CN118215710A - EPDM-containing polyolefin compositions with improved surface properties in injection molding - Google Patents

EPDM-containing polyolefin compositions with improved surface properties in injection molding Download PDF

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Publication number
CN118215710A
CN118215710A CN202180104024.XA CN202180104024A CN118215710A CN 118215710 A CN118215710 A CN 118215710A CN 202180104024 A CN202180104024 A CN 202180104024A CN 118215710 A CN118215710 A CN 118215710A
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propylene
ethylene
copolymer
polyolefin composition
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孙宁
朱胜全
沈飞
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Borouge Compounding Shanghai Co ltd
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Borouge Compounding Shanghai Co ltd
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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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—Propene
    • 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
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2310/00—Masterbatches

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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)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

A Polyolefin Composition (PC) comprising: i) 50.0 to 70.0 wt.% of a first polypropylene (PP 1) having an MFR 2 of 5.0 to 120g/10 min; ii) 5.0 to 20.0 wt.% of a first elastomeric ethylene copolymer (EC 1) having an MFR 2 of 0.2 to 15g/10 min; iii) 5.0 to 15.0 weight percent of an ethylene-propylene-diene monomer rubber masterbatch composition (MB); iv) 5.0 to 25.0% by weight of filler (F); and v) optionally 0.1 to 5.0 wt% of an additive (a), wherein the ethylene-propylene-diene monomer rubber masterbatch composition (MB) comprises: a) 40.0 to 60.0 weight percent ethylene-propylene-diene monomer rubber (EPDM); b) 15.0 to 50.0 wt.% of a second polypropylene (PP 2) having an MFR 2 of 0.2 to 50g/10 min; and c) 2.0 to 29.0 wt.% of a second elastomeric ethylene copolymer (EC 2) having an MFR 2 of 0.2 to 20g/10 min.

Description

EPDM-containing polyolefin compositions with improved surface properties in injection molding
Technical Field
The present invention relates to a Polyolefin Composition (PC) comprising a specific ethylene-propylene diene monomer rubber masterbatch composition (MB), a process for producing said Polyolefin Composition (PC) and an injection molded article comprising said Polyolefin Composition (PC).
Background
Achieving a balance of mechanical properties, whether by providing a new polymer or by compounding two or more different polymers, remains one of the key objectives in providing propylene polymer compositions. In particular, the balance between stiffness (e.g., flexural modulus and/or tensile modulus) and impact strength (e.g., simple beam NIS or cantilever beam NIS) is critical in most polymer-containing articles, as factors tending to improve stiffness generally result in reduced impact strength and vice versa.
A well-known strategy for achieving a beneficial balance of properties is by adding a so-called impact modifier to a polypropylene composition that already has good stiffness properties. These impact modifiers are typically elastomeric ethylene copolymers that improve impact strength without reducing stiffness to unacceptable levels. Although this strategy has been used for decades, there are still a number of drawbacks. Most prominent among these are compositions containing more than 5% by weight of elastomeric ethylene copolymer, which tend to exhibit surface defects when subjected to injection molding, especially for large molded articles. One manifestation of these surface defects is the appearance of so-called "tiger stripes (TIGER STRIPE)" (or "flow marks") in which alternating bands of magnificent and dark bands are observed on the polymer surface. These defects are assumed to give a negative impression of the quality of the product due to slip-stick phenomena or unstable flow fronts during mold filling.
Another major manifestation of surface defects is the occurrence of so-called pinhole defects, which are usually formed by microbubbles and/or gel particles, which may be the result of elastomers and/or fillers in the composition.
The automotive market is very demanding polypropylene-containing injection molded articles with a spray-free and metal-like surface, but the requirements on their surface quality are very stringent, especially for visible defects on the gloss finishing surface (glossy-finished surface) of the molded articles, including tiger stripes and pinholes, which should be kept as low as possible. The gloss finish of the injection molded article is produced by a mold having an interior cavity with a gloss finish interior surface.
Some surface defects, such as microbubbles and gel particles, with particle sizes of 200 μm or more, are typically eliminated by optimizing the process parameters during compounding. Some surface defects with particle size of 80 μm or less are not visible and do not affect the surface quality. Surface defects (e.g. so-called pinholes) with particle sizes of 80-200 μm are visible and affect the surface quality. These should be controlled and limited to an acceptable range. For example, it is required that the number of visual defects (pinholes) on the area of 150mm (L). Times.100 mm (W) on the gloss finish surface of the injection molded plate is less than 10.
Accordingly, there is a need in the marketplace to provide polyolefin compositions with better surface quality, such as reducing the incidence of tiger stripes and reducing the incidence of pinhole defects, particularly in injection molded articles having a glossy surface (glossy surface). In particular, pinhole counts of no more than 10 were considered acceptable for an area of 150mm x 100 mm.
Disclosure of Invention
The present invention is based on the finding that: the addition of a masterbatch comprising elastomeric ethylene copolymer and EPDM rubber to the PP compound results in avoiding tiger stripes on the surface of the PP compound, which is inhibited by the presence of EPDM. Furthermore, the polyolefin composition thus obtained has a low pinhole count, which can be even further reduced by carefully adjusting the relative viscosity of the individual components.
The masterbatch improves the dispersibility of the EPDM in the polypropylene composition to which the masterbatch has been added and promotes the properties of the EPDM in the composition.
Accordingly, in a first aspect, the present invention relates to a Polyolefin Composition (PC) comprising:
i) A first polypropylene (PP 1) having a melt flow rate (MFR 2) in the range of 5.0 to 120g/10min, measured according to ISO 1133 at 230 ℃ under a load of 2.16 kg;
ii) a first elastomeric ethylene copolymer (EC 1) having a melt flow rate (MFR 2) according to ISO 1133, measured at 190 ℃ under a load of 2.16kg, in the range of 0.2 to 15g/10 min;
iii) Ethylene-propylene-diene monomer rubber (or ethylene-propylene-diene monomer rubber) masterbatch composition (MB);
iv) a filler (F); and
V) optionally an additive (A),
Wherein the ethylene-propylene-diene monomer rubber masterbatch composition (MB) comprises:
a) 40.0 to 60.0 weight percent of an ethylene-propylene-diene monomer rubber (EPDM) relative to the total weight of the ethylene-propylene-diene monomer rubber masterbatch composition (MB);
b) 15.0 to 50.0 wt% of a second polypropylene (PP 2) having a melt flow rate (MFR 2) in the range of 0.2 to 50g/10min, measured according to ISO 1133 at 230 ℃ under a load of 2.16kg, relative to the total weight of the ethylene-propylene-diene monomer rubber masterbatch composition (MB); and
C) 2.0 to 29.0 wt.%, relative to the total weight of the ethylene-propylene-diene monomer rubber masterbatch composition (MB), of a second elastomeric ethylene copolymer (EC 2) having a melt flow rate (MFR 2) according to ISO 1133, determined at 190℃under a load of 2.16kg, in the range of 0.2 to 20g/10min,
Wherein the respective content of the ethylene-propylene-diene monomer rubber (EPDM), the second polypropylene (PP 2) and the second elastomeric ethylene copolymer (EC 2) amounts to at least 90 wt%, more preferably at least 95 wt%, still more preferably at least 98 wt%, most preferably 100 wt%, relative to the total weight of the ethylene-propylene-diene monomer rubber masterbatch composition (MB).
In another aspect, the present invention relates to a process for producing a Polyolefin Composition (PC) according to the first aspect, comprising the steps of:
a) Providing a first polypropylene (PP 1), a first elastomeric ethylene copolymer (EC 1), an ethylene-propylene-diene monomer masterbatch composition (MB), a filler (F) and optionally an additive (a);
b) The first polypropylene (PP 1), the first elastomeric ethylene copolymer (EC 1), the ethylene-propylene-diene monomer masterbatch composition (MB), the filler (F) and optionally the additives (a) are blended and extruded in an extruder, preferably a twin screw extruder at a temperature in the range of 120 to 250 ℃, thereby producing a polyolefin composition, preferably in pellet form.
