CA3202882A1 - Polypropylene blend - Google Patents
Polypropylene blendInfo
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- CA3202882A1 CA3202882A1 CA3202882A CA3202882A CA3202882A1 CA 3202882 A1 CA3202882 A1 CA 3202882A1 CA 3202882 A CA3202882 A CA 3202882A CA 3202882 A CA3202882 A CA 3202882A CA 3202882 A1 CA3202882 A1 CA 3202882A1
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- ethylene
- plastomer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Ethene-propene or ethene-propene-diene copolymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
- A61M5/00—Devices for bringing media into the body in a subcutaneous, intra-vascular or intramuscular way; Accessories therefor, e.g. filling or cleaning devices, arm-rests
- A61M5/178—Syringes
- A61M5/31—Details
- A61M5/3129—Syringe barrels
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms
- C08L23/0815—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms with aliphatic 1-olefins containing one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/02—Applications for biomedical use
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/24—Crystallisation aids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Anesthesiology (AREA)
- Engineering & Computer Science (AREA)
- Vascular Medicine (AREA)
- Biomedical Technology (AREA)
- Heart & Thoracic Surgery (AREA)
- Hematology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
A composition is disclosed comprising a blend of 90 - 99 wt%, based on the blend, of a random propylene copolymer having an melt flow rate (MFR 230°C/2.16kg) of 15 - 40 g/10min and containing 1.5 ? 2.5 wt% ethylene, and 1 - 10 wt%, based on the blend, of an ethylene based plastomer having a density of 860 - 915 kg/m3 and an MI2 (190°C/2.16kg) of 0.5 to 25 g/10 min. The blend preferably has an MFR of 15-35 g/10min and a flexural modulus of 700-1300 MPa.
Description
POLYPROPYLENE BLEND
The present invention concerns polypropylene compositions suitable for fabrication into rigid articles such as syringe barrels. More particularly, the invention concerns blends of a random propylene copolymer and a small amount of an ethylene based plastomer.
Syringe barrels of the type commonly used in medical applications require a particular balance of rigidity, impact resistance and optical properties, and the compositions from which they are made must also be suited for the injection moulding process as well as being suitable for sterilisation by radiation. Ionizing radiation, particularly gamma radiation, is known to degrade some polymers.
It is well known to construct containers useful as medical devices, and particularly syringes, out of polypropylene. For example WO 02/14045 discloses injection moulded compositions for syringe barrels made from random propylene ethylene copolymers containing up to 5wt% ethylene and having an MFR in the range 2-100 g/10min, more particularly 15-30 g/10min.
Tt is also well known to incorporate into such polypropylene compositions other components in order to improve the properties. WO 02/14045 itself discloses the addition of slip agents such as polyethylene wax to improve operation of the syringe without adversely impacting the optical properties. EP 735089A discloses the addition of unsaturated aliphatic compounds such as safflower oil to improve the radiation stability of polypropylene compositions used in medical devices.
It is also known to blend polypropylene with other polymers such as polyethylenes in order to obtain properties suitable for different applications. WO 2016/091924 discloses films made from a blend of 75-98wt% of a polypropylene random copolymer with 2-15wt%
of an ethylene-based plastomer having a density below 915 kg/m3 and an MI2 of 2-30 g/10min.
EP 847420A discloses blends of up to 99wt% of a polypropylene homopolymer or copolymer with at least lwt% of polyethylene produced by single site catalysis and having a narrow molecular weight distribution. The polypropylene is preferably a homopolymer, but random copolymers are also mentioned, although amounts of comonomer are not disclosed, and nor is the MFR of the polypropylene. Examples of the polyethylene have densities in the range 865-910 kg/m3 and MI2 from 1.1 ¨ 10 g/10min, and are blended with a polypropylene homopolymer having an MFR of 1 g/10min. The blends are said to be resistant to degradation by sterilising radiation and to have good optical properties. Applications disclosed include medical devices such as syringe barrels. However, due to the use of propylene homopolymers
The present invention concerns polypropylene compositions suitable for fabrication into rigid articles such as syringe barrels. More particularly, the invention concerns blends of a random propylene copolymer and a small amount of an ethylene based plastomer.
Syringe barrels of the type commonly used in medical applications require a particular balance of rigidity, impact resistance and optical properties, and the compositions from which they are made must also be suited for the injection moulding process as well as being suitable for sterilisation by radiation. Ionizing radiation, particularly gamma radiation, is known to degrade some polymers.
It is well known to construct containers useful as medical devices, and particularly syringes, out of polypropylene. For example WO 02/14045 discloses injection moulded compositions for syringe barrels made from random propylene ethylene copolymers containing up to 5wt% ethylene and having an MFR in the range 2-100 g/10min, more particularly 15-30 g/10min.
Tt is also well known to incorporate into such polypropylene compositions other components in order to improve the properties. WO 02/14045 itself discloses the addition of slip agents such as polyethylene wax to improve operation of the syringe without adversely impacting the optical properties. EP 735089A discloses the addition of unsaturated aliphatic compounds such as safflower oil to improve the radiation stability of polypropylene compositions used in medical devices.
It is also known to blend polypropylene with other polymers such as polyethylenes in order to obtain properties suitable for different applications. WO 2016/091924 discloses films made from a blend of 75-98wt% of a polypropylene random copolymer with 2-15wt%
of an ethylene-based plastomer having a density below 915 kg/m3 and an MI2 of 2-30 g/10min.
EP 847420A discloses blends of up to 99wt% of a polypropylene homopolymer or copolymer with at least lwt% of polyethylene produced by single site catalysis and having a narrow molecular weight distribution. The polypropylene is preferably a homopolymer, but random copolymers are also mentioned, although amounts of comonomer are not disclosed, and nor is the MFR of the polypropylene. Examples of the polyethylene have densities in the range 865-910 kg/m3 and MI2 from 1.1 ¨ 10 g/10min, and are blended with a polypropylene homopolymer having an MFR of 1 g/10min. The blends are said to be resistant to degradation by sterilising radiation and to have good optical properties. Applications disclosed include medical devices such as syringe barrels. However, due to the use of propylene homopolymers
2 in the blends, they have relatively high stiffness and haze values. This can be a disadvantage for syringe barrels which need a certain level of flexibility in order to accommodate the plunger and provide a tight seal between the plunger and the barrel. Low haze is also desired to enable the precise determination of the volume to be measured in the syringe.
