Classifications

• • 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
  • 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
  • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
• • 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
  • 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
  • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
  • C08F2500/05—Bimodal or multimodal molecular weight distribution
• • 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
  • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
  • C08F2500/12—Melt flow index or melt flow ratio
• • 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
  • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
  • C08F2500/27—Amount of comonomer in wt% or mol%
• • 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
  • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
  • C08F2500/30—Flexural modulus; Elasticity modulus
• • 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
  • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
  • C08F2500/35—Crystallinity, e.g. soluble or insoluble content as determined by the extraction of the polymer with a solvent
• • 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

Definitions

• HETEROPHASIC PROPYLENE COPOLYMER COMPOSITION HAVING EXCELLENT IMPACT STRENGTH, STIFFNESS AND PROCESSABILITY
• the present invention relates to a heterophasic propylene copolymer (HECO) composition, an article comprising the heterophasic propylene copolymer (HECO) composition, preferably a molded article like an injection molded article or a compression molded article, such as parts of car seats, paint pails, strollers, baby walkers, toys, heavy duty pails or transport packagings, as well as the use of the heterophasic propylene copolymer (HECO) composition for the preparation of such an article.
• HECO heterophasic propylene copolymer
• Heterophasic propylene copolymers are widely used for the preparation of moulded articles such as injection moulded articles. Typically, producers of such articles are looking for better stiffness, impact strength combined with a better processability. The balance between stiffness, processability and impact strength is often delicate as high impact strength leads to a significant reduction of stiffness and processability and vice versa. However, it is of high importance that both stiffness and impact strength remain on a high level. Accordingly, there is a need in the art for heterophasic propylene copolymer (HECO) compositions featuring excellent impact properties and stiffness. Said heterophasic propylene copolymer (HECO) compositions should have a good processability as well.
• HECO heterophasic propylene copolymer
• the present invention is directed to a heterophasic propylene copolymer (HECO) composition
• HECO heterophasic propylene copolymer
• M propylene polymer
• E elastomeric ethylene-propylene copolymer
• the elastomeric ethylene-propylene copolymer (E) has an intrinsic viscosity (IV) in the range from 3.3 to 5.0 dl/g and an ethylene content in the range from 34 to 60 wt.% based on the total weight of the elastomeric ethylene-propylene copolymer (E), wherein the xylene cold soluble fraction (XCS) is in the range from 25.0 to 50.0 wt.-%, based on the total weight of the composition.
• IV intrinsic viscosity
• XCS xylene cold soluble fraction
• the heterophasic propylene copolymer (HECO) composition has i) a melt flow rate MFR2 (230°C, 2.16 kg) determined according to ISO 1133 in the range of 10 to 30 g/10min, preferably 12 to 18 g/10 min, and/or ii) a flexural modulus measured according to ISO 178 on injection molded specimen of1000 to 1400 MPa, preferably from 1050 to 1250 MPa, and/or iii) a Charpy notched impact strength measured according to ISO 179-1eA:2000 at 23°C in the range from 14.0 to 25.0 kJ/m 2 , preferably 15.0 to 20.0 kJ/m 2 , and/or iv) Charpy notched impact strength measured according to ISO 179-1eA:2000 at -20°C in the range from 6.0 to 10.0 kJ/m 2 , more preferably in the range from 6.2 to 9.0 kJ/m 2 .
• MFR2 230°C, 2.16 kg
• the propylene polymer (M) is a propylene homopolymer, preferably the propylene polymer (M) is bimodal ortrimodal.
• the propylene polymer (M) comprises at least two propylene polymer fractions (M-A) and (M-B), preferably the at least two propylene polymer fractions (M-A) and (M-B) differ from each other by the melt flow rate MFR2 (230 °C / 2.16 kg) measured according to ISO 1133 and/or the melt flow rate MFR2 (230 °C / 2.16 kg) measured according to ISO 1133 of the propylene polymer fraction (M-B) is lower than the melt flow rate MFR2 (230 °C / 2.16 kg) measured according to ISO 1133 of the propylene polymer fraction (M-A).
