WO2022110036A1 - Mélange-maître d'epdm pour compositions de polypropylène - Google Patents

Mélange-maître d'epdm pour compositions de polypropylène Download PDF

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Publication number
WO2022110036A1
WO2022110036A1 PCT/CN2020/132319 CN2020132319W WO2022110036A1 WO 2022110036 A1 WO2022110036 A1 WO 2022110036A1 CN 2020132319 W CN2020132319 W CN 2020132319W WO 2022110036 A1 WO2022110036 A1 WO 2022110036A1
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range
propylene
ethylene
copolymer
elastomeric
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PCT/CN2020/132319
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English (en)
Inventor
Ning Sun
Shengquan ZHU
Feild SHEN
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Borouge Compounding Shanghai Co., Ltd.
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Priority to CN202080107132.8A priority Critical patent/CN117980397A/zh
Priority to PCT/CN2020/132319 priority patent/WO2022110036A1/fr
Publication of WO2022110036A1 publication Critical patent/WO2022110036A1/fr

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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—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • 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
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • 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
    • C08L2207/02—Heterophasic composition

Definitions

  • EPDM ethylene-propylene-diene monomer rubbers
  • the present invention is based on the finding that a masterbatch incorporating both an elastomeric ethylene copolymer and an EPDM rubber within a polypropylene results in improved EPDM dispersion within the masterbatch, the master batch in turn aiding with the dispersion of EPDM within polypropylene compositions to which the masterbatch has been added. This effect is in addition to the avoidance of tiger stripe formation, which is suppressed by the presence of the EPDM, regardless of the fact that the composition comprises an elastomeric ethylene copolymer.
  • MB masterbatch composition
  • the individual contents of the polypropylene (PP) , the ethylene-propylene-diene monomer rubber (EPDM) and the elastomeric ethylene copolymer (EC) add up to at least 90 wt. -%, more preferably at least 95 wt. -%, most preferably at least 98 wt. -%, relative to the total weight of the masterbatch composition (MB) .
  • polypropylene is a propylene homopolymer or propylene copolymer, preferably a propylene copolymer.
  • the propylene copolymer is a propylene random copolymer or a propylene block copolymer, more preferably a propylene block copolymer.
  • the propylene block copolymer is preferably a heterophasic propylene copolymer.
  • polypropylene is a heterophasic propylene copolymer (HECO) , more preferably a heterophasic propylene-ethylene copolymer, which comprises:
  • heterophasic propylene copolymer HECO
  • heterophasic propylene-ethylene copolymer preferably has one or more, more preferably all, of the following properties:
  • melt flow rate (MFR 2 ) , measured according to ISO 1133 at 230 °C and 2.16 kg, in the range from 0.5 to 100 g/10 min, most preferably in the range from 1.0 to 80 g/10 min;
  • XCS xylene cold solubles
  • a total comonomer content more preferably a total ethylene (C2) content, in the range from 5.0 to 30.0 wt. -%, preferably in the range from 5.5 to 25.0 wt. -%, most preferably in the range from 6.0 to 20.0 wt. -%;
  • a comonomer content of the xylene cold soluble fraction more preferably an ethylene content of the xylene cold soluble fraction (C2 (XCS) ) , in the range from 10 to 50 wt. -%, preferably in the range from 15 to 45 wt. -%, most preferably in the range from 20 to 40 wt. -%; and
  • the crystalline propylene homopolymer matrix (M) of the heterophasic propylene copolymer (HECO) preferably the heterophasic propylene-ethylene copolymer
  • MFR 2 melt flow rate
  • the elastomeric ethylene copolymer (EC) is a copolymer of ethylene and one or more comonomers selected from C5 to C12 alpha olefins.
  • the elastomeric ethylene copolymer (EC) has one or more, preferably all, of the following properties:
  • melt flow rate (MFR 2 ) , measured according to ISO 1133 at 190 °C and 2.16 kg, in the range from 0.3 to 40 g/10 min, more preferably in the range from 0.5 to 35 g/10 min;
  • a density measured according to ISO 1183-187, in the range from 860 to 880 g/cm 3 , preferably in the range from 865 to 875 g/cm 3 , most preferably in the range from 867 to 871 g/cm 3 ;
  • a melting temperature measured according to ISO 11357, is in the range from 30 to 120 °C, more preferably in the range from 50 to 100 °C, most preferably in the range from 60 to 80 °C.
  • the ethylene-propylene-diene monomer rubber is a terpolymer of ethylene, propylene and ethylidene norbornene (ENB) , preferably having one or more of, preferably all of, the following properties:
  • a Mooney viscosity M L (1+4) measured according to ASTM D1646 at 125 °C, in the range from 40 to 100 MU, preferably in the range from 60 to 95 MU, most preferably in the range from 75 to 90 MU;
  • an ethylidene norbornene content in the range from 1.0 to 10.0 wt. -%, preferably 2.0 to 8.0 wt. -%, more preferably in the range from 3.0 to 7.0 wt. -%; and
  • a density measured according to ISO 1183-187, in the range from 0.80 to 0.96 g/cm 3 , preferably in the range from 0.83 to 0.93 g/cm 3 , most preferably in the range from 0.86 to 0.90 g/cm 3 .