WO 2016/200335 discloses blends of a propylene copolymer or terpolymer and 2-15wt% of an elastomer having a density of 860-899 kg/m3, together with an organic peroxide, for use in moulded articles such as containers or syringes. The compositions are said to provide improved impact strength compared with equivalent compositions where the organic peroxide is absent.
Whilst the blending of polypropylene with other components can improve radiation tolerance, it is also important to maintain physical properties such as impact resistance and stiffness as well as optical properties such as clarity and haze.
Additionally, processability during the injection moulding process is important. For example, the lower the crystallisation temperature, the longer the cooling step required and hence the longer the cycle time, which obviously reduces productivity.
We have found a polypropylene blend which has an excellent balance of good impact resistance, rigidity and haze as well as a high crystallisation temperature which permits a fast cycle time during injection moulding.
Accordingly in a first aspect the present invention provides a composition comprising a blend of 90¨ 99wt%, based on the blend, of a random propylene copolymer having an melt flow rate (MFR 230 C/2.16kg) of 15 -40 g/10min and containing 1.5 ¨ 2.5wt%
ethylene, and 1 -10 wt%, based on the blend, of an ethylene based plastomer having a density of 860 - 915 kg/m1 and an MI2 (190 C/2.16kg) from 0.5 to 25 g/10 min.
Both MIR (230 C/2.16kg) and MI2 (190 C/2.16kg) are determined according to ISO
1133.
The blend preferably comprises 92 ¨ 98 wt%, more preferably 93 - 97wt%, based on the blend, of the propylene copolymer and 2 - 8 wt%, more preferably 3 - 7wt%, based on the blend, of the plastomer. Most preferred ranges of propylene copolymer and plastomer are 94 ¨ 96wt% and 4 ¨ 6wt% respectively.
The blend preferably has an MIR of 15 to 35 g/10 min, more preferably 17 to 33 g/10 min, and most preferably 19 to 29 g/10 min.
The blend preferably has a flexural modulus of 700 ¨ 1300 MPa, preferably 800-1VIPa and more preferably 900-1100 MPa.
WO 2016/200335 discloses blends of a propylene copolymer or terpolymer and 2-15wt% of an elastomer having a density of 860-899 kg/m3, together with an organic peroxide, for use in moulded articles such as containers or syringes. The compositions are said to provide improved impact strength compared with equivalent compositions where the organic peroxide is absent.
Whilst the blending of polypropylene with other components can improve radiation tolerance, it is also important to maintain physical properties such as impact resistance and stiffness as well as optical properties such as clarity and haze.
Additionally, processability during the injection moulding process is important. For example, the lower the crystallisation temperature, the longer the cooling step required and hence the longer the cycle time, which obviously reduces productivity.
We have found a polypropylene blend which has an excellent balance of good impact resistance, rigidity and haze as well as a high crystallisation temperature which permits a fast cycle time during injection moulding.
Accordingly in a first aspect the present invention provides a composition comprising a blend of 90¨ 99wt%, based on the blend, of a random propylene copolymer having an melt flow rate (MFR 230 C/2.16kg) of 15 -40 g/10min and containing 1.5 ¨ 2.5wt%
ethylene, and 1 -10 wt%, based on the blend, of an ethylene based plastomer having a density of 860 - 915 kg/m1 and an MI2 (190 C/2.16kg) from 0.5 to 25 g/10 min.
Both MIR (230 C/2.16kg) and MI2 (190 C/2.16kg) are determined according to ISO
1133.
The blend preferably comprises 92 ¨ 98 wt%, more preferably 93 - 97wt%, based on the blend, of the propylene copolymer and 2 - 8 wt%, more preferably 3 - 7wt%, based on the blend, of the plastomer. Most preferred ranges of propylene copolymer and plastomer are 94 ¨ 96wt% and 4 ¨ 6wt% respectively.
The blend preferably has an MIR of 15 to 35 g/10 min, more preferably 17 to 33 g/10 min, and most preferably 19 to 29 g/10 min.
The blend preferably has a flexural modulus of 700 ¨ 1300 MPa, preferably 800-1VIPa and more preferably 900-1100 MPa.
3 When no nucleating agent is present, the blend preferably has a melting temperature Tm of at least 146 C, more preferably at least 147 C. It preferably has a crystallisation temperature Tc of at least 107 C, more preferably at least 108 C. It preferably has a haze of less than 50%, more preferably less than 45%.
The blend preferably contains less than 0.001 wt% (based on total polymer) of peroxides or peroxide residues, and is preferably free of peroxides or peroxide residues.
Random propylene copolymer The random propylene copolymer comprises units derived from propylene and ethylene and/or another C4 to C20 a-olefin, preferably 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene or 1-decene. Ethylene and/or 1-butene are preferred. Most preferably the copolymer is a propylene-ethylene copolymer.
The MFR (MFR 230 C/2.16kg) of the random propylene copolymer is determined according to IS01133, and is preferably from 20 to 30 g/10min, more preferably in the range of 22 to 28 g/10min.
The random propylene copolymer preferably has an XCS content in the range 3 ¨
wt%, preferably 4 ¨ 9 wt%.
A first preferred random propylene copolymer has an MFR of 15 to 40 g/10min and an XCS content in the range 3 ¨ 10 wt%.
A second preferred random propylene copolymer has an MFR of 15 to 40 g/10min and an XCS content in the range 4 ¨ 9 wt%.
Random propylene copolymers are widely available commercially. They can be produced by polymerization in the presence of any conventional coordination catalyst system including Ziegler-Natta and single site catalysts such as metallocenes, and in any conventional polymerisation process such as gas phase, slurry and propylene bulk processes known in the art.
A preferred polymerisation process is a fluidised bed gas phase process comprising a single reactor or two reactors in series, in which the same copolymer is made in both reactors.
Polymerization of propylene and comonomer is conducted in the first reactor.
Hydrogen is used to obtain the desired MFR value. The catalyst system components are added at a rate to obtain the desired rate of polymerization.
The polymer powder containing active catalyst residues is intermittently transferred to a depressurization vessel to remove unreacted monomer and other gaseous components. The depressurization vessel is pressurized with nitrogen to convey the polymer powder into the
The blend preferably contains less than 0.001 wt% (based on total polymer) of peroxides or peroxide residues, and is preferably free of peroxides or peroxide residues.
Random propylene copolymer The random propylene copolymer comprises units derived from propylene and ethylene and/or another C4 to C20 a-olefin, preferably 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene or 1-decene. Ethylene and/or 1-butene are preferred. Most preferably the copolymer is a propylene-ethylene copolymer.