• the propylene polymer (M) comprises two propylene polymer fractions (M-A) and (M-B), wherein
• the first propylene polymer fraction (M-A) has a melt flow rate MFR2 (230 °C / 2.16 kg) measured according to ISO 1133 in the range from 80.0 to 120.0 g/10min, preferably in the range from 85.0 to 110.0 g/10min, more preferably in the range from 90.0 to 105.0 g/1 Omin; and/or
• the second propylene polymer fraction (M-B) has a lower melt flow rate MFR2 (230 °C / 2.16 kg) measured according to ISO 1133 than the first propylene polymer fraction (M-A) so that the melt flow rate MFR2 (230 °C / 2.16 kg) measured according to ISO 1133 of the propylene polymer (M) is in the range from 60.0 to 90.0 g/1 Omin, preferably in the range from 65.0 to 85.0 g/1 Omin, more preferably in the range from 70.0 to 80.0 g/1 Omin.
• the propylene polymer (M) comprises three propylene polymer fractions (M-A), (M-B) and (M-C), wherein
• the first propylene polymer fraction (M-A) has a melt flow rate MFR2 (230 °C / 2.16 kg) measured according to ISO 1133 in the range from 200.0 to 250.0 g/1 Omin, preferably in the range from 204.0 to 240.0 g/1 Omin, more preferably in the range from > 204.0 to 235.0 g/1 Omin; and/or
• the second propylene polymer fraction (M-B) has a melt flow rate MFR2 (230 °C / 2.16 kg) measured according to ISO 1133 being lower than the melt flow rate MFR2 (230 °C / 2.16 kg) measured according to ISO 1133 of the first propylene polymer fraction (M-A) so that the mixture of (a) and (b) has a melt flow rate MFR2 (230 °C / 2.16 kg) measured according to ISO 1133 in the range from 150.0 to 210.0 g/1 Omin, preferably in the range from 155.0 to ⁇ 204.0 g/1 Omin, more preferably in the range from 165.0 to ⁇ 204.0 g/1 Omin, and/or (c) the third propylene polymer fraction (M-C) has a melt flow rate MFR2 (230 °C / 2.16 kg) measured according to ISO 1133 of the mixture of (a) and (b) so that the melt flow rate MFR2 (230 °C / 2.16 kg) measured according to ISO 1133
• one of the propylene polymer fractions (M-A) and (M-B) and optional (M-C) is a propylene homopolymer, preferably each of the propylene polymer fractions (M-A), (M-B) and optional (M-C) is a propylene homopolymer, and/or each of the propylene polymer fractions (M-A), (M-B) and optional (M- C) has a xylene cold soluble (XCS) content in the range from 0 to 5 wt.-%.
• XCS xylene cold soluble
• the elastomeric ethylene-propylene copolymer (E) has a comonomer content in the range from 33 to 39 wt.-%, preferably from 33.5 to 38.5 wt.-%, determined as the comonomer content of the xylene cold soluble (XCS) fraction of the heterophasic propylene copolymer (HECO).
• the elastomeric ethylene- propylene copolymer (E) comprises one or two elastomeric ethylene-propylene copolymer fractions (E-A) and optionally (E-B).
• the present invention relates to an article comprising the heterophasic propylene copolymer (HECO) composition as defined herein.
• HECO heterophasic propylene copolymer
• the article is a molded article like an injection molded article or a compression molded article, such as parts of car seats, paint pails, strollers, baby walkers, toys, heavy duty pails or transport packagings.
• the present invention relates to the use of the heterophasic propylene copolymer (HECO) composition as defined herein for the preparation of an article as defined herein.
• HECO heterophasic propylene copolymer
• heterophasic propylene copolymer (HECO) composition is described in more detail.
• HECO heterophasic propylene copolymer
• the heterophasic propylene copolymer (HECO) composition preferably comprises at least 80.0 wt.-% of a heterophasic propylene copolymer (HECO), said heterophasic propylene copolymer (HECO) comprising a matrix being a propylene polymer (M), and an elastomeric ethylene-propylene copolymer (E) being dispersed in said matrix, the elastomeric ethylene- propylene copolymer (E) having an intrinsic viscosity (IV) in the range from 3.3 to 5.0 dl/g and an ethylene content in the range from 34 to 60 wt.% based on the total weight of the elastomeric ethylene-propylene copolymer (E).