  • the ratio of ethylene-propylene-diene monomer rubber (EPDM) to elastomeric ethylene copolymer (EC) is in the range from 1.0: 1.0 to 5.0: 1.0, more preferably in the range from 1.3: 1.0 to 4.0: 1.0, most preferably in the range from 1.5: 1.0 to 3.0: 1.0.
  • the masterbatch composition (MB) has a melt flow rate (MFR 2 ) , measured according to ISO 1133 at 230 °C and 2.16 kg, in the range from 0.05 to 5.0 g/10 min, preferably in the range from 0.10 to 3.0 g/10 min, most preferably in the range from 0.15 to 1.0 g/10 min.
  • the present invention is directed to a use of an elastomeric ethylene copolymer (EC) for improving the dispersion of ethylene-propylene-diene monomer rubber (EPDM) in a composition comprising polypropylene (PP) and ethylene diene monomer rubber (EPDM) relative to an analogous composition without the elastomeric ethylene copolymer (EC) .
  • EC elastomeric ethylene copolymer
  • the polypropylene (PP) is the polypropylene (PP)
  • the main component of the masterbatch composition is the polypropylene (PP) .
  • This component serves as the carrier polymer of the masterbatch composition (MB) , for introducing the other components into a polypropylene composition.
  • the polypropylene (PP or PP1) is, for example, a propylene homopolymer, a propylene random copolymer, a propylene block copolymer or a heterophasic propylene copolymer. Consequently, it is preferred that, when the polypropylene (PP1) of the polypropylene composition is a heterophasic propylene copolymer, the polypropylene (PP) of the masterbatch composition (MB) is also a heterophasic propylene copolymer. Similarly, if the polypropylene (PP1) of the polypropylene composition is a propylene homopolymer, the polypropylene (PP) of the masterbatch composition (MB) should also be a propylene homopolymer.
  • the polypropylene (PP) of the masterbatch composition (MB) may be a propylene homopolymer, or a propylene copolymer, more preferably a propylene copolymer.
  • the propylene copolymer may be a propylene random copolymer or a propylene block copolymer, more preferably a propylene block copolymer, most preferably a heterophasic propylene copolymer.
  • the polypropylene (PP) of the masterbatch composition (MB) is a propylene copolymer, preferably a propylene block copolymer, more preferably a heterophasic propylene copolymer (HECO) , even more preferably a heterophasic propylene-ethylene copolymer.
  • a propylene copolymer preferably a propylene block copolymer, more preferably a heterophasic propylene copolymer (HECO) , even more preferably a heterophasic propylene-ethylene copolymer.
  • HECO heterophasic propylene copolymer
  • the propylene copolymer preferably the propylene block copolymer, more preferably the heterophasic propylene copolymer (HECO) of the masterbatch composition (MB) comprises comonomer (s) selected from the group consisting of ethylene and alpha olefins containing 4 to 12 carbon atoms, more preferably from the group consisting of ethylene, butene, hexene and octene, yet more preferably selected from ethylene or butene, most preferably ethylene. It is particularly preferred that the only comonomer present is ethylene.
  • the polypropylene (PP) more preferably the propylene copolymer, yet more preferably the propylene block copolymer, still more preferably the heterophasic propylene copolymer (HECO) , even more preferably the heterophasic propylene-ethylene copolymer, has a melt flow rate (MFR 2 ) , measured according to ISO 1133 at 230 °C and 2.16 kg, in the range from 0.2 to 120 g/10 min, more preferably in the range from 0.5 to 100 g/10 min, most preferably in the range from 1.0 to 80 g/10 min.
  • MFR 2 melt flow rate
  • the comonomer content is preferably in the range from 0.1 to 5.0 wt. -%, more preferably in the range from 0.2 to 4.5 wt. -%, most preferably in the range from 0.5 to 4.0 wt. -%, relative to the total weight of the propylene random copolymer.
  • the comonomer content is preferably in the range from 5.0 to 30.0 wt. -%, more preferably in the range from 5.5 to 25.0 wt. -%, most preferably in the range from 6.0 to 20.0 wt. -%, relative to the total weight of the propylene block copolymer.
  • heterophasic propylene copolymer HECO
  • heterophasic propylene-ethylene copolymer XCS
  • XCS xylene cold solubles
  • heterophasic propylene copolymer HECO
  • the heterophasic propylene-ethylene copolymer has a total comonomer content, more preferably a total ethylene (C2) content, in the range from 5.0 to 30.0 wt. -%, preferably in the range from 5.5 to 25.0 wt. -%, most preferably in the range from 6.0 to 20.0 wt. -%.
  • the heterophasic propylene copolymer HECO
  • the heterophasic propylene-ethylene copolymer has a comonomer content of the xylene cold soluble fraction, more preferably an ethylene content of the xylene cold soluble fraction (C2 (XCS) ) , in the range from 10 to 50 wt.-%, preferably in the range from 15 to 45 wt. -%, most preferably in the range from 20 to 40 wt. -%.
  • heterophasic propylene copolymer HECO
  • heterophasic propylene-ethylene copolymer has an intrinsic viscosity of the xylene cold soluble fraction (IV (XCS) ) in the range from 1.0 to 4.0 dl/g, preferably in the range from 1.5 to 3.5 dl/g, most preferably in the range from 2.0 to 3.0 dl/g.