The MFR (MFR 230 C/2.16kg) of the random propylene copolymer is determined according to IS01133, and is preferably from 20 to 30 g/10min, more preferably in the range of 22 to 28 g/10min.
The random propylene copolymer preferably has an XCS content in the range 3 ¨
wt%, preferably 4 ¨ 9 wt%.
A first preferred random propylene copolymer has an MFR of 15 to 40 g/10min and an XCS content in the range 3 ¨ 10 wt%.
A second preferred random propylene copolymer has an MFR of 15 to 40 g/10min and an XCS content in the range 4 ¨ 9 wt%.
Random propylene copolymers are widely available commercially. They can be produced by polymerization in the presence of any conventional coordination catalyst system including Ziegler-Natta and single site catalysts such as metallocenes, and in any conventional polymerisation process such as gas phase, slurry and propylene bulk processes known in the art.
A preferred polymerisation process is a fluidised bed gas phase process comprising a single reactor or two reactors in series, in which the same copolymer is made in both reactors.
Polymerization of propylene and comonomer is conducted in the first reactor.
Hydrogen is used to obtain the desired MFR value. The catalyst system components are added at a rate to obtain the desired rate of polymerization.
The polymer powder containing active catalyst residues is intermittently transferred to a depressurization vessel to remove unreacted monomer and other gaseous components. The depressurization vessel is pressurized with nitrogen to convey the polymer powder into the
4 second reactor for further polymerization. Further propylene, comonomer and hydrogen are added in a ratio to obtain the desired composition. The polymer powder is intermittently removed from the second reactor for subsequent removal of all volatile materials followed by compounding to obtain the target composition in the form of pellets.
The random propylene copolymer may optionally be nucleated with at least one a-nucleating agent. Generally any a-nucleating agent can be used. Examples of suitable cc-nucleating agents include (i) salts of monocarboxylic acids and polycarboxylic acids, e.g. sodium benzoate or aluminum tert-butylbenzoate, (ii) dibenzylidenesorbitol (e.g. 1,3 : 2,4 dibenzylidenesorbitol) and C18-C-alkyl-substituted dibenzylidenesorbitol derivatives, such as methyldibenzylidenesorbitol, ethyldibenzylidenesorbitol or dimethyldibenzylidenesorbitol (e.g. 1,3 : 2,4 di(methylbenzylidene) sorbitol), nonito1,1,2,3,-trideoxy-4,6:5,7-bis-044-propylphenyl)methylene]-nonitol, (iii) salts of diesters of phosphoric acid, e.g. sodium 2,2'-methylenebis (4, 6,-di-tert-butylphenyl) phosphate or aluminium-hydroxy-bis[2,2'-methylene-bis(4,6-di-t-butylphenyl)phosphate], and (iv) vinylcycloalkane polymer and vinylalkane polymers.
Any nucleating agent is preferably present in the random propylene copolymer in an amount of from 10 to 10000ppm, preferably from 200 to 5000ppm based on the weight of the copolymer.
Ethylene based plastomer The ethylene based plastomer is a copolymer of ethylene and a C3 - C10 alpha-olefin Suitable C3 - C10 alpha-olefins include 1-propylene, 1-butene, 1-hexene and 1-octene, preferably 1-butene or 1-hexene and most preferably 1-hexene.
The comonomer content of the ethylene based plastomer is typically between 4 and 7 mol%, preferably between 4.5 and 6.5 mol% and most preferably between 5.0 and 6.0 mol%.
The plastomer preferably has a density in the range of 870 - 910 kg/m3, more preferably in the range of 890 - 910 kg/m3 and most preferably in the range 898 - 905 kg/m3.
The plastomer preferably has an MI? (ISO 1133; 190 C; 2.16kg) in the range of 0.5 -15 g/10 min, preferably in the range of 0.5 - 5 g/10 min and more preferably in the range of 0.5 - 3.0 g/min. Particularly preferred ranges are 0.3 ¨ 2.5 g/10min and 1.0 to 1.6 g/10 min.
The random propylene copolymer may optionally be nucleated with at least one a-nucleating agent. Generally any a-nucleating agent can be used. Examples of suitable cc-nucleating agents include (i) salts of monocarboxylic acids and polycarboxylic acids, e.g. sodium benzoate or aluminum tert-butylbenzoate, (ii) dibenzylidenesorbitol (e.g. 1,3 : 2,4 dibenzylidenesorbitol) and C18-C-alkyl-substituted dibenzylidenesorbitol derivatives, such as methyldibenzylidenesorbitol, ethyldibenzylidenesorbitol or dimethyldibenzylidenesorbitol (e.g. 1,3 : 2,4 di(methylbenzylidene) sorbitol), nonito1,1,2,3,-trideoxy-4,6:5,7-bis-044-propylphenyl)methylene]-nonitol, (iii) salts of diesters of phosphoric acid, e.g. sodium 2,2'-methylenebis (4, 6,-di-tert-butylphenyl) phosphate or aluminium-hydroxy-bis[2,2'-methylene-bis(4,6-di-t-butylphenyl)phosphate], and (iv) vinylcycloalkane polymer and vinylalkane polymers.
Any nucleating agent is preferably present in the random propylene copolymer in an amount of from 10 to 10000ppm, preferably from 200 to 5000ppm based on the weight of the copolymer.
Ethylene based plastomer The ethylene based plastomer is a copolymer of ethylene and a C3 - C10 alpha-olefin Suitable C3 - C10 alpha-olefins include 1-propylene, 1-butene, 1-hexene and 1-octene, preferably 1-butene or 1-hexene and most preferably 1-hexene.
The comonomer content of the ethylene based plastomer is typically between 4 and 7 mol%, preferably between 4.5 and 6.5 mol% and most preferably between 5.0 and 6.0 mol%.
The plastomer preferably has a density in the range of 870 - 910 kg/m3, more preferably in the range of 890 - 910 kg/m3 and most preferably in the range 898 - 905 kg/m3.
The plastomer preferably has an MI? (ISO 1133; 190 C; 2.16kg) in the range of 0.5 -15 g/10 min, preferably in the range of 0.5 - 5 g/10 min and more preferably in the range of 0.5 - 3.0 g/min. Particularly preferred ranges are 0.3 ¨ 2.5 g/10min and 1.0 to 1.6 g/10 min.
5 The plastomer preferably has a molecular weight distribution (Mw/Mn) in the range 3 to 5, more preferably 3.2 to 4.5 and most preferably 3.4 to 4.5.