• HECO heterophasic propylene copolymer
• the heterophasic propylene copolymer (HECO) composition comprises at least 84.0 wt.-% of a heterophasic propylene copolymer (HECO), said heterophasic propylene copolymer (HECO) comprising a matrix being a propylene polymer (M), and an elastomeric ethylene-propylene copolymer (E) being dispersed in said matrix, the elastomeric ethylene-propylene copolymer (E) having an intrinsic viscosity (IV) in the range from 3.3 to 5.0 dl/g and an ethylene content in the range from 34 to 60 wt.% based on the total weight of the elastomeric ethylene-propylene copolymer (E).
• HECO heterophasic propylene copolymer
• the heterophasic propylene copolymer (HECO) composition comprises at least 86.0 wt.-% of a heterophasic propylene copolymer (HECO), said heterophasic propylene copolymer (HECO) comprising a matrix being a propylene polymer (M), and an elastomeric ethylene-propylene copolymer (E) being dispersed in said matrix, the elastomeric ethylene-propylene copolymer (E) having an intrinsic viscosity (IV) in the range from 3.3 to 5.0 dl/g and an ethylene content in the range from 34 to 60 wt.% based on the total weight of the elastomeric ethylene-propylene copolymer (E).
• HECO heterophasic propylene copolymer
• the heterophasic propylene copolymer (HECO) composition of the present invention may include additives (AD).
• the heterophasic propylene copolymer (HECO) composition comprises, more preferably consists of, 80.0 to 98.0 wt.-%, more preferably 84.0 to 96.0 wt.- %, still more preferably 86.0 to 94.0 wt.-%, like 88.0 to 92.0 wt.-% of the heterophasic propylene copolymer (HECO), and 2.0 to 20.0 wt.-%, more preferably 4.0 to 16.0 wt.-%, still more preferably 6.0 to 14.0 wt.-%, like 8.0 to 12.0 wt.-% of additives (AD), based on the overall weight of the heterophasic propylene copolymer (HECO) composition.
• the additives (AD) are described in more detail below.
• the heterophasic propylene copolymer (HECO) composition of the invention does not comprise (a) further polymer(s) different to the matrix being a propylene polymer (M) and the elastomeric ethylene-propylene copolymer (E) being dispersed in said matrix in an amount exceeding 15 wt.-%, preferably in an amount exceeding 10 wt.-%, more preferably in an amount exceeding 9 wt. %, based on the overall weight of the heterophasic propylene copolymer (HECO) composition.
• M propylene polymer
• E elastomeric ethylene-propylene copolymer
• heterophasic propylene copolymer is preferably the only polymer present in the heterophasic propylene copolymer (HECO) composition.
• the heterophasic propylene copolymer (HECO) composition consists of the heterophasic propylene copolymer (HECO) comprising a matrix being a propylene polymer (M), and an elastomeric ethylene-propylene copolymer (E) being dispersed in said matrix, the elastomeric ethylene-propylene copolymer (E) having an intrinsic viscosity (IV) in the range from 3.3 to 5.0 dl/g and an ethylene content in the range from 34 to 60 wt.% based on the total weight of the elastomeric ethylene-propylene copolymer (E).
• HECO heterophasic propylene copolymer
• M propylene polymer
• E elastomeric ethylene-propylene copolymer
• IV intrinsic viscosity
• the heterophasic propylene copolymer (HECO) composition has a moderate melt flow rate and thus provides a sufficient processability.
• the melt flow rate MFR2 (230 °C, 2.16 kg) determined according to ISO 1133 of the heterophasic propylene copolymer (HECO) composition is in the range of 10.0 to 30.0 g/10 min, more preferably in the range of 12.0 to 18.0 g/10 min, still more preferably in the range of 13.0 to 18.0 g/10 min, like in the range of 14.0 to 17.0 g/10 min.
• heterophasic propylene copolymer (HECO) composition is a rather stiff material. Accordingly, it is preferred that the heterophasic propylene copolymer (HECO) composition has a flexural modulus determined according to ISO 178 on injection molded specimen of 1000 to 1400 MPa, more preferably in the range of 1050 to 1250 MPa.
