain an adduct in which the number of moles of alcohol is generally lower than 3 preferably between 0.1 and 2.5.

[0084] This controlled dealcoholation step may carried out in order to increase the morphological stability of the catalyst during polymerization and/or to increase the catalyst porosity as described in EP395083A2.

[0085] The reaction with the Ti compound can be carried out by suspending the optionally dealcoholated adduct in cold TiCh (generally at 0°C). The mixture is heated up to 80-130°C and kept at this temperature for 0,5-2 hours. The treatment with TiC14 can be carried out one or more times. The stereoregulating internal donor can be added during the treatment with TiCl-i. The treatment with the internal donor can be repeated one or more times.

[0086] The preparation of catalyst components according to this general method is described for example in European Patent Applications US4,399,054, US4,469,648, W098/44009A1 and as already mentioned, in EP395083A2.

[0087] In one embodiment, the catalyst component (1) is in the form of spherical particles having an average diameter ranging from 10 to 350 pm, a surface area ranging from 20 to 250 m 2 /g, preferably from 80 to 200 m 2 /g and porosity greater that 0.2 ml/g, preferably of from 0.25 to 0.5 ml/g, wherein the surface area and the porosity are measured by BET.

[0088] In some preferred embodiments, the catalyst system comprises an Al-containing cocatalyst (2) selected from Al-trialkyls, preferably selected from the group consisting of Al- tryethyl, Al-triisobutyl and Al-tri-n-butyl.

[0089] In one embodiment, the Al/Ti weight ratio in the catalyst system is from 1 to 1000, preferably from 20 to 800.

[0090] In a preferred embodiment, the catalyst system comprises a further electron donor compound (3) (external electron donor) selected among silicon compounds, ethers, esters, amines, heterocyclic compounds, particularly 2,2,6,6-tetramethylpiperidine, and ketones.

[0091] Preferably, the external donor is selected among silicon compounds of formula (R2)a(R3)bSi(OR4)c, where a and b are integers from 0 to 2, c is an integer from 1 to 4 and the sum (a+b+c) is 4; R2, R3, and R4, are alkyl, cycloalkyl or aryl radicals with 1-18 carbon atoms, optionally containing heteroatoms. Particularly preferred are the silicon compounds in which a is 1, b is 1, c is 2, at least one of R2 and R3 is selected from branched alkyl, cycloalkyl or aryl groups with 3-10 carbon atoms, optionally containing heteroatoms, and R4 is a Cl -CIO alkyl group, in particular methyl.

[0092] Examples of such preferred silicon compounds are selected among methylcyclohexyldimethoxysilane (C-donor), diphenyldimethoxysilane, methyl-t- butyldimethoxysilane, dicyclopentyldimethoxysilane (D-donor), diisopropyldimethoxysilane, (2- ethylpiperidinyl)t-butyldimethoxysilane, (2-ethylpiperidinyl)thexyldimethoxysilane, (3,3,3- trifluoro-n-propyl)(2-ethylpiperidinyl)dimethoxysilane, methyl(3,3,3-trifluoro-n- propyl)dimethoxysilane and combinations thereof.

[0093] The silicon compounds in which a is 0, c is 3, R3 is a branched alkyl or cycloalkyl group, optionally containing heteroatoms, and R4 is methyl are also preferred. Examples of such silicon compounds are cyclohexyltrimethoxysilane, t-butyltrimethoxysilane and hexyltrimethoxysilane.

[0094] Even if several combinations of the components of the catalyst system allow to obtain the polyolefin compositions of the present disclosure, a particularly suitable catalyst system comprises di-isobutyl phthalate as internal electron donor and dicyclopentyl dimethoxy silane (D- donor) as external electron donor (3).

[0095] In one embodiment, the catalyst system is pre-contacted with small quantities of olefin (prepolymerization), maintaining the catalyst in suspension in a hydrocarbon solvent, and polymerizing at temperatures from 25° to 60°C producing a quantity of polymer from about 0.5 to about 3 times the weight of the catalyst system.

[0096] In an alternative embodiment, the prepolymerization is carried out in liquid monomer, producing a quantity of polymer 1000 times the weight of the catalyst system.