A first preferred plastomer has a density in the range 890 - 910 kg/m3 and an MI2 in the range of 0.5 -3.0 g/min, preferably 0.3 ¨ 2.5 g/10min and more preferably 1.0 to 1.6 g/10min. It preferably also has a molecular weight distribution (Mw/Mn) in the range 3 to 5.
A second preferred plastomer has a density in the range 898 - 905 kg/m3 and an in the range 0.5 - 3.0 g/min, preferably 0.3 ¨2.5 g/10min and more preferably 1.0 to 1.6 g/10 min. It preferably also has a molecular weight distribution (Mw/Mn) in the range 3 to 5.
Furthermore suitable ethylene based plastomers have a glass transition temperature Tg (measured with DMTA according to ISO 6721-7) of below -25 C, preferably below -30 C, more preferably below -35 C.
Suitable plastomers our those disclosed in our copending application WO
2017/005867.
The plastomer may suitably be prepared by a process such as that disclosed in WO
2017/005867, using a metallocene catalyst system which is preferably a monocylcopentadienyl metallocene complex having a 'constrained geometry' configuration together with a suitable activator as described in the earlier application.
The plastomer is most suitably prepared in a gas phase process, and most preferably in a gas phase process operating in a fluidised bed. Particularly preferred gas phase processes are those operating in "condensed mode" as described in EP 89691 and EP
699213, the latter being a particularly preferred process. By "condensed mode" is meant the "process of purposefully introducing a recycle stream having a liquid and a gas phase into a reactor such that the weight percent of liquid based on the total weight of the recycle stream is typically greater than about 2.0 weight percent".
The blend One preferred blend comprises the first preferred random propylene copolymer defined above, having an MFR of 15 to 40 g/10min and an XCS content in the range 3 ¨ 10 wt%, in combination with a plastomer having a density in the range 890 - 910 kg/m3 and an M12 in the range of 0.5 -3.0 g/min, preferably 0.3 ¨2.5 g/10min and more preferably 1.0 to 1.6 g/10min.
Another preferred blend comprises the first preferred random propylene copolymer defined above, having an MFR of 15 to 40 g/10min and an XCS content in the range 3 ¨ 10 wt%, in combination with a plastomer having a density in the range 898 - 905 kg/m3 and an
A first preferred plastomer has a density in the range 890 - 910 kg/m3 and an MI2 in the range of 0.5 -3.0 g/min, preferably 0.3 ¨ 2.5 g/10min and more preferably 1.0 to 1.6 g/10min. It preferably also has a molecular weight distribution (Mw/Mn) in the range 3 to 5.
A second preferred plastomer has a density in the range 898 - 905 kg/m3 and an in the range 0.5 - 3.0 g/min, preferably 0.3 ¨2.5 g/10min and more preferably 1.0 to 1.6 g/10 min. It preferably also has a molecular weight distribution (Mw/Mn) in the range 3 to 5.
Furthermore suitable ethylene based plastomers have a glass transition temperature Tg (measured with DMTA according to ISO 6721-7) of below -25 C, preferably below -30 C, more preferably below -35 C.
Suitable plastomers our those disclosed in our copending application WO
2017/005867.
The plastomer may suitably be prepared by a process such as that disclosed in WO
2017/005867, using a metallocene catalyst system which is preferably a monocylcopentadienyl metallocene complex having a 'constrained geometry' configuration together with a suitable activator as described in the earlier application.
The plastomer is most suitably prepared in a gas phase process, and most preferably in a gas phase process operating in a fluidised bed. Particularly preferred gas phase processes are those operating in "condensed mode" as described in EP 89691 and EP
699213, the latter being a particularly preferred process. By "condensed mode" is meant the "process of purposefully introducing a recycle stream having a liquid and a gas phase into a reactor such that the weight percent of liquid based on the total weight of the recycle stream is typically greater than about 2.0 weight percent".
The blend One preferred blend comprises the first preferred random propylene copolymer defined above, having an MFR of 15 to 40 g/10min and an XCS content in the range 3 ¨ 10 wt%, in combination with a plastomer having a density in the range 890 - 910 kg/m3 and an M12 in the range of 0.5 -3.0 g/min, preferably 0.3 ¨2.5 g/10min and more preferably 1.0 to 1.6 g/10min.
Another preferred blend comprises the first preferred random propylene copolymer defined above, having an MFR of 15 to 40 g/10min and an XCS content in the range 3 ¨ 10 wt%, in combination with a plastomer having a density in the range 898 - 905 kg/m3 and an
6 MI2 in the range of 0.5 -3.0 g/min, preferably 0.3 ¨ 2.5 g/10min and more preferably 1.0 to 1.6 g/10min.
A further preferred blend comprises the second preferred random propylene copolymer defined above, having an MFR of 15 to 40 g/10min and an XCS content in the range 4 ¨ 9 wt%, in combination with a plastomer having a density in the range kg/m3 and an MI2 in the range of 0.5 -3.0 g/min, preferably 0.3 ¨2.5 g/10min and more preferably 1.0 to 1.6 g/10min.
A further preferred blend comprises the second preferred random propylene copolymer defined above, having an MFR of 15 to 40 g/10min and an XCS content in the range 4 ¨ 9 wt%, in combination with a plastomer having a density in the range kg/m3 and an MI2 in the range of 0.5 -3.0 g/min, preferably 0.3 ¨2.5 g/10min and more preferably 1.0 to 1.6 g/10min.
The blend can be produced by any suitable melt mixing process at temperatures above the melting point of the respective blend. Typical devices for performing said melt mixing process are twin screw extruders, single screw extruders optionally combined with static mixers, chamber kneaders like Farrel kneaders, Banbury type mixers and reciprocating co-kneaders like Buss co-kneaders. Preferably, the melt mixing process is carried out in a twin screw extruder with high intensity mixing segments and preferably at a temperature of 170 to 270 C, more preferably of 180 to 250 C.
It is also possible to produce the blend of the present invention by dry-blending in a suitable mixing equipment, like horizontal and vertical agitated chambers, tumbling vessels, and Turbula mixers, as long as sufficient homogeneity is obtained.
The composition of the invention which comprises the blend may also contain other additives, as is well known in the art. Typical additives used in such compositions are listed below.
Examples of antioxidants are sterically hindered phenols (such as CAS No. 6683-8, also sold as Irganox 1010 FFTM by BASF), phosphorous based antioxidants (such as CAS
No. 31570-04-4, also sold as Hostanox PAR 24 (FF)TM by Clariant, or Irgafos 168 (FF)TM by BASF), sulphur based antioxidants (such as CAS No. 693-36-7, sold as Irganox by BASF), nitrogen-based antioxidants (such as 4,4'-bis(1,1'-dimethylbenzyl)diphenylamine), or antioxidant blends.