  • the crystalline propylene homopolymer matrix (M) has a melt flow rate (MFR 2 ) , measured according to ISO 1133 at 230°C and 2.16 kg, in the range from 10 to 150 g/10 min, more preferably in the range from 20 to 120 g/10 min, most preferably in the range from 30 to 100 g/10 min.
  • MFR 2 melt flow rate
  • heterophasic propylene copolymer HECO
  • the heterophasic propylene copolymer has a flexural modulus, measured according to according to ISO 178 on 80x10x4 mm 3 test bars injection molded in line with EN ISO 1873-2, in the range from 700 to 2000 MPa, more preferably in the range from 800 to 1500 MPa, most preferably in the range from 900 to 1200 MPa.
  • the heterophasic propylene copolymer (HECO) , more preferably the heterophasic propylene-ethylene copolymer, has a Charpy notched impact strength, measured at 23 °C according to ISO 179-1 1eA using injection-molded bar test specimens of 80x10x4 mm 3 prepared in accordance with ISO 1873-2: 2007, in the range from 30 to 120 kJ/m 2 , more preferably in the range from 40 to 100 kJ/m 2 , most preferably in the range from 50 to 80 kJ/m 2 .
  • HECO heterophasic propylene copolymer
  • the heterophasic propylene copolymer (HECO) , more preferably the heterophasic propylene-ethylene copolymer, has a Charpy notched impact strength, measured at -20 °C according to ISO 179-1 1eA using injection-molded bar test specimens of 80x10x4 mm 3 prepared in accordance with ISO 1873-2: 2007, in the range from 5.0 to 30.0 kJ/m 2 , more preferably in the range from 7.0 to 20.0 kJ/m 2 , most preferably in the range from 9.0 to 15.0 kJ/m 2 .
  • HECO heterophasic propylene copolymer
  • the polypropylene (PP) more preferably the propylene copolymer, yet more preferably the propylene block copolymer, still more preferably the heterophasic propylene copolymer (HECO) , even more preferably the heterophasic propylene-ethylene copolymer, preferably comprises a polymeric nucleating agent.
  • PP polypropylene
  • HECO heterophasic propylene copolymer
  • a preferred example of such a polymeric nucleating agent is a vinyl polymer, such as a vinyl polymer derived from monomers of the formula
  • R 1 and R 2 together with the carbon atom they are attached to, form an optionally substituted saturated or unsaturated or aromatic ring or a fused ring system, wherein the ring or fused ring moiety contains four to 20 carbon atoms, preferably 5 to 12 membered saturated or unsaturated or aromatic ring or a fused ring system or independently represent a linear or branched C4-C30 alkane, C4-C20 cycloalkane or C4-C20 aromatic ring.
  • R 1 and R 2 together with the C-atom wherein they are attached to, form a five-or six-membered saturated or unsaturated or aromatic ring or independently represent a lower alkyl group comprising from 1 to 4 carbon atoms.
  • Preferred vinyl compounds for the preparation of a polymeric nucleating agent to be used in accordance with the present invention are in particular vinyl cycloalkanes, in particular vinyl cyclohexane (VCH) , vinyl cyclopentane, and vinyl-2-methyl cyclohexane, 3-methyl-1-butene, 3-ethyl-1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene or mixtures thereof.
  • the vinyl polymer is a vinyl cycloalkane polymer, preferably selected from vinyl cyclohexane (VCH) , vinyl cyclopentane and vinyl-2-methyl cyclohexane, with vinyl cyclohexane polymer being a particularly preferred embodiment.
  • VCH vinyl cyclohexane
  • vinyl cyclopentane vinyl cyclopentane
  • vinyl-2-methyl cyclohexane vinyl cyclohexane
  • the vinyl polymer of the polymeric nucleating agent is a homopolymer, most preferably a vinyl cyclohexane homopolymer.
  • the polypropylene (PP) more preferably the propylene copolymer, yet more preferably the propylene block copolymer, still more preferably the heterophasic propylene copolymer (HECO) , even more preferably the heterophasic propylene-ethylene copolymer, of the present invention may either be synthesized or selected from commercially available polypropylenes. It is particularly preferred that the polypropylene (PP) is a heterophasic propylene copolymer (HECO) prepared according to the following process.
  • HECO heterophasic propylene copolymer
  • heterophasic propylene copolymer (HECO) , more preferably the heterophasic propylene-ethylene copolymer, comprised in the composition according to this invention is preferably produced in a sequential polymerization process in the presence of a Ziegler-Natta catalyst, more preferably in the presence of a catalyst (system) as defined below.
  • heterophasic propylene copolymer is reactor made, preferably has been produced in a sequential polymerization process, wherein the crystalline matrix (M) has been produced in at least one reactor, preferably in two reactors, and subsequently the elastomeric propylene-ethylene copolymer (E) has been produced in at least two further reactors, preferably in two further reactors, wherein a first elastomeric propylene-ethylene copolymer fraction (E1) has been produced in one of the two further reactors and the second elastomeric propylene-ethylene copolymer fraction (E2) has been produced in the other one of the two further reactors. It is especially preferred that first the first elastomeric propylene-ethylene copolymer fraction (E1) is produced and subsequently the second elastomeric propylene-ethylene copolymer fraction (E2) .
  • polymerization reactor shall indicate that the main polymerization takes place. Thus in case the process consists of four polymerization reactors, this definition does not exclude the option that the overall process comprises for instance a pre-polymerization step in a pre-polymerization reactor.