In a final aspect, the present invention relates to an injection molded article comprising at least 90 wt.%, more preferably at least 95 wt.%, still more preferably at least 98 wt.% of the Polyolefin Composition (PC) of the first aspect, more preferably a glossy surface injection molded article.
Definition of the definition
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although any methods and materials similar or equivalent to those described herein can be used in the practice for testing the present invention, the preferred materials and methods are described herein. In describing and claiming the present invention, the following terminology will be used in accordance with the definitions set out below.
The use of the terms "a," "an," etc., refer to one or more unless otherwise specifically indicated.
Hereinafter, unless otherwise indicated, amounts are given in weight percent (wt%).
Propylene homopolymers are polymers consisting essentially of propylene monomer units. Due to impurities, especially in commercial polymerization processes, the propylene homopolymer may comprise up to 0.1 mole% of comonomer units, preferably up to 0.05 mole% of comonomer units, most preferably up to 0.01 mole% of comonomer units.
The propylene copolymer is a copolymer of propylene monomer units and comonomer units, preferably selected from ethylene and C 4-C8 alpha-olefins. Propylene random copolymers are propylene copolymers in which the comonomer units are randomly distributed along the polymer chain, whereas propylene block copolymers comprise blocks of propylene monomer units and blocks of comonomer units. The propylene random copolymer may comprise comonomer units derived from one or more comonomers having different amounts of carbon atoms.
Heterophasic propylene copolymers generally comprise:
a) A crystalline propylene homo-or copolymer matrix (M); and
B) An elastomer rubber, preferably a propylene-ethylene copolymer (E);
The present invention will now be described in more detail.
Detailed Description
First Polypropylene (PP 1)
The main component of the Polyolefin Composition (PC) is the first polypropylene (PP 1).
The first polypropylene (PP 1) of the Polyolefin Composition (PC) may be a first propylene homopolymer, or a first propylene copolymer, more preferably a first propylene copolymer. The first propylene copolymer is preferably a first propylene-ethylene copolymer. The first propylene copolymer may be a first propylene random copolymer or a first propylene block copolymer, more preferably a first propylene block copolymer.
In a preferred embodiment, the first propylene block copolymer is a first heterophasic propylene copolymer (HECO 1), even more preferably a first heterophasic propylene-ethylene copolymer.
The first heterophasic propylene copolymer (HECO 1), more preferably the first heterophasic propylene-ethylene copolymer comprises:
c) A crystalline propylene homopolymer matrix (M); and
D) Elastomeric propylene-ethylene copolymer (E);
The first propylene copolymer, preferably the first propylene block copolymer, more preferably the first heterophasic propylene copolymer (HECO 1) of the Polyolefin Composition (PC) comprises a comonomer selected from the group consisting of ethylene and alpha-olefins having 4 to 12 carbon atoms, more preferably selected from the group consisting of ethylene, butene, hexene and octene, still more preferably selected from ethylene or butene, most preferably ethylene. Particularly preferably, the only comonomer present is ethylene.
The melt flow rate (MFR 2) of the first polypropylene (PP 1), more preferably the propylene copolymer, still more preferably the first propylene block copolymer, still more preferably the first heterophasic propylene copolymer (HECO 1), even more preferably the first heterophasic propylene-ethylene copolymer, measured according to ISO 1133 at 230 ℃ and 2.16kg, is in the range of 5.0 to 120g/10min, more preferably in the range of 8.0 to 115g/10min, most preferably in the range of 10.0 to 100g/10 min.
If the first polypropylene (PP 1) is a first propylene copolymer, the comonomer content, more preferably the ethylene (C2) content, is preferably in the range of 2.0 to 30.0 wt. -%, more preferably in the range of 3.0 to 25.0 wt. -%, most preferably in the range of 5.0 to 20.0 wt. -%, relative to the total weight of the first propylene copolymer.
Preferably, the Xylene Cold Soluble (XCS) content of the first heterophasic propylene copolymer (HECO 1), more preferably of the first heterophasic propylene-ethylene copolymer, is in the range of 5 to 50 wt%, preferably in the range of 10 to 45 wt%, most preferably in the range of 12 to 40 wt%.
Preferably, the total comonomer content, more preferably the total ethylene (C2) content, of the first heterophasic propylene copolymer (HECO 1), more preferably the first heterophasic propylene-ethylene copolymer is in the range of 2.0 to 30.0 wt%, preferably in the range of 3.0 to 25.0 wt%, most preferably in the range of 5.0 to 20.0 wt%.
Preferably, the comonomer content of the xylene cold soluble fraction of the first heterophasic propylene copolymer (HECO 1), more preferably of the first heterophasic propylene-ethylene copolymer, more preferably the ethylene content (C2 (XCS)) of the xylene cold soluble fraction is in the range of 10 to 50 wt. -%, preferably in the range of 20 to 45 wt. -%, most preferably in the range of 30 to 40 wt. -%.
Preferably, the intrinsic viscosity (IV (XCS)) of the xylene cold soluble fraction of the first heterophasic propylene copolymer (HECO 1), more preferably of the first heterophasic propylene-ethylene copolymer, is in the range of 1.0 to 4.0dl/g, preferably in the range of 1.5 to 3.5dl/g, most preferably in the range of 2.0 to 3.0 dl/g.
Preferably, the melt flow rate (MFR 2) of the crystalline propylene homopolymer matrix (M) of the first heterophasic propylene copolymer (HECO 1), more preferably of the first heterophasic propylene-ethylene copolymer, measured according to ISO 1133 at 230 ℃ and 2.16kg, is in the range of 10 to 220g/10min, more preferably in the range of 20 to 210g/10min, most preferably in the range of 30 to 200g/10 min.
The first polypropylene (PP 1), more preferably the first propylene copolymer, still more preferably the first propylene block copolymer, still more preferably the first heterophasic propylene copolymer (HECO 1), even more preferably the first heterophasic propylene-ethylene copolymer, preferably comprises a polymeric nucleating agent.
Preferred examples of such polymeric nucleating agents are vinyl polymers, such as vinyl polymers derived from monomers of the formula
H2C＝CH-CHR1R2
Wherein R 1 and R 2 together with the carbon atoms to which they are attached form an optionally substituted saturated or unsaturated or aromatic or fused ring system wherein the cyclic or fused ring moiety contains from 4 to 20 carbon atoms, preferably from 5 to 12 membered saturated or unsaturated or aromatic or fused ring system, or independently represent a straight or branched C4-C30 alkane, C4-C20 cycloalkane, or C4-C20 aromatic ring. Preferably, R 1 and R 2 together with the C atom to which they are attached form a five-or six-membered saturated or unsaturated or aromatic ring or independently represent a lower alkyl group containing 1 to 4 carbon atoms. Preferred vinyl compounds for the preparation of the polymeric nucleating agents used according to the present invention are in particular vinylcycloalkanes, in particular Vinylcyclohexane (VCH), vinylcyclopentane and vinyl-2-methylcyclohexane, 3-methyl-1-butene, 3-ethyl-1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene or mixtures thereof. Particularly preferably, the vinyl polymer is a vinylcycloalkane polymer, preferably selected from Vinylcyclohexane (VCH), vinylcyclopentane and vinyl-2-methylcyclohexane, wherein a vinylcyclohexane polymer is a particularly preferred embodiment.
Further preferably, the vinyl polymer of the polymeric nucleating agent is a homopolymer, most preferably a vinylcyclohexane homopolymer.
The first polypropylene (PP 1), more preferably the first propylene copolymer, still more preferably the first propylene block copolymer, still more preferably the first heterophasic propylene copolymer (HECO 1), even more preferably the first heterophasic propylene-ethylene copolymer of the present invention may be synthesized or selected from commercially available polypropylenes.
The first polypropylene (PP 1), more preferably the first propylene copolymer, still more preferably the first propylene block copolymer, still more preferably the first heterophasic propylene copolymer (HECO 1), even more preferably the first heterophasic propylene-ethylene copolymer of the present invention is preferably produced in a sequential multistage polymerization process in the presence of a ziegler-natta catalyst.