Examples of acid scavengers are calcium stearates, sodium stearates, zinc stearates, magnesium and zinc oxides, synthetic hydrotalcite (e.g. SHT, CAS-no. 11097-59-9), lactates and lactylates, as well as calcium and zinc stearates.
A further preferred blend comprises the second preferred random propylene copolymer defined above, having an MFR of 15 to 40 g/10min and an XCS content in the range 4 ¨ 9 wt%, in combination with a plastomer having a density in the range kg/m3 and an MI2 in the range of 0.5 -3.0 g/min, preferably 0.3 ¨2.5 g/10min and more preferably 1.0 to 1.6 g/10min.
A further preferred blend comprises the second preferred random propylene copolymer defined above, having an MFR of 15 to 40 g/10min and an XCS content in the range 4 ¨ 9 wt%, in combination with a plastomer having a density in the range kg/m3 and an MI2 in the range of 0.5 -3.0 g/min, preferably 0.3 ¨2.5 g/10min and more preferably 1.0 to 1.6 g/10min.
The blend can be produced by any suitable melt mixing process at temperatures above the melting point of the respective blend. Typical devices for performing said melt mixing process are twin screw extruders, single screw extruders optionally combined with static mixers, chamber kneaders like Farrel kneaders, Banbury type mixers and reciprocating co-kneaders like Buss co-kneaders. Preferably, the melt mixing process is carried out in a twin screw extruder with high intensity mixing segments and preferably at a temperature of 170 to 270 C, more preferably of 180 to 250 C.
It is also possible to produce the blend of the present invention by dry-blending in a suitable mixing equipment, like horizontal and vertical agitated chambers, tumbling vessels, and Turbula mixers, as long as sufficient homogeneity is obtained.
The composition of the invention which comprises the blend may also contain other additives, as is well known in the art. Typical additives used in such compositions are listed below.
Examples of antioxidants are sterically hindered phenols (such as CAS No. 6683-8, also sold as Irganox 1010 FFTM by BASF), phosphorous based antioxidants (such as CAS
No. 31570-04-4, also sold as Hostanox PAR 24 (FF)TM by Clariant, or Irgafos 168 (FF)TM by BASF), sulphur based antioxidants (such as CAS No. 693-36-7, sold as Irganox by BASF), nitrogen-based antioxidants (such as 4,4'-bis(1,1'-dimethylbenzyl)diphenylamine), or antioxidant blends.
Examples of acid scavengers are calcium stearates, sodium stearates, zinc stearates, magnesium and zinc oxides, synthetic hydrotalcite (e.g. SHT, CAS-no. 11097-59-9), lactates and lactylates, as well as calcium and zinc stearates.
7 Examples of antiblocking agents are natural silica such as diatomaceous earth (such as CAS-no. 60676-86-0 (SuperfFlossTm), CAS-no. 60676-86-0 (SuperFloss ETm), or CAS-no.
60676-86-0 (Celite 499Tm)), synthetic silica (such as CAS-no. 7631-86-9, CAS-no. 7631-86-9, CAS-no. 7631-86-9, CAS-no. 7631-86-9, CAS-no. 7631-86-9, CAS-no. 7631-86-9, CAS-no. 112926-00-8, CAS-no. 7631-86-9, or CAS-no. 7631-86-9), silicates (such as aluminum silicate (Kaolin) CAS-no. 1318-74-7, sodium aluminum silicate CAS-no. 1344-00-9, calcined kaolin CAS-no. 92704-41-1, aluminum silicate CAS-no. 1327-36-2, or calcium silicate CAS-no. 1344-95-2), synthetic zeolites (such as sodium calcium aluminosilicate hydrate CAS-no.
1344-01-0, CAS-no. 1344-01-0, or sodium calcium aluminosilicate, hydrate CAS-no. 1344-01-0).
Examples of UV-stabilisers are, for example, bis-(2,2,6,6-tetramethy1-4-piperidy1)-sebacate (CAS 52829-07-9, Tinuvin 770); 2-hydroxy-4-n-octoxy-benzophenone (CAS
05-6, Chimassorb 81).
Examples of nucleating agents are sodium benzoate (CAS 532-32-1) and 1,3:2,4-bis(3,4-dimethylbenzylidene)sorbitol (CAS 135861-56-2, Millad 3988).
The above additives are typically incorporated in the composition in quantities of 100 - 10000ppm for each additive.
When a nucleating agent is present in the composition, the composition preferably has a melting temperature Tin of at least 149 C, more preferably at least 150 C, It preferably has a crystallisation temperature Tc of at least 120 C, more preferably at least 122 C. It preferably has haze of less than 20%, more preferably less than 18%.
The compositions of the invention are suitable for fabrication into articles, particularly rigid articles such as medical devices, which can also be subject to sterilisation procedures known in the art. A particularly preferred application is syringe barrels.
EXAMPLES
The meanings of the symbols used in these examples and the units expressing the properties mentioned and the methods for measuring these properties are explained below.
Melt index The melt flow rate of the polypropylene (MFR) and the melt index of the polyethylene (MI2) are determined according to IS01133 at temperatures of 230 C (MFR) and 190 C (MI2) under a load of 2.16 kg and are indicated in g/10min.
60676-86-0 (Celite 499Tm)), synthetic silica (such as CAS-no. 7631-86-9, CAS-no. 7631-86-9, CAS-no. 7631-86-9, CAS-no. 7631-86-9, CAS-no. 7631-86-9, CAS-no. 7631-86-9, CAS-no. 112926-00-8, CAS-no. 7631-86-9, or CAS-no. 7631-86-9), silicates (such as aluminum silicate (Kaolin) CAS-no. 1318-74-7, sodium aluminum silicate CAS-no. 1344-00-9, calcined kaolin CAS-no. 92704-41-1, aluminum silicate CAS-no. 1327-36-2, or calcium silicate CAS-no. 1344-95-2), synthetic zeolites (such as sodium calcium aluminosilicate hydrate CAS-no.
1344-01-0, CAS-no. 1344-01-0, or sodium calcium aluminosilicate, hydrate CAS-no. 1344-01-0).
Examples of UV-stabilisers are, for example, bis-(2,2,6,6-tetramethy1-4-piperidy1)-sebacate (CAS 52829-07-9, Tinuvin 770); 2-hydroxy-4-n-octoxy-benzophenone (CAS
05-6, Chimassorb 81).