  • consist of is only a closing formulation in view of the main polymerization reactors, i.e. does not exclude prepolymerisation reactors prior to said main polymerization reactors.
  • said process comprises the steps of
  • step (d1) transferring the crystalline propylene homopolymer matrix (M) of step (c1) into a third reactor (R3) ,
  • step (e1) polymerizing propylene and ethylene in the third reactor (R3) in the presence of the crystalline propylene homopolymer matrix (M) obtained in step (c1) , obtaining thereby the first elastomeric propylene-ethylene copolymer fraction (E1) , said crystalline propylene homopolymer matrix (M) and said first elastomeric propylene-ethylene copolymer fraction (E1) forming a mixture (M1) ,
  • xylene cold soluble (XCS) of said mixture (M1) is regarded as the first elastomeric propylene-ethylene copolymer fraction (E1) .
  • heterophasic propylene copolymer HECO
  • the heterophasic propylene copolymer HECO
  • the crystalline matrix (M) the first propylene homopolymer (h-PP1)
  • the second propylene homopolymer (h-PP2) first elastomeric propylene-ethylene copolymer fraction (E1)
  • E2 second elastomeric propylene-ethylene copolymer fraction
  • the first reactor (R1) is preferably a slurry reactor (SR) and can be any continuous or simple stirred batch tank reactor or loop reactor operating in bulk or slurry.
  • Bulk means a polymerization in a reaction medium that comprises of at least 60 % (w/w) monomer.
  • the slurry reactor (SR) is preferably a (bulk) loop reactor (LR) .
  • the second reactor (R2) , the third reactor (R3) and the fourth reactor (R4) are preferably gas phase reactors (GPR) .
  • gas phase reactors (GPR) can be any mechanically mixed or fluid bed reactors.
  • the gas phase reactors (GPR) comprise a mechanically agitated fluid bed reactor with gas velocities of at least 0.2 m/sec.
  • the gas phase reactor is a fluidized bed type reactor preferably with a mechanical stirrer.
  • the first reactor (R1) is a slurry reactor (SR) , like loop reactor (LR)
  • the second reactor (R2) , the third reactor (R3) and the fourth reactor (R4) are gas phase reactors (GPR)
  • at least four, preferably four polymerization reactors namely a slurry reactor (SR) , like loop reactor (LR) , a first gas phase reactor (GPR-1) , a second gas phase reactor (GPR-2) and a third gas phase reactor (GPR-3) connected in series are used. If needed prior to the slurry reactor (SR) a pre-polymerization reactor is placed.
  • a preferred multistage process is a “loop-gas phase” -process, such as developed by Borealis A/S, Denmark (known as technology) described e.g. in patent literature, such as in EP 0 887 379, WO 92/12182 WO 2004/000899, WO 2004/111095, WO 99/24478, WO 99/24479 or in WO 00/68315.
  • a further suitable slurry-gas phase process is the process of Basell described e.g. in figure 20 of the paper by Galli and Vecello, Prog. Polym. Sci. 26 (2001) 1287-1336.
  • the conditions for the first reactor (R1) i.e. the slurry reactor (SR) , like a loop reactor (LR) , of step (a1) may be as follows:
  • the temperature is within the range of 40 °C to 110 °C, preferably between 60 °C and 100 °C, like 68 to 95 °C,
  • the pressure is within the range of 20 bar to 80 bar, preferably between 40 bar to 70 bar,
  • reaction mixture from step (a1) containing preferably the first propylene copolymer fraction (PP1) is transferred to the second reactor (R2) , i.e. the first gas phase reactor (GPR-1) , whereby the conditions are preferably as follows:
  • the temperature is within the range of 50 °C to 130 °C, preferably between 60 °C and 100 °C,
  • the pressure is within the range of 5 bar to 50 bar, preferably between 15 bar to 35 bar,
  • the polymerization may be effected in a known manner under supercritical conditions in the first reactor (R1) , i.e. in the slurry reactor (SR) , like in the loop reactor (LR) , and/or as a condensed mode in the gas phase reactor (GPR-1) .
  • R1 first reactor
  • SR slurry reactor
  • LR loop reactor
  • GPR-1 gas phase reactor
  • gas phase reactors (GPR-2) and (GPR-3) of steps (e1) and (g1) are preferably also operated within the above conditions, preferably with the exception that in gas phase reactors (GPR-2) and (GPR-3)
  • the pressure is within the range of 5 bar to 50 bar, preferably between 10 bar to 30 bar.
  • the residence time can vary in the above different reactors.
  • the residence time the first reactor (R1) i.e. the slurry reactor (SR) , like a loop reactor (LR)
  • the residence time in the gas phase reactors (GPR1 to GPR3) will generally be 0.2 to 6.0 hours, like 0.5 to 4.0 hours.
  • a well-known prepolymerization step may precede before the actual polymerization in the reactors (R1) to (R4) .
  • the prepolymerisation step is typically conducted at a temperature of 0 to 50 °C, preferably from 10 to 45 °C, and more preferably from 15 to 40 °C.