A preferred multistage process is a "loop gas phase" process, for example developed by the Denmark Borealis A/S (known asTechnology) described, for example, in the patent literature, for example, in EP 0 887 379, WO 92/12182, WO 2004/000899, WO 2004/111095, WO 99/24478, WO 99/24479 or WO 00/68315.
Another suitable slurry-gas phase process is BasellThe process is described in FIG. 20 of the paper, for example, galli and Vecello, prog. Polym. Sci.26 (2001) 1287-1336.
First elastomer ethylene copolymer (EC 1)
Another essential component of the Polyolefin Composition (PC) is the first elastomeric ethylene copolymer (EC 1).
The melt flow rate (MFR 2) of the first elastomeric ethylene copolymer (EC 1) measured according to ISO 1133 at 190℃and 2.16kg is in the range of 0.2 to 15g/10min, more preferably in the range of 0.3 to 10g/10min, most preferably in the range of 0.5 to 7.0g/10 min.
Preferably, the first elastomeric ethylene copolymer (EC 1) has a density, measured according to ISO 1183-187, in the range 860 to 880g/cm 3, preferably in the range 865 to 875g/cm 3, most preferably in the range 867 to 871g/cm 3.
Preferably, the melting temperature of the first elastomeric ethylene copolymer (EC 1) measured according to ISO 11357 is in the range of 30 to 120 ℃, more preferably in the range of 50 to 100 ℃, most preferably in the range of 60 to 80 ℃.
Preferably, the first elastomeric ethylene copolymer (EC 1) is a copolymer of ethylene and one or more comonomers selected from C5 to C12 alpha-olefins, more preferably from C6 to C10 alpha-olefins, most preferably the first elastomeric ethylene copolymer (EC 1) is an ethylene-octene copolymer or an ethylene-hexene copolymer.
The comonomer content of the first elastomeric ethylene copolymer (EC 1) is preferably in the range of 10 to 65 wt. -%, more preferably in the range of 20 to 60 wt. -%, most preferably in the range of 30 to 50 wt. -%, based on the total weight of the first elastomeric ethylene copolymer (EC 1).
Ethylene-propylene-diene monomer rubber masterbatch composition (MB)
Another essential component of the Polyolefin Composition (PC) is an ethylene-propylene-diene monomer rubber masterbatch composition (MB).
The ethylene-propylene-diene monomer rubber masterbatch composition (MB) comprises an ethylene-propylene-diene monomer rubber (EPDM), a second polypropylene (PP 2) and a second elastomeric ethylene copolymer (EC 2), the properties of which are discussed below.
The ethylene-propylene-diene monomer rubber masterbatch composition (MB) comprises, more preferably consists of:
a) 40.0 to 60.0 weight percent of an ethylene-propylene-diene monomer rubber (EPDM) relative to the total weight of the ethylene-propylene-diene monomer rubber masterbatch composition (MB);
b) 15.0 to 50.0 wt% of a second polypropylene (PP 2) relative to the total weight of the ethylene-propylene-diene monomer rubber masterbatch composition (MB);
c) 2.0 to 29.0 wt% of a second elastomeric ethylene copolymer (EC 2) relative to the total weight of the ethylene-propylene-diene monomer rubber masterbatch composition (MB); and
D) Optionally, 0.1 to 5.0 wt% of an additive relative to the total weight of the ethylene-propylene-diene monomer rubber masterbatch composition (MB).
In a preferred embodiment, the ethylene-propylene-diene monomer rubber masterbatch composition (MB) comprises, more preferably consists of:
a) 42.0 to 58.0 weight percent of an ethylene-propylene-diene monomer rubber (EPDM) relative to the total weight of the ethylene-propylene-diene monomer rubber masterbatch composition (MB);
b) 18.0 to 40.0 wt% of a second polypropylene (PP 2) relative to the total weight of the ethylene-propylene-diene monomer rubber masterbatch composition (MB);
c) 10.0 to 28.0 wt% of a second elastomeric ethylene copolymer (EC 2) relative to the total weight of the ethylene-propylene-diene monomer rubber masterbatch composition (MB); and
D) Optionally, 0.1 to 2.0 wt% of an additive relative to the total weight of the ethylene-propylene-diene monomer rubber masterbatch composition (MB).
In another preferred embodiment, the ethylene-propylene-diene monomer rubber masterbatch composition (MB) comprises, more preferably consists of:
a) 45.0 to 55.0 wt% of an ethylene-propylene-diene monomer rubber (EPDM) relative to the total weight of the ethylene-propylene-diene monomer rubber masterbatch composition (MB);
b) 20.0 to 30.0 wt% of a second polypropylene (PP 2) relative to the total weight of the ethylene-propylene-diene monomer rubber masterbatch composition (MB);
c) 20.0 to 27.0 wt% of a second elastomeric ethylene copolymer (EC 2) relative to the total weight of the ethylene-propylene-diene monomer rubber masterbatch composition (MB); and
D) Optionally, 0.1 to 1.0 wt% of an additive relative to the total weight of the ethylene-propylene-diene monomer rubber masterbatch composition (MB).
The respective content of ethylene-propylene-diene monomer rubber (EPDM), second polypropylene (PP 2) and second elastomeric ethylene copolymer (EC 2) amounts to at least 90 wt%, more preferably at least 95 wt%, relative to the total weight of the ethylene-propylene-diene monomer rubber masterbatch composition (MB). Still more preferably at least 98 wt%, most preferably 100 wt%.
The additive, if present, is preferably selected from pigments, antioxidants, UV stabilizers, scratch inhibitors, mold release agents, acid scavengers, lubricants, antistatic agents and mixtures thereof.
Preferably, the ratio of ethylene-propylene-diene monomer rubber (EPDM) to second elastomeric ethylene copolymer (EC 2) in the ethylene-propylene-diene monomer masterbatch composition (MB) is in the range of 1.0:1 to 5.0:1, more preferably in the range of 1.3:1 to 4.0:1, most preferably in the range of 1.5:1 to 3.0:1.
Preferably, the melt flow rate (MFR 2) of the ethylene-propylene-diene monomer rubber masterbatch composition (MB) measured according to ISO 1133 at 230℃and 2.16kg is in the range of 0.05 to 5.0g/10min, more preferably in the range of 0.10 to 3.0g/10min, most preferably in the range of 0.15 to 1.0g/10 min.
Preferably, the ethylene-propylene-diene monomer rubber masterbatch composition (MB) is obtainable by a process comprising, preferably by a process comprising:
a) Providing a second polypropylene (PP 2), a second elastomeric ethylene copolymer (EC 2) and an ethylene-propylene-diene monomer rubber (EPDM);
b) The second polypropylene (PP 2), the second elastomeric ethylene copolymer (EC 2) and the ethylene-propylene-diene monomer rubber (EPDM) are blended and extruded in an extruder, preferably a twin screw extruder, at a temperature of 120 to 250 ℃, thereby producing an ethylene-propylene-diene monomer rubber masterbatch composition (MB), preferably in pellet form.
In particular, it is preferable to use conventional compounding or blending equipment such as a Banbury mixer, a 2-roll rubber mill, a Buss co-kneader or a twin-screw extruder. More preferably, the mixing is accomplished in a co-rotating twin screw extruder. The polymeric material recovered from the extruder is typically in the form of pellets. These pellets can then be used as EPDM masterbatch for incorporation of EPDM into other polypropylene compositions, in particular polypropylene compositions for forming molded articles.
Ethylene-propylene-diene monomer rubber (EPDM)
The main component of the masterbatch composition is ethylene-propylene-diene monomer rubber (EPDM).
Preferably, the ethylene-propylene-diene monomer rubber (EPDM) is a terpolymer of ethylene, propylene and Ethylidene Norbornene (ENB).
Preferably, the ethylene-propylene-diene monomer rubber (EPDM), more preferably a terpolymer of ethylene, propylene and Ethylidene Norbornene (ENB), has a mooney viscosity M L (1+4) measured at 125 ℃ according to ASTM D1646 in the range of 40 to 100MU, preferably in the range of 60 to 95MU, most preferably in the range of 75 to 90 MU.