Examples of nucleating agents are sodium benzoate (CAS 532-32-1) and 1,3:2,4-bis(3,4-dimethylbenzylidene)sorbitol (CAS 135861-56-2, Millad 3988).
The above additives are typically incorporated in the composition in quantities of 100 - 10000ppm for each additive.
When a nucleating agent is present in the composition, the composition preferably has a melting temperature Tin of at least 149 C, more preferably at least 150 C, It preferably has a crystallisation temperature Tc of at least 120 C, more preferably at least 122 C. It preferably has haze of less than 20%, more preferably less than 18%.
The compositions of the invention are suitable for fabrication into articles, particularly rigid articles such as medical devices, which can also be subject to sterilisation procedures known in the art. A particularly preferred application is syringe barrels.
EXAMPLES
The meanings of the symbols used in these examples and the units expressing the properties mentioned and the methods for measuring these properties are explained below.
Melt index The melt flow rate of the polypropylene (MFR) and the melt index of the polyethylene (MI2) are determined according to IS01133 at temperatures of 230 C (MFR) and 190 C (MI2) under a load of 2.16 kg and are indicated in g/10min.
8 Density Density of the polyethylene was measured according to ISO 1183-1 (Method A) and the sample plaque was prepared according to ASTM D4703 (Condition C) where it was cooled under pressure at a cooling rate of 15 C/min from 190 C to 40 C.
Melting temperature (Tm) and crystallisation temperature (Tc) These were measured by Differential Scanning Calorimetry (DSC) with a cooling rate of 10 C/min.
Flexural Modulus Flexural modulus was measured according to ISO 178 at 23 C on ISO lA plaques of mm width and 4mm thickness, injection moulded according to ISO 294-1.
Haze Haze was measured using a "Haze-Guard plus" haze meter from BYK Garder referred to in ASTM-D1003.
Xylene cold soluble fraction (XCS) XCS was determined at 25 C according to ISO 16152 by putting 3g of polymer in a solution in 200m1 of metaxylene at boiling temperature, cooling the solution to 25 C by immersion in a water bath and maintaining the solution at that temperature for 1 hour, and filtering the soluble fraction at 25 C on filter paper.
Resilience Resilience was measured according to ISO 6603 at room temperature using an instrumented drop tower. A striker with a diameter of 20mm and a total weight of 21.03 kg was dropped from a height of 1 metre, giving an impact speed of 4.43 m/s and an impact energy of 206 J.
Random propylene copolymer Copolymers having ethylene contents ranging from 1.6 to 3.0wt% were made in a single reactor continuous fluidised bed gas phase polymerisation reactor system having a vertical cylindrical section of 2.7m height and 0.5m diameter.
Melting temperature (Tm) and crystallisation temperature (Tc) These were measured by Differential Scanning Calorimetry (DSC) with a cooling rate of 10 C/min.
Flexural Modulus Flexural modulus was measured according to ISO 178 at 23 C on ISO lA plaques of mm width and 4mm thickness, injection moulded according to ISO 294-1.
Haze Haze was measured using a "Haze-Guard plus" haze meter from BYK Garder referred to in ASTM-D1003.
Xylene cold soluble fraction (XCS) XCS was determined at 25 C according to ISO 16152 by putting 3g of polymer in a solution in 200m1 of metaxylene at boiling temperature, cooling the solution to 25 C by immersion in a water bath and maintaining the solution at that temperature for 1 hour, and filtering the soluble fraction at 25 C on filter paper.
Resilience Resilience was measured according to ISO 6603 at room temperature using an instrumented drop tower. A striker with a diameter of 20mm and a total weight of 21.03 kg was dropped from a height of 1 metre, giving an impact speed of 4.43 m/s and an impact energy of 206 J.
Random propylene copolymer Copolymers having ethylene contents ranging from 1.6 to 3.0wt% were made in a single reactor continuous fluidised bed gas phase polymerisation reactor system having a vertical cylindrical section of 2.7m height and 0.5m diameter.
9 Polymerisation was initiated by the introduction of a high activity supported titanium containing Ziegler-Natta catalyst component commercially available from Grace under the trade name C602 through a liquid propylene-flushed catalyst addition nozzle. A
mixture of selectivity control agent (SCA), commercially available from Grace under the trade name D-9600, plus trialkylaluminum (TEA) co-catalyst in hexane was fed separately to the first reactor through a different liquid propylene-flushed addition nozzle to obtain a Al/SCA ratio of about 3 and a Al/Ti ratio of about 160. Hydrogen, ethylene and propylene were fed to the reactor through separate mass-flow meters in order to achieve the desired powder melt flow rate (MFR) and ethylene content. The reactor temperature was maintained at 57 C.
Polymer was continuously with drawn from the reactor and subjected to a reduction in pressure to remove all volatile materials, followed by a final degassing step.
The polymer powder was then homogenised in an Ancheschi F6950 cylinder-conical discontinuous homogeniser. The properties of the random propylene copolymer powders are given in Tables 1 and 2.
Ethylene-based plastomer The plastomer was made as described in the Examples of WO 2017/005867 in a fluidized bed gas phase reactor of 5m diameter, with a vertical cylindrical section of 15.8m.
The resulting polymer powder was pelletized in an extruder together with 800ppm Irgafos 168 and 275ppm Irganox 1010. The properties of the ethylene plastomer pellets are given in Tables 1 and 2.
The composition The random propylene copolymer powder and plastomer pellets were blended in a Papenmeier mixer (volume 17.5 dm', rotation speed 1500 tr/min for 5 mins), together with additives in the amounts given in Table 1 and 2. The additives used were the following:
IRGANOX 1010 (tetrakis-(methylene-(3,5-di-(tert)-buty1-4- hydrocinnamate))-methane available from BASF
IRGAFOS PEP-Q (tetrakis(2,4-di-tert-butylpheny1)[1,1-bipheny1]-4,41diylbisphosphonite available from BASF
IRGAFOS 168 (tris(2,4-di-tert.-butylphenyl)phosphite) available from BASF
MILLAD 3988 (1,3:2,4-bis(3,4-dimethylbenzylidene)sorbitol) available from Milliken Chemicals DHT-4A (hydrotalcite) available from Kyowa Chemical.
mixture of selectivity control agent (SCA), commercially available from Grace under the trade name D-9600, plus trialkylaluminum (TEA) co-catalyst in hexane was fed separately to the first reactor through a different liquid propylene-flushed addition nozzle to obtain a Al/SCA ratio of about 3 and a Al/Ti ratio of about 160. Hydrogen, ethylene and propylene were fed to the reactor through separate mass-flow meters in order to achieve the desired powder melt flow rate (MFR) and ethylene content. The reactor temperature was maintained at 57 C.