  • heterophasic propylene copolymer HECO
  • heterophasic propylene-ethylene copolymer HECO
  • process according to the present invention includes the following process steps:
  • a vinyl compound as defined above preferably vinyl cyclohexane (VCH)
  • VCH vinyl cyclohexane
  • the weight ratio (g) of the polymer of the vinyl compound to the solid catalyst system is up to 5 (5: 1) , preferably up to 3 (3: 1) most preferably is from 0.5 (1: 2) to 2 (2: 1)
  • the obtained modified catalyst system is fed to polymerization step (a1) of the process for producing the heterophasic propylene copolymer (HECO) , more preferably the heterophasic propylene-ethylene copolymer.
  • HECO heterophasic propylene copolymer
  • the used catalyst is preferably a Ziegler-Natta catalyst system and even more preferred a modified Ziegler Natta catalyst system as defined in more detail below.
  • Such a Ziegler-Natta catalyst system typically comprises a solid catalyst component, preferably a solid transition metal component, and a cocatalyst, and optionally an external donor.
  • the solid catalyst component comprises most preferably a magnesium halide, a titanium halide and an internal electron donor.
  • Such catalysts are well known in the art. Examples of such solid catalyst components are disclosed, among others, in WO 87/07620, WO 92/21705, WO 93/11165, WO 93/11166, WO 93/19100, WO 97/36939, WO 98/12234, WO 99/33842.
  • Suitable electron donors are, among others, esters of carboxylic acids, like phthalates, citraconates, and succinates. Also oxygen-or nitrogen-containing silicon compounds may be used. Examples of suitable compounds are shown in WO 92/19659, WO 92/19653, WO 92/19658, US 4,347,160, US 4,382,019, US 4,435,550, US 4,465,782, US 4,473,660, US 4,530,912 and US 4,560,671.
  • said solid catalyst components are preferably used in combination with well known external electron donors, including without limiting to, ethers, ketones, amines, alcohols, phenols, phosphines and silanes, for example organosilane compounds containing Si-OCOR, Si-OR, or Si-NR 2 bonds, having silicon as the central atom, and R is an alkyl, alkenyl, aryl, arylalkyl or cycloalkyl with 1-20 carbon atoms; and well known cocatalysts, which preferably comprise an aluminium alkyl compound as known in the art, to polymerise the propylene copolymer.
  • well known external electron donors including without limiting to, ethers, ketones, amines, alcohols, phenols, phosphines and silanes, for example organosilane compounds containing Si-OCOR, Si-OR, or Si-NR 2 bonds, having silicon as the central atom, and R is an alkyl, alkenyl,
  • the amount of polymeric nucleating agent present in the heterophasic propylene copolymer (HECO) , more preferably the heterophasic propylene-ethylene copolymer, is preferably not more than 500 ppm, more preferably is 0.025 to 200 ppm, still more preferably is 1 to 100 ppm, and most preferably is 5 to 100 ppm, based on the heterophasic propylene copolymer (HECO) , more preferably the heterophasic propylene-ethylene copolymer, and the nucleating agent, preferably based on the total weight of the heterophasic propylene copolymer (HECO) , more preferably the heterophasic propylene-ethylene copolymer, including all additives.
  • the polypropylene (PP) is other than a heterophasic propylene copolymer, and comprises a polymeric nucleating agent as described above or below, it is preferred that the polymer nucleating agent is formed and introduced during the polymerization process in the same manner as in the preparation process for the heterophasic propylene copolymer as described above.
  • EPDM ethylene-propylene-diene monomer rubber
  • EPDM ethylene-propylene-diene monomer rubber
  • EPDM ethylene-propylene-diene monomer rubber
  • ENB ethylidene norbornene
  • the ethylene-propylene-diene monomer rubber EPDM
  • EPDM ethylene-propylene-diene monomer rubber
  • the terpolymer of ethylene, propylene and ethylidene norbornene ENB
  • Mooney viscosity M L (1+4) measured according to ASTM D1646 at 125 °C, in the range from 40 to 100 MU, preferably in the range from 60 to 95 MU, most preferably in the range from 75 to 90 MU.
  • the ethylene-propylene-diene monomer rubber EPDM
  • EPDM ethylene-propylene-diene monomer rubber
  • ENB ethylidene norbornene
  • C2 ethylene content in the range from 50 to 90 wt. -%, preferably in the range from 55 to 85 wt. -%most preferably in the range from 60 to 80 wt. -%.
  • the ethylene-propylene-diene monomer rubber EPDM
  • EPDM ethylene-propylene-diene monomer rubber
  • the terpolymer of ethylene, propylene and ethylidene norbornene ENB
  • ENB ethylidene norbornene
  • the diene content more preferably an ethylidene norbornene content (ENB) , in the range from 1.0 to 10.0 %, preferably in the range from 2.0 to 8.0 %, most preferably in the range from 3.0 to 7.0 %.
  • the ethylene-propylene-diene monomer rubber EPDM
  • EPDM ethylene-propylene-diene monomer rubber
  • the terpolymer of ethylene, propylene and ethylidene norbornene ENB
  • EPDM ethylene-propylene-diene monomer rubber
  • EMB ethylidene norbornene
  • the ethylene-propylene-diene monomer rubber (EPDM) more preferably the terpolymer of ethylene, propylene and ethylidene norbornene (ENB) , of the present invention may either be synthesized or selected from commercially available EPDM rubbers, such as Nordel TM IP 4785HM commercially available from Dow Chemical Company (Shanghai, China) .