[0097] Sequential polymerization processes for preparing the polyolefin compositions of the present disclosure are described in EP472946 and WO03/011962, whose content is incorporated in this patent application for reference purposes.

[0098] The components (A) and (B) can be produced in any one of the polymerization stages. [0099] In one embodiment, the polymerization process comprises polymerizations stages carried out in the presence of a highly stereospecific Ziegler-Natta catalyst system, wherein: (a) in the first copolymerization stage monomers are polymerized to form the propylene copolymer (A); and

(b) in the second copolymerization stage the relevant monomers are polymerized to form the propylene copolymer (B).

[0100] In one embodiment, the second copolymerization stage (b) comprises a copolymerization stage (bl) and a copolymerization stage (b2), wherein the comonomers are polymerized to form the propylene copolymer (Bl) in the stage (bl) and copolymer (B2) in the stage (b2).

[0101] In one embodiment, the second copolymerization stage (b) comprises a copolymerization stage (bl) and a copolymerization stage (b2), wherein the propylene copolymer (B2) is formed in the copolymerization stage (bl) and the propylene copolymer (Bl) is formed in the polymerization stage (b2).

[0102] The polymerization, which can be continuous or batch, can be carried out according to known cascade techniques operating either in mixed liquid phase/gas phase or totally in gas phase. [0103] The liquid-phase polymerization can be either in slurry, solution or bulk (liquid monomer). This latter technology is the most preferred and can be carried out in various types of reactors such as continuous stirred tank reactors, loop reactors or plug-flow reactors.

[0104] The gas-phase polymerization stages can be carried out in gas-phase reactors, such as fluidized or stirred, fixed bed reactors.

[0105] In one embodiment, the copolymerization stage (a) is carried out in liquid phase using liquid propylene as diluent and the copolymerization stage (b), or the copolymerization stages (bl) and (b2), are carried out in the gas phase.

[0106] In a preferred embodiment, also the copolymerization stage (a) is carried out in the gas phase.

[0107] In one embodiment, the reaction temperatures of the polymerization stages (a), (b), (bl) and (b2) are independently selected from values comprised in the range from 40° to 90°C.

[0108] In one embodiment, the polymerization pressure of the copolymerization stage (a) carried out in liquid phase is from 3.3 to 4.3 MPa.

[0109] In one embodiment, the polymerization pressure of the copolymerization stages (a), (b), (bl) and (b2) carried out in gas-phase is independently selected from values comprised in the range from 0.5 to 3.0 MPa. [0110] The residence time of each polymerization stage depends upon the desired ratio of component (A) and (B), or of component (A), (Bl) and (B2), of the polyolefin composition.

[0111] In one embodiment, the residence time in each polymerization stage ranges from 15 minutes to 8 hours.

[0112] When the polyolefin composition of the present disclosure is prepared by a sequential polymerization process, the amounts of components (A) and (B), or of components (A), (Bl) and (B2), correspond to the split between the polymerization reactors.

[0113] The molecular weight of the propylene copolymers obtained in the polymerization stages is regulated using chain transfer agents, such as hydrogen or ZnEt2

[0114] In some preferred embodiments of the present disclosure, the polyolefin composition is blended with additives at the end of the polymerization reaction.

[0115] In one embodiment, the polyolefin composition is an additivated polyolefin composition (ADI) comprising a total amount up to 0.3 % by weight, based on the total weight of the additivated polyolefin composition (ADI), preferably from 0.01 to 0.3% by weight, of the at least one first additive (C) selected from the group consisting of antistatic agents, anti-oxidants, anti-acids, melt stabilizers and combinations thereof, of the type used in the polyolefin field.

[0116] In one embodiment, the polyolefin composition is an additivated polyolefin composition (ADI) consisting of component (A), component (B) and the at least one first additive (C), preferably in amounts as described above.

[0117] In some embodiments, the polyolefin composition further comprises at least one second additive (D) selected from the group consisting of fillers, pigments, nucleating agents, extension oils, flame retardants (e. g. aluminum trihydrate), UV resistants (e. g. titanium dioxide), UV stabilizers, lubricants (e. g., oleamide), antiblocking agents, waxes, coupling agents for fillers, and combinations thereof, the second additives (D) being known in the polymer compounding art.