Preferably, the ethylene content (C2) of the terpolymer of ethylene, propylene and Ethylidene Norbornene (ENB) is in the range of 50 to 90 wt%, preferably in the range of 55 to 85 wt%, most preferably in the range of 60 to 80 wt%, of the ethylene-propylene-diene monomer rubber (EPDM).
Preferably, the diene content of the ethylene-propylene-diene monomer rubber (EPDM), more preferably of a terpolymer of ethylene, propylene and Ethylidene Norbornene (ENB), more preferably of Ethylidene Norbornene (ENB) is in the range of 1.0 to 10.0%, preferably in the range of 2.0 to 8.0%, most preferably in the range of 3.0 to 7.0%.
Preferably, the ethylene-propylene-diene monomer rubber (EPDM), more preferably a terpolymer of ethylene, propylene and Ethylidene Norbornene (ENB), has a density, measured according to ISO 1183-187, in the range of 0.80 to 0.96g/cm 3, preferably in the range of 0.83 to 0.93g/cm 3, most preferably in the range of 0.86 to 0.90g/cm 3.
The ethylene-propylene-diene monomer rubber (EPDM) of the present invention, more preferably a terpolymer of ethylene, propylene and Ethylidene Norbornene (ENB), may be synthesized or selected from commercially available EPDM rubbers such as Nordel TM IP 4785HM commercially available from the dow chemical company (Dow Chemical Company) (Shanghai, china).
Second polypropylene (PP 2)
Another essential component of the ethylene-propylene-diene monomer rubber masterbatch composition (MB) is a second polypropylene (PP 2).
The second polypropylene (PP 2) of the Polyolefin Composition (PC) may be a second propylene homopolymer, or a second propylene copolymer, more preferably a second propylene copolymer. The second propylene copolymer is preferably a second propylene-ethylene copolymer. The second propylene copolymer may be a second propylene random copolymer or a second propylene block copolymer, more preferably a second propylene block copolymer, most preferably a second heterophasic propylene copolymer (HECO 2).
Other properties of the second polypropylene (PP 2) or the second heterophasic propylene copolymer, including the choice of comonomer, comonomer/ethylene content, xylene Cold Soluble (XCS) content, comonomer/ethylene content of XCS fraction, intrinsic viscosity of XCS fraction, matrix melt flow rate (MFR 2) and all properties regarding the optional polymer nucleating agent and the preparation method are the same as those described above for the first polypropylene (PP 1) or the first heterophasic propylene copolymer, except for the following ranges of melt flow rate (MFR 2) of the second polypropylene (PP 2).
The second heterophasic propylene copolymer (HECO 2), more preferably the second heterophasic propylene-ethylene copolymer comprises:
a) A crystalline propylene homopolymer matrix (M); and
B) Elastomeric propylene-ethylene copolymer (E);
The melt flow rate (MFR 2) of the second polypropylene (PP 2), more preferably the propylene copolymer, still more preferably the second propylene block copolymer, still more preferably the second heterophasic propylene copolymer (HECO 2), even more preferably the second heterophasic propylene-ethylene copolymer, measured according to ISO 1133 at 230 ℃ and 2.16kg, is in the range of 0.2 to 50g/10min, more preferably in the range of 0.3 to 35g/10min, most preferably in the range of 0.5 to 30g/10 min.
In the Polyolefin Composition (PC), the second polypropylene (PP 2) may be the same as the first polypropylene (PP 1), or the second polypropylene (PP 2) may be different from the first polypropylene (PP 1). Preferably, the second polypropylene (PP 2) has a lower MFR than the first polypropylene (PP 1).
Second elastomeric ethylene copolymer (EC 2)
Another essential component of the ethylene-propylene-diene monomer rubber masterbatch composition (MB) is a second elastomeric ethylene copolymer (EC 2).
The definition of the second elastomeric ethylene copolymer (EC 2) with respect to density, melting temperature, comonomer selection and comonomer content is the same as the definition of the first elastomeric ethylene copolymer (EC 1) as described above.
The melt flow rate (MFR 2) of the second elastomeric ethylene copolymer (EC 2) measured according to ISO 1133 at 190℃and 2.16kg is in the range of 0.2 to 20g/10min, more preferably in the range of 0.3 to 15g/10min, most preferably in the range of 0.5 to 10g/10 min.
In the Polyolefin Composition (PC), the second elastomeric ethylene copolymer (EC 2) may be the same as the first elastomeric ethylene copolymer (EC 1), or the second elastomeric ethylene copolymer (EC 2) may be different from the first elastomeric ethylene copolymer (EC 1). Preferably, the second elastomeric ethylene copolymer (EC 2) has a higher MFR 2 than the first elastomeric ethylene copolymer (EC 1).
Filler (F)
Another essential component of the Polyolefin Composition (PC) is a filler (F).
Preferably, the filler is an inorganic filler, more preferably selected from the group comprising talc, calcium carbonate, barium sulfate, mica and mixtures thereof.
Most preferably, the inorganic filler (F) is talc.
Additive (A)
The Polyolefin Composition (PC) of the invention may contain the additive (a) in an amount of 0.1 to 5.0% by weight. Those skilled in the art will be able to select suitable additives well known in the art.
The additive (a) is preferably selected from pigments, antioxidants, UV stabilizers, scratch inhibitors, mold release agents, acid scavengers, lubricants, antistatic agents and mixtures thereof.
It is understood that the content of additive (a) given with respect to the total weight of the Polyolefin Composition (PC) includes any carrier polymer used to introduce additives into said Polyolefin Composition (PC), i.e. a masterbatch carrier polymer. An example of such a carrier polymer is a polypropylene homopolymer in powder form.
Polyolefin Composition (PC)
The Polyolefin Composition (PC) of the present invention comprises a first polypropylene (PP 1), a first elastomeric ethylene copolymer (EC 1), an ethylene-propylene-diene monomer rubber masterbatch composition (MB), a filler (F) and optionally an additive (a).
The respective content of the first polypropylene (PP 1), the first elastomeric ethylene copolymer (EC 1), the ethylene-propylene-diene monomer rubber masterbatch composition (MB), the filler (F) and the optional additives (a) is preferably at least 90 wt%, more preferably at least 95 wt%, still more preferably at least 98 wt%, most preferably 100 wt%, with respect to the total weight of the Polyolefin Composition (PC).
The Polyolefin Composition (PC) preferably comprises, more preferably consists of:
i) 50.0 to 70.0 wt% of a first polypropylene (PP 1) relative to the total weight of the Polyolefin Composition (PC);
ii) 5.0 to 20.0 wt% of a first elastomeric ethylene copolymer (EC 1) relative to the total weight of the Polyolefin Composition (PC);
iii) 5.0 to 15.0 wt% of an ethylene-propylene-diene monomer rubber masterbatch composition (MB) relative to the total weight of the Polyolefin Composition (PC);
iv) 5.0 to 25.0 wt% of filler (F) relative to the total weight of the Polyolefin Composition (PC); and
V) optionally, 1.0 to 5.0 wt.% of additive (a) relative to the total weight of the Polyolefin Composition (PC).
In a preferred embodiment, the Polyolefin Composition (PC) comprises, more preferably consists of:
i) 55.0 to 67.0 wt% of a first polypropylene (PP 1) relative to the total weight of the Polyolefin Composition (PC);
ii) from 7.0 to 17.0% by weight of a first elastomeric ethylene copolymer (EC 1) relative to the total weight of the Polyolefin Composition (PC);
iii) 7.0 to 13.0 wt% of an ethylene-propylene-diene monomer rubber masterbatch composition (MB) relative to the total weight of the Polyolefin Composition (PC);
iv) 7.0 to 20.0 wt% of filler (F) relative to the total weight of the Polyolefin Composition (PC); and
V) optionally, 1.0 to 5.0 wt.% of additive (a) relative to the total weight of the Polyolefin Composition (PC).
In each of these embodiments, the respective content of the first polypropylene (PP 1), the first elastomeric ethylene copolymer (EC 1), the ethylene-propylene-diene monomer rubber masterbatch composition (MB), the filler (F) and the optional additive (a) is preferably total at least 90 wt%, more preferably at least 95 wt%, still more preferably at least 98 wt%, most preferably 100 wt%, relative to the total weight of the Polyolefin Composition (PC).