• heterophasic propylene copolymer (HECO) composition according to the present invention has excellent impact properties at room temperature as well as low temperature. Therefore, it is preferred that the heterophasic propylene copolymer (HECO) composition has a Charpy notched impact strength determined according to ISO 179 / 1eA:2000 at 23 °C in the range of 14.0 to 25.0 kJ/m 2 , more preferably in the range of 15.0 to 20.0 kJ/m 2 .
• the heterophasic propylene copolymer (HECO) composition has a Charpy notched impact strength determined according to ISO 179 / 1eA:2000 at -20 °C in the range of 6.0 to 10.0 kJ/m 2 , more preferably in the range of 6.2 to 9.0 kJ/m 2 .
• the heterophasic propylene copolymer (HECO) composition preferably has i) a melt flow rate MFR2 (230°C, 2.16 kg) determined according to ISO 1133 in the range of 10 to 30 g/10min, preferably 12 to 18 g/10 min, and/or ii) a flexural modulus measured according to ISO 178 on injection molded specimen of 1000 to 1400 MPa, preferably from 1050 to 1250 MPa, and/or iii) a Charpy notched impact strength measured according to ISO 179- 1eA:2000 at 23°C in the range from 14.0 to 25.0 kJ/m 2 , preferably 15.0 to 20.0 kJ/m 2 , and/or iv) Charpy notched impact strength measured according to ISO 179-1eA:2000 at -20°C in the range from 6.0 to 10.0 kJ/m 2 , more preferably in the range from 6.2 to 9.0 kJ/m 2 .
• MFR2 230°C,
• the heterophasic propylene copolymer (HECO) composition preferably has i) a melt flow rate MFR2 (230°C, 2.16 kg) determined according to ISO 1133 in the range of 10 to 30 g/10min, preferably 12 to 18 g/10 min, and ii) a flexural modulus measured according to ISO 178 on injection molded specimen of1000 to 1400 MPa, preferably from 1050 to 1250 MPa, and iii) a Charpy notched impact strength measured according to ISO 179- 1eA:2000 at 23°C in the range from 14.0 to 25.0 kJ/m 2 , preferably 15 to 20 kJ/m 2 , and iv) Charpy notched impact strength measured according to ISO 179-1eA:2000 at -20°C in the range from 6.0 to 10.0 kJ/m 2 , more preferably in the range from 6.2 to 9.0 kJ/m 2 .
• the heterophasic propylene copolymer (HECO) composition is thermo mechanically stable. Accordingly, it is appreciated that the heterophasic propylene copolymer (HECO) composition has a melting temperature of at least 160 °C, more preferably in the range of 162 to 170 °C, still more preferably in the range of 163 to 168 °C.
• the heterophasic propylene copolymer (HECO) composition according to the present invention comprises a matrix being propylene polymer (M) and dispersed therein an elastomeric ethylene-propylene copolymer (E).
• the matrix contains (finely) dispersed inclusions being not part of the matrix (M) and said inclusions contain the elastomeric ethylene-propylene copolymer.
• inclusion indicates that the matrix (M) and the inclusion form different phases within the heterophasic propylene copolymer (HECO) composition.
• the presence of second phases or the so called inclusions are for instance visible by high resolution microscopy, like electron microscopy or atomic force microscopy, or by dynamic mechanical thermal analysis (DMTA). Specifically, in DMTA the presence of a multiphase structure can be identified by the presence of at least two distinct glass transition temperatures.
• heterophasic propylene copolymer (HECO) composition preferably comprises
• the overall amount of the elastomeric ethylene-propylene copolymer (E) within the heterophasic propylene copolymer (HECO) composition is rather high. Therefore, it is preferred that the weight ratio between the propylene polymer (M) and the elastomeric ethylene-propylene copolymer (E) [M/E] of the heterophasic propylene copolymer (HECO) is in the range of 75/25 to 70/30, more preferably in the range of 74/26 to 71/29, yet more preferably in the range of 74/26 to 72/28.