[0118] In one embodiment, the additivated polyolefin composition comprises up to 50% by weight, preferably from 0.01 to 50% by weight, more preferably from 0.5 to 30% by weight, of the at least one second additive (D), the amount of the at least one second additive (D) being based the total weight of the polyolefin composition comprising the additive.

[0119] In some embodiments, the polyolefin composition is an additivated polyolefin composition (AD2) comprising the polyolefin composition as described above and

(C) up to 0.3 % by weight, preferably 0.01-0.3% by weight, of at least one first additive; and (D) up to 50% by weight, preferably from 0.01 to 50% by weight, more preferably from 0.5 to 30% by weight, of the at least one second additive, wherein the amounts are (A) and (B) are based on the total weight of (A)+(B) and the amount of the first additive (C) and the second additive (D) are based on the total weight of the additivated polyolefin composition (AD2).

[0120] In one embodiment, the first additive (C) and the second additive (D) are selected from the groups described above.

[0121] In one embodiment, the additivated polyolefin composition (AD2) consists of the components (A), (B), (C) and (D).

[0122] The physical-mechanical properties of the polyolefin composition renders it suitable for producing sheets or membranes.

[0123] A further object of the present disclosure is therefore a sheet or membrane comprising the polyolefin composition as described above.

[0124] In one embodiment, the sheet or membrane comprises the additivated polyolefin (ADI) or the additivated polyolefin composition (AD2).

[0125] In some embodiments, the sheet or membrane has total thickness in the range from 1000 to 2000 pm, preferably from 1200 to 1800 pm.

[0126] The sheet or membrane is a monolayer or a multilayer sheet or membrane.

[0127] In one embodiment, the sheet or membrane is a monolayer sheet or membrane comprising the polyolefin composition or the additivated polyolefin composition (ADI) or the additivated polyolefin composition (AD2).

[0128] In one embodiment, the monolayer sheet or membrane consists of the polyolefin composition or of the additivated polyolefin composition (ADI) or of the additivated polyolefin composition (AD2).

[0129] In some embodiments, the sheet or membrane is a multilayer sheet or membrane comprising at least one layer X, wherein the layer X comprises the polyolefin composition or the additivated polyolefin composition (ADI) or the additivated polyolefin composition (AD2).

[0130] In one embodiment, the layer X comprised in the multilayer sheet or membrane consists of the polyolefin composition or of the additivated polyolefin composition (ADI) or of the additivated polyolefin composition (AD2). [0131] In one embodiment, the multilayer sheet or membrane comprises a layer X and a layer Y, wherein the layer X and the layer Y comprise a polyolefin independently selected from the group consisting of the polyolefin composition, the additivated polyolefin composition (ADI) and the additivated polyolefin composition (AD2).

[0132] In one embodiment, the multilayer sheet or membrane comprises a layer X and a layer Y, wherein the layer X and the layer Y consist of a polyolefin independently selected from the group consisting of the polyolefin composition, the additivated polyolefin composition (ADI), and the additivated polyolefin composition (AD2).

[0133] In one embodiment, the multilayer sheet or membrane consists of a layer X and of a layer Y, wherein the layer X and the layer Y comprise a polyolefin independently selected from the group consisting of the polyolefin composition, the additivated polyolefin composition (ADI), and the additivated polyolefin composition (AD2).

[0134] In one embodiment, the multilayer sheet or membrane consists of a layer X and of a layer Y, wherein the layer X and the layer Y consist of a polyolefin independently selected from the group consisting of the polyolefin composition, the additivated polyolefin composition (ADI), and the additivated polyolefin composition (AD2).

[0135] In one embodiment, the multilayer sheet or membrane has layers structure X/Z/Y, wherein the layer X and the layer Y are as described above, and the layer Z is a reinforcing layer comprising a plastic material selected from the group consisting of propylene homopolymers, propylene copolymers, polyethylene, polyethylene terephthalate and combinations thereof.

[0136] In one embodiment, the layer Z is a woven fabric or a non-woven fabric.

[0137] Monolayer sheets or membranes are obtainable by calendaring, extrusion or spread coating. In one preferred embodiment, the sheet or membrane is obtained by extrusion.