In another preferred embodiment, the Polyolefin Composition (PC) comprises, more preferably consists of:
i) 60.0 to 65.0 wt% of a first polypropylene (PP 1) relative to the total weight of the Polyolefin Composition (PC);
ii) 9.0 to 14.0 wt% of a first elastomeric ethylene copolymer (EC 1) relative to the total weight of the Polyolefin Composition (PC);
iii) 8.0 to 12.0 wt% of an ethylene-propylene-diene monomer rubber masterbatch composition (MB) relative to the total weight of the Polyolefin Composition (PC);
iv) 10.0 to 15.0 wt% of filler (F) relative to the total weight of the Polyolefin Composition (PC); and
V) optionally, 1.0 to 5.0 wt.% of additive (a) relative to the total weight of the Polyolefin Composition (PC).
Preferably, the melt flow rate (MFR 2) of the first polypropylene (PP 1) measured according to ISO 1133 at 230 ℃ under a load of 2.16kg is higher than the melt flow rate (MFR 2) of the second polypropylene (PP 2) measured according to ISO 1133 at 230 ℃ under a load of 2.16 kg.
Furthermore, it is preferred that the melt flow rate (MFR 2) of the first elastomeric ethylene copolymer (EC 1) measured according to ISO 1133 at 190 ℃ under a load of 2.16kg is lower than the melt flow rate (MFR 2) of the second elastomeric ethylene copolymer (EC 2) measured according to ISO 1133 at 190 ℃ under a load of 2.16 kg.
It is also preferred that the ratio [ eta (MB)/eta (PP 1) ] between the viscosity eta (MB) of the ethylene-propylene-diene monomer rubber masterbatch composition and the viscosity eta (PP 1) of the first polypropylene is in the range of 1.00 to 5.00, more preferably in the range of 1.20 to 4.75, most preferably in the range of 1.50 to 4.50, wherein the viscosities are determined in accordance with ISO 11443 at a temperature of 250 ℃ and a shear rate of 640s -1, respectively, which match the typical temperature and shear rate of the polyolefin during compounding in a twin screw extruder.
It is also preferred that the ratio [ eta (MB)/eta (EC 1) ] between the viscosity eta (MB) of the ethylene-propylene-diene monomer rubber masterbatch composition and the viscosity eta (EC 1) of the first elastomeric ethylene copolymer is in the range of 0.10 to 1.50, more preferably in the range of 0.30 to 1.45, most preferably in the range of 0.50 to 1.25, wherein the viscosity is measured according to ISO 11443 at a temperature of 250 ℃ and a shear rate of 640s -1.
It has been found in particular that the surface quality of the injection-molded articles, for example pinholes, is further improved with excellent results when any of the viscosity ratios given above is met.
Preferably, the ratio [ η (MB)/η (PP 1) ] between the viscosity η (MB) of the ethylene-propylene-diene monomer rubber masterbatch composition and the viscosity η (PP 1) of the first polypropylene is in the range of 1.00 to 5.00, more preferably in the range of 1.20 to 4.85, most preferably in the range of 1.50 to 4.75, all viscosity values being determined according to ISO 11443 at a temperature in the range of 200 to 300 ℃ and a shear rate in the range of 80 to 1280s -1, which matches the shear rate and the range of temperature of the polyolefin during compounding of the twin-screw or single-screw extruder or injection molding machine, respectively.
It is also preferred that the ratio [ eta (MB)/eta (EC 1) ] between the viscosity eta (MB) of the ethylene-propylene-diene monomer rubber masterbatch composition and the viscosity eta (EC 1) of the first elastomeric ethylene copolymer is in the range of 0.10 to 1.50, more preferably in the range of 0.3 to 1.45, most preferably in the range of 0.50 to 1.25, all viscosity values being determined in accordance with ISO 11443 at a temperature in the range of 200 to 300 ℃ and a shear rate in the range of 80 to 1280s -1.
It has been found in particular that the surface quality (e.g.pinholes) of the injection-molded articles is further improved with excellent results when any of the viscosity ratios given above (in the temperature range of 200-300 ℃ and in the shear rate range of 80-1280s -1) is met.
The melt flow rate (MFR 2) of the Polyolefin Composition (PC) measured according to ISO 1133 at 230℃under a load of 2.16kg is preferably in the range of 5.0 to 100g/10min, more preferably in the range of 7.0 to 80g/10min, most preferably in the range of 10.0 to 60g/10 min.
In an EPDM masterbatch, the choice of the second elastomeric ethylene copolymer (EC 2) and the second polypropylene (PP 2) improves the dispersibility of the EPDM in the masterbatch, while the masterbatch in turn contributes to the dispersibility of the EPDM in the polypropylene composition to which the masterbatch has been added. Thus, the final polypropylene composition not only has a uniform phase dispersion, but also has better surface quality due to the introduction of EPDM.
In addition, the polypropylene composition of the present invention can be compounded during compounding at a lower specific energy input (.ltoreq.0.20 kw h/kg) than the usual specific energy input (0.25 kw h/kg or higher) for polypropylene compositions, even if EPDM has been incorporated.
In addition, the final polypropylene composition has good mechanical properties acceptable to the end user, including flexural modulus, impact resistance, etc., in addition to improved surface quality.
The Polyolefin Composition (PC) can be obtained by the following method, more preferably by the following method.
Process for producing Polyolefin Composition (PC)
In another aspect, the present invention relates to a process for producing a Polyolefin Composition (PC) according to the first aspect, comprising the steps of:
a) Providing a first polypropylene (PP 1), a first elastomeric ethylene copolymer (EC 1), an ethylene-propylene-diene monomer rubber masterbatch composition (MB), a filler (F) and optionally an additive (a);
b) The first polypropylene (PP 1), the first elastomeric ethylene copolymer (EC 1), the ethylene-propylene-diene monomer rubber masterbatch composition (MB), the filler (F) and optionally the additives (a) are blended and extruded in an extruder, preferably a twin screw extruder at a temperature in the range of 120 to 250 ℃, thereby producing the Polyolefin Composition (PC), preferably in pellet form.
In particular, it is preferable to use conventional compounding or blending equipment, such as a Banbury mixer, a 2-roll rubber mill, a Buss co-kneader or a twin-screw extruder. More preferably, the mixing is accomplished in a co-rotating twin screw extruder. The polymeric material recovered from the extruder is typically in the form of pellets.
Particularly preferably, the Polyolefin Composition (PC) of the invention is used for the production of injection molded articles. Thus, preferably, the method further comprises the following step after step b):
c) Injection molding the Polyolefin Composition (PC) produced in step b) to form an injection molded article,
Wherein the injection molding is preferably gloss surface injection molding.
Those skilled in the art will appreciate that gloss surface injection molding involves the use of highly specialized so-called class a molds having a high gloss finish (finish) resulting in very smooth injection molded articles. Suitable injection molds are commercially available and well known in the art.
Article of manufacture
The invention also relates to injection molded articles comprising the Polyolefin Composition (PC) of the invention.
Preferably, the injection molded article is a glossy surface injection molded article.
The injection molded article, more preferably the glossy surface injection molded article, comprises at least 90 wt%, more preferably at least 95 wt%, still more preferably at least 98 wt% of the Polyolefin Composition (PC).
In a particularly preferred embodiment, the injection molded article, more preferably the glossy surface injection molded article, consists of a Polyolefin Composition (PC).
Particularly preferably, the injection molded article, more preferably the glossy surface injection molded article, is obtainable by a process having steps a) to c) as described above, more preferably by a process having steps a) to c) as described above.
Preferably, the article is part of an automotive article, in particular an automotive exterior part, such as a bumper, or an interior part, such as an instrument carrier (instrumental carrier), an instrument panel, an interior trim, or the like.
Examples
1. Definition/measurement method
Unless otherwise defined, the following definitions of terms and assay methods apply to the above general description of the invention as well as to the following examples.
The density is measured according to ISO 1183-187. Sample preparation was accomplished by compression molding (compression moulding) according to ISO 1872-2:2007.