Polymer was continuously with drawn from the reactor and subjected to a reduction in pressure to remove all volatile materials, followed by a final degassing step.
The polymer powder was then homogenised in an Ancheschi F6950 cylinder-conical discontinuous homogeniser. The properties of the random propylene copolymer powders are given in Tables 1 and 2.
Ethylene-based plastomer The plastomer was made as described in the Examples of WO 2017/005867 in a fluidized bed gas phase reactor of 5m diameter, with a vertical cylindrical section of 15.8m.
The resulting polymer powder was pelletized in an extruder together with 800ppm Irgafos 168 and 275ppm Irganox 1010. The properties of the ethylene plastomer pellets are given in Tables 1 and 2.
The composition The random propylene copolymer powder and plastomer pellets were blended in a Papenmeier mixer (volume 17.5 dm', rotation speed 1500 tr/min for 5 mins), together with additives in the amounts given in Table 1 and 2. The additives used were the following:
IRGANOX 1010 (tetrakis-(methylene-(3,5-di-(tert)-buty1-4- hydrocinnamate))-methane available from BASF
IRGAFOS PEP-Q (tetrakis(2,4-di-tert-butylpheny1)[1,1-bipheny1]-4,41diylbisphosphonite available from BASF
IRGAFOS 168 (tris(2,4-di-tert.-butylphenyl)phosphite) available from BASF
MILLAD 3988 (1,3:2,4-bis(3,4-dimethylbenzylidene)sorbitol) available from Milliken Chemicals DHT-4A (hydrotalcite) available from Kyowa Chemical.
10 The homogenized mixture was then pelletized in an APV 19TC25 extruder. The barrel temperature used was 210 C, the screw speed was 300 rpm and the throughput was 5 kg/h. The barrel diameter D was 19mm and the barrel length to diameter (LID) ratio was 25.
Examples labelled "CE" below are comparative examples.
Random ethylene-propylene copolymer MFR (g/10min) 24.0 23.3 C2 content (wt%) 2.0 2.8 XCS (wt%) 7.5 nm Amount (wt%) 100 98 95 100 98 Ethylene-based plastomer Amount (wt%) 0 2 5 0 2 MI2 (g/10min) L3 Density (kg/m3) 902 Additives added during blending Millad 3988 (ppm) 1800 Irganox 1010 (ppm) 500 Irgafos PEPQ (ppm) 500 Ca Stearate (ppm) 1000 Composition MFR (g/10min) 21.0 21.3 19.6 21.5 20.4 19.9 Flexural modulus (MPa) 1210 1180 1133 1051 1029 Tm ( C) 151.5 151.6 151.4 148.6 148.3 -- 148.5 Tc ( C) 122.6 122.3 122.4 119.6 119.7 -- 119.7 Haze (%) 14.9 14.9 16.6 13.2 14.1 15.1 Resilience (J/mm) 7.7 10.56 11.8 12.25 11.67 12.27 nm = not measured A comparison of comparative Example CE1 (which contains no plastomer) with Examples 2 and 3 shows that the pure copolymer has relatively poor resilience.
Resilience is typically improved by increasing the comonomer content, but that reduces the crystallisation temperature and rigidity. However it can be seen that inventive Examples 2 and 3 have much better resilience, but still have essentially the same crystallisation temperature and similar flexural modulus.
However in Examples CE4-CE6 no such improvement in resilience is observed upon addition of the plastomer, indicating that there is an optimum level of comonomer in the random copolymer.
Examples labelled "CE" below are comparative examples.
Random ethylene-propylene copolymer MFR (g/10min) 24.0 23.3 C2 content (wt%) 2.0 2.8 XCS (wt%) 7.5 nm Amount (wt%) 100 98 95 100 98 Ethylene-based plastomer Amount (wt%) 0 2 5 0 2 MI2 (g/10min) L3 Density (kg/m3) 902 Additives added during blending Millad 3988 (ppm) 1800 Irganox 1010 (ppm) 500 Irgafos PEPQ (ppm) 500 Ca Stearate (ppm) 1000 Composition MFR (g/10min) 21.0 21.3 19.6 21.5 20.4 19.9 Flexural modulus (MPa) 1210 1180 1133 1051 1029 Tm ( C) 151.5 151.6 151.4 148.6 148.3 -- 148.5 Tc ( C) 122.6 122.3 122.4 119.6 119.7 -- 119.7 Haze (%) 14.9 14.9 16.6 13.2 14.1 15.1 Resilience (J/mm) 7.7 10.56 11.8 12.25 11.67 12.27 nm = not measured A comparison of comparative Example CE1 (which contains no plastomer) with Examples 2 and 3 shows that the pure copolymer has relatively poor resilience.
Resilience is typically improved by increasing the comonomer content, but that reduces the crystallisation temperature and rigidity. However it can be seen that inventive Examples 2 and 3 have much better resilience, but still have essentially the same crystallisation temperature and similar flexural modulus.
However in Examples CE4-CE6 no such improvement in resilience is observed upon addition of the plastomer, indicating that there is an optimum level of comonomer in the random copolymer.
11 Random ethylene-propylene copolymer MFR (g/10min) 24.0 23.3 20.6 C2 content (wt%) 2.0 2.8 3.0 XCS (wt%) 7.5 nm nm Amount (wt%) 100 98 95 100 98 95 Ethylene-based plastomer Amount (wt%) 0 2 5 0 2 5 0 2 ML (g/10min) 1.3 Density (kg/m3) 902 Additives added during blending Irgafos 168 (ppm) 500 Irganox 1010 (ppm) 500 DHT-4A (ppm) 400 Composition MFR (g/10min) 23 21.8 19.7 20.8 20.5 18.9 18.8 18.3 Flexural modulus (MPa) 1070 1044 1013 941 926 915 856 850 840 Tm ( C) 147.9 147.4 147.8 144.3 144.1 144.0 142.2 142.4 141.9 Tc ( C) 110.3 108.5 109.9 106.9 106.3 105.4 104.9 103.7 103.4 Haze (%) 43 43 41 41 41 40 39 Resilience (J/mm) 3.5 9.6 12 11.8 13.1 14.1 11.9 14.7 13.7 nm = not measured Unlike the compositions of Table 1, those of Table 2 do not contain a nucleating agent. It can be seen that in the absence of a nucleating agent the blend has, as expected, a higher haze value and higher crystallisation temperature, but a comparison of Examples 8 and 9 with CE7 shows an improvement in resilience. Comparative Examples CE11 -CE15 show that at higher ethylene content of the random propylene copolymer the crystallisation temperature and the flexural modulus is low.