  • Another essential component of the masterbatch composition is the elastomeric ethylene copolymer (EC) .
  • the elastomeric ethylene copolymer (EC) has a melt flow rate (MFR 2 ) , measured according to ISO 1133 at 190°C and 2.16 kg, in the range from 0.1 to 45 g/10 min, more preferably in the range from 0.3 to 40 g/10 min, most preferably in the range from 0.5 to 35 g/10 min
  • the elastomeric ethylene copolymer (EC) has a density, measured according to ISO 1183-187, in the range from 860 to 880 g/cm 3 , preferably in the range from 865 to 875 g/cm 3 , most preferably in the range from 867 to 871 g/cm 3 .
  • the elastomeric ethylene copolymer (EC) has a melting temperature, measured according to ISO 11357, is in the range from 30 to 120 °C, more preferably in the range from 50 to 100 °C, most preferably in the range from 60 to 80 °C.
  • the elastomeric ethylene copolymer (EC) is a copolymer of ethylene and one or more comonomers selected from C5 to C12 alpha olefins, more preferably selected from C6 to C10 alpha olefins, most preferably the elastomeric ethylene copolymer (EC) is an ethylene-octene copolymer or an ethylene-hexene copolymer.
  • the comonomer content of the elastomeric ethylene copolymer (EC) is preferably in the range from 10 to 55 wt. -%, more preferably from 20 to 50 wt. -%, most preferably from 30 to 47 wt. -%, based on the total weight of the elastomeric ethylene copolymer (EC) .
  • the elastomeric ethylene copolymer (EC) is a random copolymer.
  • the masterbatch composition of the present invention comprises the polypropylene (PP) , the ethylene-propylene-diene monomer rubber (EPDM) , and the elastomeric ethylene copolymer (EC) , wherein the individual contents of the polypropylene (PP) , the ethylene-propylene-diene monomer rubber (EPDM) and the elastomeric ethylene copolymer (EC) add up to at least 90 wt. -%, more preferably at least 95 wt. -%, yet more preferably at least 98 wt. -%, most preferably 100 wt. -%, relative to the total weight of the masterbatch composition (MB) .
  • PP polypropylene
  • EPDM ethylene-propylene-diene monomer rubber
  • EC elastomeric ethylene copolymer
  • the masterbatch composition comprises:
  • the individual contents of the polypropylene (PP) , the ethylene-propylene-diene monomer rubber (EPDM) and the elastomeric ethylene copolymer (EC) add up to at least 90 wt. -%, more preferably at least 95 wt. -%, most preferably at least 98 wt. -%, relative to the total weight of the masterbatch composition (MB) .
  • the masterbatch composition consists of:
  • the polypropylene (PP) is present in the masterbatch composition (MB) in an amount of from 15 to 50 wt.-%, based on the total weight of the composition, more preferably in an amount of from 18 to 40 wt. -%, yet more preferably in an amount of from 20 to 35 wt. -%, based on the total weight of the composition.
  • the ethylene-propylene-diene monomer rubber (EPDM) is present in the masterbatch composition (MB) in an amount of from 30 to 70 wt. -%, based on the total weight of the composition, more preferably in an amount of from 35 to 65 wt. -%, yet more preferably in an amount of from 40 to 60 wt. -%, based on the total weight of the composition.
  • the elastomeric ethylene copolymer (EC) is present in the masterbatch composition (MB) in an amount of from 2 to 29 wt. -%, based on the total weight of the composition, more preferably in an amount of from 5 to 29 wt. -%, yet more preferably in an amount of from 10 to 25 wt. -%, based on the total weight of the composition.
  • the polyolefin composition comprises, alternatively consists of:
  • the polyolefin composition comprises, alternatively consists of:
  • the ratio of ethylene-propylene-diene monomer rubber (EPDM) to elastomeric ethylene copolymer (EC) in the masterbatch composition (MB) is in the range from 1.0: 1 to 5.0: 1, more preferably in the range from 1.3: 1 to 4.0: 1, most preferably in the range from 1.5: 1 to 3.0: 1
  • the masterbatch composition (PC) has a melt flow rate (MFR 2 ) , measured according to ISO 1133 at 230 °C and 2.16 kg, in the range from 0.05 to 5.0 g/10 min, more preferably in the range from 0.10 to 3.0 g/10 min, most preferably in the range from 0.15 to 1.0 g/10 min.
  • MFR 2 melt flow rate
  • the present invention is additionally directed to a process for the preparation of the masterbatch composition (MB) of the present invention, comprising the steps of:
  • PP polypropylene
  • EPDM ethylene-propylene-diene monomer rubber
  • EC elastomeric ethylene copolymer
  • a conventional compounding or blending apparatus e.g. a Banbury mixer, a 2-roll rubber mill, Buss-co-kneader or a twin-screw extruder. More preferably, mixing is accomplished in a co-rotating twin-screw extruder.
  • the polymer materials recovered from the extruder are usually in the form of pellets. These pellets may then be used as an EPDM masterbatch for the introduction of EPDM into other polypropylene compositions, in particular polypropylene compositions for forming molded articles.
  • the dispersion of the elastomeric EPDM phase within the inventive masterbatch composition (MB) is greatly improved due to the presence of elastomeric ethylene copolymer.