MFR 2: melt Flow Rate (MFR) is determined according to ISO 1133 and is expressed in g/10 min. MFR is an indication of the flowability and thus processability of the polymer. The higher the melt flow rate, the lower the viscosity of the polymer. The MFR 2 of the polypropylene was determined at a temperature of 230℃and a load of 2.16 kg. The MFR 2 of the elastomeric ethylene copolymer was determined at a temperature of 190℃and a load of 2.16 kg.
Melting temperature Tm: the melting temperature is measured according to ISO 11357-3.
Method for quantifying propylene copolymer microstructure by NMR spectroscopy
Quantitative Nuclear Magnetic Resonance (NMR) spectroscopy was used to quantify the comonomer content of the propylene polymer.
Quantitative 13C{1 H } NMR spectra were recorded in solution using a Bruker ADVANCE III NMR spectrometer, operating at 400.15 and 100.62MHz for 1 H and 13 C, respectively. All spectra were recorded at 125℃using a 13 C optimized 10mm extended temperature probe and all pneumatic devices were nitrogen. About 200mg of the material was dissolved in 3ml of 1, 2-tetrachloroethane-d 2(TCE-d2 together with chromium (III) acetylacetonate (Cr (acac) 3) to form a 65mM solution of the relaxation agent in a solvent, as described in G.Singh, A.Kothari, V.Gupta, polymer Testing 2009,28 (5), 475.
To ensure a homogeneous solution, after initial sample preparation in the heating block, the NMR tube was further heated in a rotary oven for at least 1 hour. After insertion into the magnet, the tube was rotated at 10 Hz. This setting is chosen primarily for high resolution and is quantitatively required for accurate ethylene content quantification. With standard single pulse excitation, no NOE is required, using optimized tip angle, 1s cycle delay, and dual stage WALTZ16 decoupling schemes, 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.Carbonniere,R.Cipullo,C.Pellecchia,J.Severn,G.Talarico,Macromol.Rapid Commun.2007,28,1128. A total of 6144 (6 k) transients were acquired per spectrum. Quantitative 13C{1 H } NMR spectra were processed, integrated, and relevant quantitative properties were determined from the integration. All chemical shifts use chemical shifts of the solvent to indirectly reference the central methylene of the ethylene block (EEE) at 30.00 ppm. This method allows for comparable references even if the building block is not present.
With the characteristic signals corresponding to the observed 2,1 erythro region defects (as described in L.Resconi,L.Cavallo,A.Fait,F.Piemontesi,Chem.Rev.2000,100(4),1253;Cheng,H.N.,Macromolecules 1984,17,1950; and W-j. Wang and s.zhu, macromolecules 2000,33 1157), it is necessary to correct the effect of the region defects on the measured properties. No characteristic signals corresponding to other types of region defects are observed.
Characteristic signals corresponding to the incorporation of ethylene (as described in Cheng, h.n., macromolecules 1984,17,1950) were observed and the comonomer fraction was calculated as the fraction of ethylene in the polymer relative to all monomers in the polymer.
Comonomer fractions were quantified by integrating multiple signals over the entire spectral region in the 13C{1 H } spectrum using the method of W-J.Wang and S.Zhu, macromolecules 2000,33 1157. This method is chosen for its robust nature and ability to take into account the presence of region defects when needed. The integration region is slightly adjusted to increase applicability across the entire range of comonomer content encountered.
The mole percent of comonomer incorporation was calculated from the mole fraction.
The weight percent of comonomer incorporation was calculated from the weight fractions.
Comonomer content in elastomeric Ethylene Copolymer (EC) and ethylene-propylene-diene monomer rubber (EPDM) was measured in a known manner based on fourier transform infrared spectroscopy (FTIR) calibrated with 13 C-NMR using a Nicolet Magna 550IR spectrometer and Nicolet Omnic FTIR software. Films with a thickness of about 250 μm were compression molded from the samples. Similar films were prepared from calibration samples with known comonomer content. The comonomer content was determined by spectroscopy at wavenumbers in the range 1430 to 1100cm -1. Absorbance is measured as the height of the peak by selecting either a so-called short baseline or long baseline or both. Short baselines are drawn through minimum points in about 1410-1320cm -1, and long baselines are drawn between about 1410 and 1220cm -1. Calibration is required specifically for each baseline type. Furthermore, the comonomer content of the unknown sample needs to be within the comonomer content range of the calibration sample.
Xylene solubles fraction (XCS) at room temperature (XCS, wt%): the amount of xylene soluble polymer was determined according to ISO 16152, first edition, 7.1.2005, at 25 ℃. The remainder was xylene cold insoluble (XCU) fraction.
Intrinsic Viscosity (IV) is measured according to ISO 1628-1 (in decalin at 135 ℃).
Mooney viscosity was measured at 125℃according to ASTM D1646.
Impact test of simple beam: the Notched Impact Strength (NIS) of a simply supported beam was measured according to ISO 179-1eA at +23℃and-20℃using 80X 10X 4mm 3 injection-molded bar samples prepared according to ISO 1873-2:2007.
Flexural modulus: flexural modulus was determined according to ISO 178 at 23℃on 80X 10X 4mm 3 test bars injection molded according to EN ISO 1873-2 at 3 point bending.
Viscosity: viscosity was determined according to ISO 11443:2021 using a Goettfert capillary rheometer "RG25" with a capillary die size of d=1 mm and l=10 mm.
Surface quality: pinhole and tiger stripe
150Mm 100mm 3mm injection molded plaques were prepared according to ISO 19069-2 using ENGEL AUSTRIAGmbH injection molding machine "Engel 120" and a mold having a glossy finish inner surface with an interior cavity.
Tiger stripe and pinhole defects of 80-200 μm in granularity of the injection molded plate were checked with naked eyes, and counted over an area of 150mm×100mm on the plate surface.
2. Examples
2.1. Synthesis of heterophasic propylene-ethylene copolymer (HECO)
The catalyst used in each polymerization was a Ziegler-Natta catalyst from Borealis having a Ti content of 1.9% by weight (as described in EP 591 224). The catalyst was prepolymerized with Vinylcyclohexane (VCH) prior to polymerization, as described in EP 1 028984 and EP 1 183 307. A ratio of VCH to catalyst of 1:1 was used in the preparation so that the final poly-VCH content was less than 100ppm.
In the first stage, the above catalyst was fed into the prepolymerization reactor together with propylene and small amounts of hydrogen (2.5 g/h) and ethylene (330 g/h). Triethylaluminum was used as cocatalyst and dicyclopentyl dimethoxy silane was used as donor. The ratio of aluminum to donor was 7.5 moles/mole and the ratio of aluminum to titanium was 300 moles/mole. The reactor was operated at a temperature of 30℃and a pressure of 55 bar gauge (barg).
The subsequent polymerization was carried out under the following conditions.
Table 1: polymerization conditions of HECO
In addition, the following commercially available polymer grades were used in the following examples:
EPDM ethylene-propylene-ethylidene norbornene terpolymer, commercially available from Dow chemical Co., ltd., MFR 2 (190 ℃ C.) < 0.2g/10min, mooney viscosity (ML 1+4,125 ℃ C.) 85MU, ethylene content 68 wt%, ethylidene norbornene content 4.9 wt%, propylene content 27.1%, and density 0.88g/cm 3.
EC1 elastomeric ethylene-octene copolymer, commercially available from Sabic (Shanghai) trade Co., ltd (China), having MFR 2 (190 ℃) of 5.0g/10min, mooney viscosity (ML 1+4,125 ℃) of 8MU, and a density of 0.868g/cm 3, under the trade name Fortify C5070D.
EC2 elastomeric ethylene-octene copolymer, commercially available from Dow chemical company (USA) under the trade name Engage XLT 8677, has an MFR 2 (190 ℃) of 0.5g/10min, a Mooney viscosity (ML 1+4,125 ℃) of 45MU, and a density of 0.870g/cm 3.
EC3 elastomeric ethylene-octene copolymer, commercially available from Dow chemical company (USA), under the trade name Engage 8100, has an MFR 2 (190 ℃) of 1.0g/10min, a Mooney viscosity (ML 1+4,125 ℃) of 24MU, and a density of 0.870g/cm 3.