Claims (16)
1. Composition comprising a blend of 90 - 99wt%, based on the blend, of a random propylene copolymer having an melt flow rate (MFR 230 C/2.16kg) of 15 - 40 g/lOmin and containing 1.5 ¨ 2.5wt%
ethylene, and 1 - 10 wt%, based on the blend, of an ethylene based plastomer having a density of 860 - 915 kg/m3 and an MI2 (190 C/2.16kg) of 0.5 to 25 g/10 min.
ethylene, and 1 - 10 wt%, based on the blend, of an ethylene based plastomer having a density of 860 - 915 kg/m3 and an MI2 (190 C/2.16kg) of 0.5 to 25 g/10 min.
2. Composition according to claim 1, which comprises 92 ¨ 98 wt%, preferably 93 - 97wt%, based on the blend, of the random propylene copolymer and 2 - 8 wt%, preferably 3 - 7wt%, based on the blend, of the plastomer.
3. Composition according to claim 2 which comprises 94 ¨ 96 wt% of the random propylene copolymer and 4 - 6wt% of the plastomer.
4. Composition according to any preceding claim, which has an MFR of 15 to g/10 min, preferably 17 to 33 g/10 min, and more preferably 19 to 29 g/10 min.
5. Composition according to any preceding claim which has a flexural modulus of 700 ¨ 1300 MI3a, preferably 800-1200 IVII3a and more preferably 900-1100 IVII3a.
6. Composition according to any preceding claim, wherein the ethylene based plastomer has a density in the range 870 - 910 kg/m3, preferably 890 - 910 kg/m3 and more preferably 898 - 905 kg/m3.
7. Composition according to any preceding claim, wherein the ethylene based plastomer has an MI2 (ISO 1133; 190 C; 2.16kg) in the range 0.5 - 5 g/10 min, preferably 0.5 ¨ 3.0 g/10 min, and more preferably 0.3 ¨ 2.5 g/min and still more preferably 1.0 ¨ 1.6 g/10min.
8. Composition according to any preceding claim, in which the random propylene copolymer has an MFR of 15 to 40 g/10min and an XCS content in the range 3 ¨
wt%, and the ethylene-based plastomer has a density in the range 898 - 905 kg/m3 and an M12 in the range of 0.5 - 3.0 g/min, preferably 0.3 ¨ 2.5 g/10min and more preferably 1.0 to 1.6 g/10min.
wt%, and the ethylene-based plastomer has a density in the range 898 - 905 kg/m3 and an M12 in the range of 0.5 - 3.0 g/min, preferably 0.3 ¨ 2.5 g/10min and more preferably 1.0 to 1.6 g/10min.
9. Composition according to any preceding claim, wherein the random propylene compolymer has an XCS content of 3 ¨ lOwt%, preferably 4 ¨ 9wt%.
10. Composition according to any preceding claim, wherein the random propylene compolymer has an MFR of 20 to 30 g/lOmin, preferably 22 to 28 g/lOmin.
11. Composition according to any preceding claim, wherein the random propylene compolymer contains at least one a-nucleating agent.
12. Composition according to any preceding claim, wherein the ethylene based plastomer is a copolymer of ethylene and a C3 - Cio alpha-olefin, preferably one of 1-propylene, 1-butene, 1-hexene and 1-octene, preferably 1-butene or 1-hexene, and most preferably 1-hexene.
13. Composition according to any preceding claim, wherein the comonomer content of the ethylene based plastomer is 4 to 7 mol%, preferably 4.5 to 6.5 mol% and most preferably 5.0 to 6.0 mol%.
14. Composition according to any preceding claim, wherein the ethylene based plastomer has a molecular weight distribution (Mw/Mn) in the range 3 to 5, preferably 3.2 to 4.5 and more preferably 3.4 to 4.5.
15. Composition according to any preceding claim, wherein the ethylene based plastomer has a glass transition temperature Tg (measured with DMTA according to ISO
6721-7) of below -25 C, preferably below -30 C, more preferably below -35 C.
6721-7) of below -25 C, preferably below -30 C, more preferably below -35 C.
16. Article, preferably a syringe barrel, comprising a composition as defined in any preceding claim.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP20216031.3 | 2020-12-21 | ||
| EP20216031 | 2020-12-21 | ||
| PCT/EP2021/086310 WO2022136131A1 (en) | 2020-12-21 | 2021-12-16 | Polypropylene blend |
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| CA3202882A1 true CA3202882A1 (en) | 2022-06-30 |
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| CA3202882A Pending CA3202882A1 (en) | 2020-12-21 | 2021-12-16 | Polypropylene blend |
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| US (1) | US20240043673A1 (en) |
| EP (1) | EP4263706B1 (en) |
| CA (1) | CA3202882A1 (en) |
| WO (1) | WO2022136131A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DZ520A1 (en) | 1982-03-24 | 2004-09-13 | Union Carbide Corp | Improved process for increasing the space-time yield of an exothermic polymerization reaction in a fluidized bed. |
| ZA943399B (en) | 1993-05-20 | 1995-11-17 | Bp Chem Int Ltd | Polymerisation process |
| EP0735089B1 (en) | 1995-03-31 | 2004-09-22 | Basell North America Inc. | Polyolefin compositions resistant to high energy radiation, and articles produced therefrom |
| WO1997008238A1 (en) | 1995-08-29 | 1997-03-06 | Exxon Chemical Patents Inc. | Radiation tolerant polypropylene and its useful articles |
| GB0020080D0 (en) | 2000-08-15 | 2000-10-04 | Borealis Tech Oy | Injection moulding |
| EP3031849B1 (en) | 2014-12-12 | 2018-10-24 | Borealis AG | Polypropylene films with improved optics and mechanical properties |
| GB201510293D0 (en) | 2015-06-12 | 2015-07-29 | Polyolefin Company Singapore Pte The Ltd | Moulded article from polypropylene composition |
| US10676550B2 (en) | 2015-07-09 | 2020-06-09 | Ineos Europe Ag | Copolymers and films thereof |
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2021
- 2021-12-16 CA CA3202882A patent/CA3202882A1/en active Pending
- 2021-12-16 EP EP21839512.7A patent/EP4263706B1/en active Active
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