[0138] Multilayers sheets or membranes are obtainable by co-extrusion of the polyolefin comprised in the layers or by lamination of the layers.

[0139] In one embodiment, the sheet or membrane is a single-ply roofing sheet or membrane.

[0140] In one embodiment, the sheet or membrane is a geomembrane.

[0141] The features describing the subject matter of the present disclosure are not inextricably linked to each other. As a consequence, a certain level of preference of one feature does not necessarily involve the same level of preference of the remaining features. Furthermore, it forms part of the present disclosure any combination of the parametric ranges and/or features, even though not explicitly described.

[0142] EXAMPLES

[0143] The following examples are illustrative only, and are not intended to limit the scope of the disclosure in any manner whatsoever.

[0144] CHARACTERIZATION METHODS

[0145] The following methods are used to determine the properties indicated in the description, claims and examples.

[0146] Melt Flow Rate: Determined according to the method ISO 1133 (230°C, 2.16kg).

[0147] Solubility in xylene at 25°C: 2.5 g of polymer sample and 250 ml of xylene are introduced in a glass flask equipped with a refrigerator and a magnetic stirrer. The temperature is raised in 30 minutes up to 135°C. The obtained clear solution is kept under reflux and stirring for further 30 minutes. The solution is cooled in two stages. In the first stage, the temperature is lowered to 100°C in air for 10 to 15 minute under stirring. In the second stage, the flask is transferred to a thermostatically controlled water bath at 25°C for 30 minutes. The temperature is lowered to 25°C without stirring during the first 20 minutes and maintained at 25°C with stirring for the last 10 minutes. The formed solid is filtered on quick filtering paper (eg. Whatman filtering paper grade 4 or 541). 100 ml of the filtered solution (SI) is poured in a previously weighed aluminum container, which is heated to 140°C on a heating plate under nitrogen flow, to remove the solvent by evaporation. The container is then kept on an oven at 80°C under vacuum until constant weight is reached. The amount of polymer soluble in xylene at 25 °C is then calculated. XS(tot) and XSA values are experimentally determined. The fraction of component (B) soluble in xylene at 25°C (XSB) can be calculated from the formula:

XS = W(A)X(XSA) + W(B)X(XSB) wherein W(A) and W(B) are the relative amounts of components (A) and (B), respectively, and W(A)+ W(B)=1.

[0148] Intrinsic viscosity of the xylene soluble fraction: to calculate the value of the intrinsic viscosity IV, the flow time of a polymer solution is compared with the flow time of the solvent (THN). A glass capillary viscometer of Ubbelohde type is used. The oven temperature is adjusted to 135°C. Before starting the measurement of the solvent flow time tO the temperature must be stable (135° ± 0.2°C). Sample meniscus detection for the viscometer is performed by a photoelectric device.

Sample preparation: 100 ml of the filtered solution (SI) is poured in a beaker and 200 ml of acetone are added under vigorous stirring. Precipitation of insoluble fraction must be complete as evidenced by a clear solid-solution separation. The suspension is filtered on a weighed metallic screen (200 mesh), the beaker is rinsed and the precipitate is washed with acetone so that the o- xylene is completely removed. The precipitate is dried in a vacuum oven at 70°C until a constant weight is reached. 0.05g of precipitate are weighted and dissolved in 50ml of tetrahydronaphthalene (THN) at a temperature of 135°C. The efflux time t of the sample solution is measured and converted into a value of intrinsic viscosity [r|] using Huggins' equation (Huggins, M.L., J. Am. Chem. Soc. 1942, 64, 11, 2716-2718) and the following data:

- concentration (g/dl) of the sample;

- the density of the solvent at a temperature of 135°C;

- the flow time tO of the solvent at a temperature of 135°C on the same viscometer.

One single polymer solution is used to determine [q],

[0149] Comonomer content: determined by IR using Fourier Transform Infrared Spectrometer (FTIR). The spectrum of a pressed film of the polymer is recorded in absorbance vs. wavenumbers (cm 4 ). The following measurements are used to calculate ethylene and hexene- 1 content:

- Area (At) of the combination absorption bands between 4482 and 3950 cm which is used for spectrometric normalization of film thickness;

- a linear baseline is subtracted in the range 790 - 660 cm 4 and the remaining constant offset is eliminated;

- the content of ethylene and hexene- 1 are obtained by applying a Partial Least Square (PLS1) multivariate regression to the 762 - 688 cm 4 range.