F talc, commercially available under the trade name HTP Ultra 5L from IMI Fabi (Italy).
CMB color master batch, commercially available under the trade name KMB-L5305HW from bo Huaihua corporation (Kestro Polychem, inc.) (china).
An additive masterbatch, based on 100% by weight of the total polyolefin composition, consisting of: 0.8% by weight of a carrier propylene homopolymer, commercially available from Hongji petrochemical (China), having an MFR 2 (230 ℃ C., 2.16 kg) of 27g/10min; 0.15% by weight of an antioxidant under the trade name Irganox 1076 (CAS-No. 2082-79-3), commercially available from BASF SE (Germany); 0.15% by weight of an antioxidant under the trade name Irgafos 168 (CAS-No. 31570-04-4), commercially available from BASF SE (Germany); 0.15% by weight of glyceryl monostearate (CAS-No. 91052-47-0), commercially available under the trade name RIKEMAL AS-005 from RIKEN VITAMIN co., ltd (japan); 0.30% by weight of a UV stabilizer, commercially available from Sorve (Solvay) (China), under the trade name Cyasorb V703; 0.30% by weight of a slip agent, commercially available from crotamide (Croda) (uk), under the trade name Crodamide VRX; and 0.15% by weight of calcium stearate (CAS-No. 1592-23-0), commercially available from hair based chemicals (FACI CHEMICALS) (Zhangjinggang) limited (China).
2.2. Compounding preparation of masterbatch composition
Masterbatch composition (MB) was prepared from 25 wt% HECO1, 25 wt% EC1 and 50 wt% EPDM by compounding in a co-rotating twin screw extruder "STS35" commercially available from Coperion (Coperion), having a barrel temperature of 210 ℃, a die temperature of 212 ℃, a screw speed of 507rpm, a throughput of 40.5kg/h, a torque of 47%, a die pressure of 3.3 bar, and a Specific Energy Input (SEI) of 0.392 kW.h/kg.
2.3. Compounding preparation of inventive and comparative examples
Inventive examples and comparative examples were prepared by compounding in a co-rotating twin screw extruder "STS35" from cobalalong under the conditions described in table 3, based on the formulations indicated in table 2.
Table 2: formulations of inventive and comparative examples
Table 3: compounding conditions of comparative example and inventive example in twin screw extruder
2.4. Viscosity Properties of the Components and compositions
The MFR 2 (table 4) and viscosity (η) of the polymer components and each of the inventive and comparative compositions were determined (table 5) and the viscosity ratio calculated (table 6). The viscosity is measured at a temperature of 200 to 300 ℃ and a shear rate of 80 to 1280s -1, reflecting typical polyolefin compounding conditions in an extruder or in an injection molding machine.
Table 4: melt flow Rate (MFR 2) measured at 230℃and 190 ℃
Table 5a: viscosity (in Pa.s) measured at a shear rate of 80 to 1280s -1 and a temperature of 200 to 300 DEG C
Table 5b: viscosity (in Pa.s) measured at a shear rate of 80 to 1280s -1 and a temperature of 200 to 300 DEG C
Table 6a: viscosity ratio between EPDM masterbatch and HECO
Table 6b: viscosity ratio between EPDM masterbatch and EC
2.5. Injection molded article
Injection molded plaques of 150mm by 100mm by 3mm were prepared from the inventive and comparative polyolefin compositions according to the injection molding method described in the determination method (at surface quality).
The injection molded plate was inspected for pinhole defects and the pinhole defects were counted on a 150mm x 100mm face of the plate. The results are summarized in table 7.
80Mm 10mm 4mm injection molded test bars were prepared from the inventive and comparative polyolefin compositions according to the injection molding method described in the determination methods (under the test of impact strength and flexural modulus of a simply supported beam) and evaluated for mechanical properties. The results are summarized in table 7.
Table 7: surface Properties of injection molded Board
As can be seen from table 7, the inventive compositions had much lower pinhole counts than the comparative examples, while all inventive and comparative compositions had no tiger stripes on the surface due to the presence of EPDM.
Furthermore, it can be seen that the examples (i.e., IE1 to IE 3) having a viscosity ratio [ eta (MB)/eta (PP 1) ] greater than 5.0 and a viscosity ratio [ eta (MB)/eta (EC 1) ] of at least 1.50 have pinhole counts exceeding 10 (on a 150mm x 100mm surface). While this is significantly better than the comparative example, it is of course desirable to achieve as low a pinhole content as possible. In particular, as noted above, threshold 10 is generally considered an acceptable threshold for a glossy finish surface of an injection molded article.
The viscosity ratio [ eta (MB)/eta (PP 1) ] of IE4 and IE5 is less than 5.00. Although the other viscosity ratio [ eta (MB)/eta (EC 1) ] is still at least 1.50, the pinhole count now falls below the threshold of 10 (on a 150mm by 100mm surface).
The viscosity ratio [ eta (MB)/eta (EC 1) ] of IE6 and IE7 is less than 1.50. Although the other viscosity ratio [ eta (MB)/eta (PP 1) ] is still greater than 5.00, the pinhole count now falls below the threshold of 10 (on a 150mm by 100mm surface).
In addition, as shown in Table 7, the mechanical properties of the compositions of the present invention are good and acceptable for injection molded articles.

Claims (16)

1. A Polyolefin Composition (PC) comprising:
i) A first polypropylene (PP 1) having a melt flow rate (MFR 2) in the range of 5.0 to 120g/10min, measured according to ISO 1133 at 230 ℃ under a load of 2.16 kg;
ii) a first elastomeric ethylene copolymer (EC 1) having a melt flow rate (MFR 2) according to ISO 1133, measured at 190 ℃ under a load of 2.16kg, in the range of 0.2 to 15g/10 min;
iii) An ethylene-propylene-diene monomer rubber masterbatch composition (MB);
iv) a filler (F); and
V) optionally an additive (A),
Wherein the ethylene-propylene-diene monomer rubber masterbatch composition (MB) comprises:
a) 40.0 to 60.0 weight percent of an ethylene-propylene-diene monomer rubber (EPDM) relative to the total weight of the ethylene-propylene-diene monomer rubber masterbatch composition (MB);
b) 15.0 to 50.0 wt% of a second polypropylene (PP 2) having a melt flow rate (MFR 2) in the range of 0.2 to 50g/10min, measured according to ISO 1133 at 230 ℃ under a load of 2.16kg, relative to the total weight of the ethylene-propylene-diene monomer rubber masterbatch composition (MB); and
C) 2.0 to 29.0 wt.%, relative to the total weight of the ethylene-propylene-diene monomer rubber masterbatch composition (MB), of a second elastomeric ethylene copolymer (EC 2) having a melt flow rate (MFR 2) according to ISO 1133, determined at 190℃under a load of 2.16kg, in the range of 0.2 to 20g/10min,
Wherein the respective content of the ethylene-propylene-diene monomer rubber (EPDM), the second polypropylene (PP 2) and the second elastomeric ethylene copolymer (EC 2) amounts to at least 90 wt%, more preferably at least 95 wt%, still more preferably at least 98 wt%, most preferably 100 wt%, relative to the total weight of the ethylene-propylene-diene monomer rubber masterbatch composition (MB).
2. Polyolefin Composition (PC) according to claim 1, wherein the melt flow rate (MFR 2) of the first polypropylene (PP 1) measured according to ISO 1133 at 230 ℃ under a load of 2.16kg is higher than the melt flow rate (MFR 2) of the second polypropylene (PP 2) measured according to ISO 1133 at 230 ℃ under a load of 2.16kg, and/or
The melt flow rate (MFR 2) of the first elastomeric ethylene copolymer (EC 1) measured according to ISO 1133 at 190 ℃ under a load of 2.16kg is lower than the melt flow rate (MFR 2) of the second elastomeric ethylene copolymer (EC 2) measured according to ISO 1133 at 190 ℃ under a load of 2.16 kg.