  • the masterbatch composition helps improve dispersion of said elastomeric EPDM phase in polypropylene compositions resulting from the addition of the masterbatch composition to a base polypropylene, relative to polypropylene compositions wherein EPDM has been added directly to the base polypropylene (i.e. not via a masterbatch) . Consequently, the polypropylene compositions resulting from the addition of the inventive masterbatch compositions to a base polypropylene can be compounded smoothly in a regular compounding process before being formed into molded articles, preferably injection molded articles.
  • the articles thus formed have improved impact properties and improved surface qualities (e.g. eliminated tiger stripes) relative to comparable articles that employ impact modifiers other than EPDM.
  • the present invention is further directed to a use of an elastomeric ethylene copolymer (EC) for improving the dispersion of ethylene-propylene-diene monomer rubber (EPDM) in a composition comprising polypropylene (PP) and ethylene diene monomer rubber (EPDM) relative to an analogous composition without the elastomeric ethylene copolymer (EC) .
  • EC elastomeric ethylene copolymer
  • Density is measured according to ISO 1183-187. Sample preparation is done by compression molding in accordance with ISO 1872-2: 2007.
  • MFR 2 The melt flow rate (MFR) is determined according to ISO 1133 and is indicated in g/10 min.
  • the MFR is an indication of the flowability, and hence the processability, of the polymer. The higher the melt flow rate, the lower the viscosity of the polymer.
  • the MFR 2 of polypropylene is determined at a temperature of 230 °C and a load of 2.16 kg.
  • the MFR 2 of elastomeric ethylene copolymers is determined at a temperature of 190°C and a load of 2.16 kg.
  • Melting temperature Tm The melting temperature is measured according to ISO 11357-3.
  • NMR nuclear-magnetic resonance
  • the NMR tube was further heated in a rotatory oven for at least 1 hour. Upon insertion into the magnet the tube was spun at 10 Hz.
  • This setup was chosen primarily for the high resolution and quantitatively needed for accurate ethylene content quantification. Standard single-pulse excitation was employed without NOE, using an optimised tip angle, 1 s recycle delay and a bi-level WALTZ16 decoupling scheme as described in Z. Zhou, R. Kuemmerle, X. Qiu, D. Redwine, R. Cong, A. Taha, D. Baugh, B. Winniford, J. Mag. Reson. 187 (2007) 225 and V. Busico, P.
  • the comonomer fraction was quantified using the method of W-J. Wang and S. Zhu, Macromolecules 2000, 33 1157, through integration of multiple signals across the whole spectral region in the 13 C ⁇ 1 H ⁇ spectra. This method was chosen for its robust nature and ability to account for the presence of regio-defects when needed. Integral regions were slightly adjusted to increase applicability across the whole range of encountered comonomer contents.
  • the mole percent comonomer incorporation was calculated from the mole fraction.
  • the weight percent comonomer incorporation was calculated from the weight fraction.
  • w (PP1) is the weight fraction [in wt. -%] of the first elastomeric propylene-ethylene copolymer fraction (E1) , e.g. the xylene cold soluble (XCS) fraction measured after the third reactor (e.g. comprising the matrix (M) and the first elastomeric fraction) ;
  • w (PP2) is the weight fraction [in wt. -%] of the second elastomeric propylene-ethylene copolymer fraction (E2) , i.e. of the amount of xylene cold soluble fraction (XCS) produced in the fourth reactor (e.g. the second elastomeric fraction produced in the fourth reactor) ;
  • C (PP1) is the comonomer content [in wt. -%] of the first elastomeric propylene-ethylene copolymer fraction (E1) , i.e. of the xylene cold soluble (XCS) fraction measured after the third reactor (e.g. comprising the matrix (M) and the first elastomeric fraction) ;
  • C (PP) is the comonomer content [in wt. -%] of the xylene soluble fraction of the final heterophasic propylene copolymer (HECO) ,
  • C (PP2) is the calculated comonomer content [in wt. -%] of the second elastomeric propylene-ethylene copolymer fraction (E2) .
  • Comonomer content in the elastomeric ethylene copolymer (EC) and the ethylene-propylene-diene monomer rubbers (EPDM) were measured in a known manner based on Fourier transform infrared spectroscopy (FTIR) calibrated with 13 C-NMR, using Nicolet Magna 550 IR spectrometer together with Nicolet Omnic FTIR software. Films having a thickness of about 250 ⁇ m were compression molded from the samples. Similar films were made from calibration samples having a known content of the comonomer. The comonomer content was determined from the spectrum from the wave number range of from 1430 to 1100 cm -1 . The absorbance is measured as the height of the peak by selecting the so-called short or long base line or both.
  • FTIR Fourier transform infrared spectroscopy
  • the short base line is drawn in about 1410 -1320 cm -1 through the minimum points and the long base line about between 1410 and 1220 cm -1 .
  • Calibrations need to be done specifically for each base line type. Also, the comonomer content of the unknown sample needs to be within the range of the comonomer contents of the calibration samples.
  • the xylene soluble fraction (XCS) at room temperature (XCS, wt. -%) : The amount of the polymer soluble in xylene is determined at 25 °C according to ISO 16152; first edition; 2005-07-01. The remaining part is the xylene cold insoluble (XCU) fraction.
  • the intrinsic viscosity (IV) is measured according to ISO 1628-1 (at 135 °C in decalin) .