The method is calibrated by using polymer standards based on 13 C NMR analyses.

Sample preparation: Using a hydraulic press, a thick sheet is obtained by pressing about 1g of sample between two aluminum foils. Pressing temperature is 180±10°C (356°F) and about 10 kg/cm 2 pressure for about one minute (minimum two pressing operations for each specimen). A small portion is cut from this sheet to mold a film. Recommended film thickness ranges between 0.02-0.05 cm. [0150] Injection molded specimens: test specimens 80 x 10 x 4 mm were obtained according to the method ISO 1873-2:2007.

[0151] Flexural modulus: Determined according to the method ISO 178:2019 on injection molded test specimens.

[0152] Strength and Elongation at break: Determined according to the method ISO 527 on injection molded test specimens.

[0153] Shore A and D on injection molded specimens: Determined according to the method ISO 868 (15 sec).

[0154] Vicat softening temperature: Determined according to the method ISO 306 (A50) on injection molded specimens.

[0155] Charpy Impact test at -40°C: measured according to ISO 179/leA 2010 on injection molded specimens.

[0156] Preparation of extruded specimens: the polymer in form of granules are fed via feed hoppers into a Leonard extruder (mono-screw extruder, 40 mm in diameter and 27 L/D in length) where the polymer was first melted (melt temperature 230°C), compressed, mixed and finally metered out at a throughput rate of 10 Kg/h with a metering pump (15 cc/rpm). The molten polymer leaves the flat die (width 200 mm, die lip at 0.8-0.9 mm) and is instantly cooled through a vertical three-rolls calendrer having roll-temperature of 60°C. Imm-thick extruded sheets are obtained.

[0157] Tensile Modulus (MD and TD): Determined according to the method ISO 527-3 on Imm-thick extruded sheets. Specimens type 2, Crosshead speed: 1 mm/min.

[0158] Tensile strength and elongation at break (MD and TD): Determined according to the method ISO527-3 on Imm-thick extruded sheets. Specimens type: 5, Crosshead speed: 500 mm/min.

[0159] Tear resistance: Determined according to the method ASTM D 1004 on Imm-thick extruded sheets. Crosshead speed: 51 mm/min; V-shaped die cut specimen.

[0160] Puncture resistance and deformation: Determined according to the method ASTM D 4833 on Imm-thick extruded sheets. Punch diameter 8 mm, crosshead speed: 300 mm/min.

[0161] Shore A and D on extruded sheets: Determined according to the method ISO 868 (15 sec) on Imm-thick extruded sheets.

[0162] Examples 1-2 and Comparative example 3 [0163] The polymerization is carried out in two gas phase reactors connected in series and equipped with devices to transfer the product from the first to the second reactor. For the polymerization a Ziegler-Natta catalyst system is used comprising:

[0164] - a titanium- containing solid catalyst component prepared with the procedure described in EP395083, Example 3, according to which di-isobutyl phthalate is used as internal electron donor compound;

[0165] - triethylaluminium (TEAL) as co-catalyst;

[0166] - Dicyclopentyl dimethoxy silane (DCPMS) as external electron donor.

[0167] The solid catalyst component is contacted with TEAL and DCPMS in a pre-contacting vessel, with a weight ratio of TEAL to the solid catalyst component of 4-5. The weight ratio TEAL/DCPMS (T/D) is reported in Table 1.

[0168] The catalyst system is then subjected to pre-polymerization by maintaining it in suspension in liquid propylene at 20°C for about 30-32 minutes before introducing it into the first polymerization reactor.

[0169] Propylene copolymer (A) is produced into the first gas phase reactor by feeding in a continuous and constant flow the pre-polymerized catalyst system, hydrogen (used as molecular weight regulator) and propylene and comonomer (hexene- 1 or ethylene) all in gaseous phase.