3. The Polyolefin Composition (PC) according to claim 1 or claim 2, wherein the ratio [ η (MB)/η (PP 1) ] between the viscosity η (MB) of the ethylene-propylene-diene monomer rubber masterbatch composition and the viscosity η (PP 1) of the first polypropylene is in the range of 1.00 to 5.00, more preferably in the range of 1.20 to 4.75, most preferably in the range of 1.50 to 4.50; and/or
Wherein the ratio [ eta (MB)/eta (EC 1) ] between the viscosity eta (MB) of the ethylene-propylene-diene monomer rubber masterbatch composition and the viscosity eta (EC 1) of the first elastomeric ethylene copolymer is in the range of 0.10 to 1.50, more preferably in the range of 0.30 to 1.45, most preferably in the range of 0.50 to 1.25,
Wherein each viscosity is determined according to ISO 11443 at a temperature of 250 ℃ and a shear rate of 640s -1.
4. The Polyolefin Composition (PC) according to any of the preceding claims, wherein the Polyolefin Composition (PC) comprises:
i) 50.0 to 70.0 wt%, preferably 55.0 to 67.0 wt%, more preferably 60.0 to 65.0 wt% of the first polypropylene (PP 1), relative to the total weight of the Polyolefin Composition (PC);
ii) 5.0 to 20.0 wt%, preferably 7.0 to 17.0 wt%, more preferably 9.0 to 14.0 wt% of the first elastomeric ethylene copolymer (EC 1), relative to the total weight of the Polyolefin Composition (PC);
iii) 5.0 to 15.0 wt%, preferably 7.0 to 13.0 wt%, more preferably 8.0 to 12.0 wt% of an ethylene-propylene-diene monomer rubber masterbatch composition (MB), relative to the total weight of the Polyolefin Composition (PC);
iv) 5.0 to 25.0 wt%, preferably 7.0 to 20.0 wt%, more preferably 10.0 to 15.0 wt% of the filler (F), relative to the total weight of the Polyolefin Composition (PC); and
V) optionally, 0.1 to 5.0% by weight, relative to the total weight of the Polyolefin Composition (PC), of an additive (A),
Wherein the respective content of the first polypropylene (PP 1), the first elastomeric ethylene copolymer (EC 1), the ethylene-propylene-diene monomer rubber masterbatch composition (MB), the filler (F) and the optional additive (a) amounts to at least 90 wt%, more preferably at least 95 wt%, still more preferably at least 98 wt%, most preferably 100 wt%, relative to the total weight of the Polyolefin Composition (PC).
5. Polyolefin Composition (PC) according to any of the preceding claims, wherein the first polypropylene (PP 1) is a first propylene copolymer, more preferably a first propylene-ethylene copolymer having an ethylene content in the range of 2.0 to 30.0 wt%,
Wherein the melt flow rate (MFR 2) of the first propylene copolymer, more preferably of the first propylene-ethylene copolymer, measured according to ISO 1133 at 230 ℃ and 2.16kg, is preferably in the range of 8.0 to 115g/10min, most preferably in the range of 10.0 to 100g/10 min.
6. Polyolefin Composition (PC) according to any of the preceding claims, wherein the first elastomeric ethylene copolymer (EC 1) is a copolymer of ethylene with one or more comonomers selected from C5 to C12 a-olefins, preferably wherein the first elastomeric ethylene copolymer (EC 1) has one or two, preferably two, of the following properties:
a) The melt flow rate (MFR 2) measured according to ISO 1133 at 190℃and 2.16kg is in the range from 0.3 to 10g/10min, more preferably in the range from 0.5 to 7.0g/10 min; and
B) The density measured according to ISO 1183-187 is in the range 860 to 880g/cm 3, preferably in the range 865 to 875g/cm 3, most preferably in the range 867 to 871g/cm 3.
7. Polyolefin Composition (PC) according to any of the preceding claims, wherein the second polypropylene (PP 2) is a second propylene copolymer, more preferably a second propylene-ethylene copolymer having an ethylene content in the range of 2.0 to 30.0 wt%,
Wherein the melt flow rate (MFR 2) of the second propylene copolymer, more preferably of the second propylene-ethylene copolymer, measured according to ISO 1133 at 230 ℃ and 2.16kg, is preferably in the range of 0.3 to 35g/10min, most preferably in the range of 0.5 to 30g/10 min.
8. Polyolefin Composition (PC) according to any of the preceding claims, wherein the second elastomeric ethylene copolymer (EC 2) is a copolymer of ethylene with one or more comonomers selected from C5 to C12 a-olefins, preferably wherein the second elastomeric ethylene copolymer (EC 2) has one or two, preferably two, of the following properties:
a) Melt flow rate (MFR 2) measured at 190℃and 2.16kg according to ISO 1133 is in the range of 0.3 to 15g/10min, more preferably in the range of 0.5 to 10g/10 min; and
B) The density measured according to ISO 1183-187 is in the range 860 to 880g/cm 3, preferably in the range 865 to 875g/cm 3, most preferably in the range 867 to 871g/cm 3.
9. Polyolefin Composition (PC) according to any of the preceding claims, wherein the ethylene-propylene-diene monomer rubber (EPDM) is a terpolymer of ethylene, propylene and Ethylidene Norbornene (ENB), preferably having one or more, preferably all, of the following properties:
i) The Mooney viscosity M L (1+4) measured at 125℃according to ASTM D1646 is in the range of 40 to 100MU, preferably in the range of 60 to 95MU, most preferably in the range of 75 to 90 MU;
ii) the ethylene content (C2) is in the range of 50 to 90 wt%, preferably in the range of 55 to 85 wt%, most preferably in the range of 60 to 80 wt%;
iii) The ethylidene norbornene content (ENB) is in the range of 1.0 to 10.0%, preferably in the range of 2.0 to 8.0%, most preferably in the range of 3.0 to 7.0%; and
Iv) a density measured according to ISO 1183-187 in the range of 0.80 to 0.96g/cm 3, preferably in the range of 0.83 to 0.93g/cm 3, most preferably in the range of 0.86 to 0.90g/cm 3.
10. Polyolefin Composition (PC) according to any of the preceding claims, wherein the filler (F) is an inorganic filler, more preferably selected from the group comprising talc, calcium carbonate, barium sulphate, mica and mixtures thereof, most preferably the inorganic filler (F) is talc.
11. A process for producing a Polyolefin Composition (PC) according to any of the preceding claims, comprising the steps of:
a) Providing a first polypropylene (PP 1) according to any one of claims 1,2,3 or 5, a first elastomeric ethylene copolymer (EC 1) according to any one of claims 1,2,3 or 6, an ethylene-propylene-diene monomer rubber masterbatch composition (MB) according to any one of claims 1,2,3, 7, 8 or 9, a filler (F) according to claim 1 or 10 and optionally an additive (a); and
B) Blending and extruding the first polypropylene (PP 1), the first elastomeric ethylene copolymer (EC 1), the ethylene-propylene-diene monomer masterbatch composition (MB), the filler (F) and optionally additives (a) in an extruder, preferably a twin screw extruder, at a temperature in the range of 120 to 250 ℃, thereby producing the Polyolefin Composition (PC), preferably in pellet form.
12. Polyolefin Composition (PC) according to any of claims 1 to 10, wherein the Polyolefin Composition (PC) is obtainable by the process according to claim 11, more preferably by the process according to claim 11.
13. The method according to claim 11, further comprising the following step after step b):
c) Injection molding the Polyolefin Composition (PC) produced in step b) to form an injection molded article,
Wherein the injection molding is preferably gloss surface injection molding.
14. An injection molded article comprising at least 90 wt.%, more preferably at least 95 wt.%, still more preferably at least 98 wt.% of the Polyolefin Composition (PC) according to any of claims 1 to 10 or claim 12, more preferably a glossy surface injection molded article.
15. Injection molded article according to claim 14, obtainable by the method according to claim 13, more preferably obtained by the method according to claim 13.
16. The injection molded article of claim 14 or 15, which is a glossy surface injection molded article having no more than 10 pinhole defects per 150mm x 100mm surface area.
CN202180104024.XA 2021-11-11 2021-11-11 EPDM-containing polyolefin compositions with improved surface properties in injection molding Pending CN118215710A (en)

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