  • Mooney viscosity is measured according to ASTM D1646 at 125 °C.
  • the Charpy impact test The Charpy notched impact strength (NIS) was measured according to ISO 179-1 eA at +23 °C and -20 °C, using injection-molded bar test specimens of 80x10x4 mm 3 prepared in accordance with ISO 1873-2: 2007.
  • Flexural Modulus The flexural modulus was determined in 3-point-bending at 23°C according to ISO 178 on 80x10x4 mm 3 test bars injection molded in line with EN ISO 1873-2.
  • SEM Microscopy A scanning electron microscope (Quanta 250 FEG of Field Electron and Ion Company (FEI, USA) is used to observe the dispersion of EPDM in the PP and elastomeric ethylene copolymer for each masterbatch.
  • the catalyst used in the polymerizations was a Ziegler-Natta catalyst from Borealis having Ti-content of 1.9 wt. -% (as described in EP 591 224) .
  • the catalyst was prepolymerized with vinyl-cyclohexane (VCH) as described in EP 1 028 984 and EP 1 183 307.
  • VCH vinyl-cyclohexane
  • the ratio of VCH to catalyst of 1: 1 was used in the preparation, thus the final Poly-VCH content was less than 100 ppm.
  • the catalyst described above was fed into prepolymerization reactor together with propylene and small amount of hydrogen (2.5 g/h) and ethylene (330 g/h) .
  • Triethylaluminium as a cocatalyst and dicyclopentyldimethoxysilane as a donor was used.
  • the aluminium to donor ratio was 7.5 mol/mol and aluminium to titanium ratio was 300 mol/mol.
  • Reactor was operated at a temperature of 30 °C and a pressure of 55 barg.
  • the subsequent polymerization has been effected under the following conditions.
  • the masterbatch compositions of Inventive examples IE1 to IE5 and comparative example CE1 were prepared based on the recipes indicated in Table 2 by compounding in a co-rotating twin-screw extruder under the conditions described in Table 3.
  • the extruder has 12 heating zones.
  • Table 3 Compounding conditions for comparative and inventive examples in twin-screw extruder
  • Figures 1-6 show scanning electron microscopy images of the microstructure of elastomer phase (EPDM together with elastomeric ethylene copolymer) in the masterbatch compositions of CE1 and IE1 to IE5 respectively.
  • the dispersion of the elastomeric phase comprising EPDM and ethylene copolymer (EC) , if present, within the masterbatch is uniformly improved for the inventive examples IE1 to IE5 over the comparative example, which has large, uneven EPDM inclusions (Fig. 1) .
  • the dispersion of the elastomeric phase improves, showing a more uniform distribution and smaller size of the dispersed elastomer particles, with this effect being most pronounced for IE3 (25 wt. -%of EC3) , with smaller effects observed for IE4 and IE5 (20 wt. -%and 15 wt. -%of EC3 respectively) , showing that the amount of EC present has an effect on the dispersion of the elastomeric phase.
  • inventive masterbatch IE3 is compounded with 94 wt. -%of a propylene homopolymer, with the resulting composition being used to form an injection molded article.
  • the resulting article exhibits far less tiger stipes on the surface than an analogous article that does not contain EDPM, having an elastomeric ethylene copolymer as the only impact modifier.

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  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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Abstract

L'invention concerne une composition de mélange-maître (MB) comprenant : a) de 15 à 50 % en poids de polypropylène (PP)) ayant un indice de fluage à chaud MFR 2 dans la plage de 0,2 à 120 g/10 minutes ; b) de 30 à 70 % en poids d'éthylène-propylène-diène monomère (EPDM) ; et c) de 2 à 29 % en poids d'un copolymère d'éthylène élastomère (EC) ayant un indice MFR 2 dans la plage de 0,1 à 45 g/10 minutes. Les teneurs individuelles en polypropylène (PP), en caoutchouc éthylène-propylène-diène monomère (EPDM) et en copolymère d'éthylène élastomère (EC) s'élèvent au moins à 90 % en poids.
PCT/CN2020/132319 2020-11-27 2020-11-27 Mélange-maître d'epdm pour compositions de polypropylène WO2022110036A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4822855A (en) * 1986-08-05 1989-04-18 Nippon Oil Company, Limited Thermoplastic elastomer compositions
US5374677A (en) * 1991-06-21 1994-12-20 Mitsubishi Petrochemical Company Limited Thermoplastic polymer composition
CN103910936A (zh) * 2014-04-02 2014-07-09 合肥杰事杰新材料股份有限公司 一种聚丙烯/三元乙丙橡胶复合材料及其制备方法
CN109810357A (zh) * 2017-11-20 2019-05-28 佛山市淼创科技有限公司 一种tpe塑料粒子

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4822855A (en) * 1986-08-05 1989-04-18 Nippon Oil Company, Limited Thermoplastic elastomer compositions
US5374677A (en) * 1991-06-21 1994-12-20 Mitsubishi Petrochemical Company Limited Thermoplastic polymer composition
CN103910936A (zh) * 2014-04-02 2014-07-09 合肥杰事杰新材料股份有限公司 一种聚丙烯/三元乙丙橡胶复合材料及其制备方法
CN109810357A (zh) * 2017-11-20 2019-05-28 佛山市淼创科技有限公司 一种tpe塑料粒子

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