[0170] The propylene copolymer (A) coming from the first reactor is discharged in a continuous flow and, after having been purged of unreacted monomers, is introduced, in a continuous flow, into the second gas phase reactor, together with quantitatively constant flows of propylene, ethylene and hydrogen, all in the gas state. In the second reactor the propylene copolymer (B) is produced.

[0171] Polymerization conditions, molar ratio of the reactants and composition of the copolymers obtained are shown in Table 1.

[0172] Table 1 - polymerization conditions

[0173] Notes: C2- = ethylene in gas phase (IR); C3- = propylene in gas phase (IR); C6- = hexene- 1 in gas phase (IR); split = amount of polymer produced in the concerned reactor.

* Calculated values.

[0174] The polymer particles exiting the second reactor are subjected to a steam treatment to remove the unreacted monomers and volatile compounds, and then dried.

[0175] The thus obtained polyolefin composition is mixed with the additives (C) in a twin screw extruder Berstorff ZE 25 (length/diameter ratio of screws: 34) and extruded under nitrogen atmosphere in the following conditions:

[0176] Rotation speed: 250 rpm;

[0177] Extruder output: 15 kg/hour;

[0178] Melt temperature: 245 °C. [0179] The additives added to the polyolefin composition are:

[0180] - 0.1% by weight of Irganox® 1010;

[0181] - 0.1% by weight of Irgafos® 168;

[0182] - 0.05% by weight of DHT-4A®.

[0183] wherein the amounts of additives are referred to the total weight of the polyolefin composition containing the additives (C).

[0184] Irganox® 1010 is 2,2-bis[3-[,5-bis(l,l-dimethylethyl)-4-hydroxyphenyl]-l- oxopropoxy]methyl]- 1 ,3-propanediyl-3,5-bis(l , 1 -dimethylethyl)-4-hydroxybenzene-propanoate; Irgafos® 168 is tris(2,4-di-tert.-butylphenyl)phosphite; DHT-4A® is Magnesium Aluminum Carbonate Hydroxide (hydrate).

[0185] Properties of the materials tested on injection molded specimens are reported in Table 3. Properties of the material tested on extruded sheets are reported in table 4.

[0186] Comparative example 4

[0187] Using the same catalyst system of example 1, a polyolefin composition is prepared in three gas phase reactors connected in series and equipped with devices to transfer the product from one reactor to the subsequent reactor.

[0188] Propylene copolymer (A) is produced into the first gas phase reactor by feeding in a continuous and constant flow the pre-polymerized catalyst system, hydrogen (used as molecular weight regulator) and propylene and ethylene all in gaseous phase. The propylene copolymer (A) coming from the first reactor is discharged in a continuous flow and, after having been purged of unreacted monomers, is introduced, in a continuous flow, into the second gas phase reactor, together with quantitatively constant flows of hydrogen and ethylene, all in the gas state. In the second reactor the propylene copolymer (Bl) is produced. The product coming from the second reactor is discharged in a continuous flow and, after having been purged of unreacted monomers, is introduced, in a continuous flow, into the third gas phase reactor, together with quantitatively constant flows of hydrogen, ethylene and propylene, all in the gas state. In the third reactor an ethylene-propylene polymer (B2) is produced.

[0189] Polymerization conditions, molar ratios of the reactants and composition of the copolymers obtained are shown in Table 2. [0190] Table 2 - polymerization conditions

[0191] Notes: C2- = ethylene in gas phase (IR); C3- = propylene in gas phase (IR); split = amount of polymer produced in the concerned reactor. * Calculated values.

[0192] The polymer particles exiting the third reactor are subjected to a steam treatment to remove the unreacted monomers and volatile compounds, dried and melt-mixed with additives as described in example 1. [0193] Properties of the materials tested on injection molded specimens are reported in Table 3. Properties of the material tested on extruded sheets are reported in Table 4.

[0194] Table 3 - characterization on injection molded specimens

(**) the polyolefin was cracked with 170 ppm of peroxide to increase the MFR and make it processable with state-of-the-art extruders used in producing sheets or membranes.

[0195] Table 4 - characterization on extruded sheets

(**) the polyolefin was cracked with 170 ppm of peroxide to increase the MFR and make it processable with state-of-the-art extruders used in producing sheets or membranes.