• heterophasic propylene copolymer (HECO) composition comprises as polymer components only the propylene polymer (M) and the elastomeric ethylene-propylene copolymer (E).
• the heterophasic propylene copolymer (HECO) composition may contain further additives but no other polymer in an amount exceeding 5.0 wt.-%, more preferably exceeding 3.0 wt.-%, like exceeding 1 .0 wt.-%, based on the total heterophasic propylene copolymer (HECO) composition.
• heterophasic propylene copolymer (HECO) composition i.e. the propylene polymer (M) as well as the elastomeric ethylene-propylene copolymer (E), can comprise monomers copolymerizable with propylene, especially ethylene and optionally C4 to Cs a- olefins, in particular C4 to Cs a-olefins, e.g. 1 -butene and/or 1 -hexene.
• the heterophasic propylene copolymer (HECO) composition according to this invention comprises, especially consists of, monomers copolymerizable with propylene selected from ethylene and optionally 1 -butene and 1 -hexene. More specifically, the heterophasic propylene copolymer (HECO) composition of this invention comprises - apart from propylene - units derivable from ethylene and optionally 1 -butene. In a preferred embodiment, the heterophasic propylene copolymer (HECO) composition according to this invention comprises units derivable from ethylene and propylene only.
• the propylene polymer (M) as well as the elastomeric ethylene-propylene copolymer (E) of the heterophasic propylene copolymer (HECO) composition contain the same comonomers, like ethylene.
• the heterophasic propylene copolymer (HECO) composition preferably has a moderate total comonomer content, preferably ethylene content.
• the comonomer content of the heterophasic propylene copolymer (HECO) composition is in the range of 9.0 to 12.5 wt.-%, preferably in the range of 9.2 to 12.5 wt.-%, more preferably in the range of 9.4 to 12.3 wt.-%, like in the range of 9.6 to 12.3 wt.-%.
• the heterophasic propylene copolymer (HECO) composition contains a high amount of a xylene cold soluble (XCS) fraction.
• XCS xylene cold soluble
• the xylene cold soluble (XCS) fraction measured according to according ISO 16152 (25 °C) of the heterophasic propylene copolymer (HECO) composition is in the range of 25.0 to 50.0 wt.-%, more preferably in the range of 25.5 to 40.0 wt.-%, still more preferably in the range of 25.5 to 35.0 wt.-%, like in the range of 25.5 to 30.0 wt.-%, based on the overall weight of the heterophasic propylene copolymer (HECO) composition.
• the xylene cold soluble (XCS) fraction of the heterophasic propylene copolymer (HECO) is specified by its intrinsic viscosity.
• the xylene cold soluble fraction (XCS) of the heterophasic propylene copolymer (HECO) has an intrinsic viscosity (IV) measured according to ISO 1628/1 (at 135 °C in decalin) in the range of 3.3 to 5.0 dl/g.
• the comonomer content, i.e. ethylene content, of the xylene cold soluble (XCS) fraction of the heterophasic propylene copolymer (HECO) is in the range of 34 to 60 wt.-%, more preferably in the range of 33 to 39 wt.-%.
• the comonomers present in the xylene cold soluble (XCS) fraction are those defined above for the propylene polymer (M) and the elastomeric ethylene-propylene copolymer (E), respectively.
• the comonomer is ethylene only.
• the heterophasic propylene copolymer can be further defined by its individual components, i.e. the propylene polymer (M) and the elastomeric ethylene-propylene copolymer (E).
• the propylene polymer (M) can be a propylene copolymer or a propylene homopolymer, the latter being preferred.
• the propylene polymer (M) is a propylene copolymer
• the propylene polymer (M) comprises monomers copolymerizable with propylene, for example comonomers such as ethylene and/or C 4 to Cs a-olefins, in particular ethylene and/or C 4 to C6 a-olefins, e.g. 1- butene and/or 1 -hexene.
• the propylene polymer (M) according to this invention comprises, especially consists of, monomers copolymerizable with propylene from the group consisting of ethylene, 1 -butene and 1 -hexene.
• the propylene polymer (M) of this invention comprises - apart from propylene - units derivable from ethylene and/or 1- butene.
• the propylene polymer (M) comprises units derivable from ethylene and propylene only.
• the propylene polymer (M) according to this invention preferably has a melt flow rate MFR 2 (230 °C/2.16 kg) measured according to ISO 1133 in the range of 50.0 to 90.0 g/10 min, more preferably in the range of 60.0 to 85.0 g/10 min, still more preferably in the range of 62.0 to 80.0 g/10 min.
• the comonomer content of the propylene polymer (M) is in the range of 0.0 to 5.0 wt.-%, yet more preferably in the range of 0.0 to 3.0 wt.-%, still more preferably in the range of 0.0 to 1.0 wt.-%. It is especially preferred that the propylene polymer (M) is a propylene homopolymer.
• the comonomer content of the propylene polymer (M) is in the range of 0.0 to 0.5 wt.-%, yet more preferably in the range of 0.0 to 0.2 wt.-%.
• the propylene polymer (M) consists of propylene units, i.e. is free of comonomer units, like ethylene units.
• the propylene polymer (M) is multimodal. That is to say, the propylene polymer (M) is at least bimodal, e.g. bimodal ortrimodal.
• the propylene polymer (M) comprises, preferably consists of, a first propylene polymer fraction (M-A), a second propylene polymer fraction (M-B) and optionally a third propylene polymer fraction (M-C).
• one of the propylene polymer fractions (M-A) and (M-B) and optional (M- C) is a propylene homopolymer.
• the propylene polymer (M) is a propylene homopolymer also its fractions are propylene homopolymer fractions, i.e. each of the propylene polymer fractions (M-A), (M-B) and optional (M-C) is a propylene homopolymer.
• each of the propylene polymer fractions (M-A), (M-B) and optional (M-C) has a xylene cold soluble (XCS) content in the range from 0 to 5 wt.-%.
• the propylene polymer (M) preferably comprises at least two propylene polymer fractions, like two or three polymer fractions, all of them are preferably propylene homopolymers. Even more preferably, the propylene polymer (M) comprises, preferably consists of, a first propylene polymer fraction (M-A) and a second propylene polymer fraction (M-B), like a first propylene homopolymer fraction (M-A) and a second propylene homopolymer fraction (M-B).
• the propylene polymer (M) comprises, preferably consists of, a first propylene polymer fraction (M-A), a second propylene polymer fraction (M- B) and a third propylene polymer fraction (M-C), like a first propylene homopolymer fraction (M-A), a second propylene homopolymer fraction (M-B) and a third propylene homopolymer fraction (M-C).
• the propylene polymer (M) comprises, preferably consists of, a first propylene polymer fraction (M-A) and a second propylene polymer fraction (M-B), like a first propylene homopolymer fraction (M-A) and a second propylene homopolymer fraction (M-B), the first propylene polymer fraction (M-A) and the second propylene polymer fraction (M-B) preferably differ from each other by the melt flow rate MFR2 (230 °C / 2.16 kg) measured according to ISO 1133.
• the second propylene polymer fraction (M-B) has a lower melt flow rate MFR2 (230 °C / 2.16 kg) measured according to ISO 1133 than the first propylene polymer fraction (M-A) so that the melt flow rate MFR2 (230 °C / 2.16 kg) measured according to ISO 1133 of the propylene polymer (M) is in the range from 60.0 to 90.0 g/1 Omin, preferably in the range from 65.0 to 85.0 g/1 Omin, more preferably in the range from 70.0 to 80.0 g/1 Omin.
• the second propylene polymer fraction (M-B) has a lower melt flow rate MFR2 (230 °C / 2.16 kg) measured according to ISO 1133 than the first propylene polymer fraction (M-A) so that the melt flow rate MFR2 (230 °C / 2.16 kg) measured according to ISO 1133 of the propylene polymer (M) is in the range from 60.0 to 90.0 g/1 Omin, preferably in the range from 65.0 to 85.0 g/1 Omin, more preferably in the range from 70.0 to 80.0 g/1 Omin. It is preferred that the melt flow rate MFR2 (230 °C / 2.16 kg) measured according to ISO 1133 of the propylene polymer fraction (M-B) is lower than the melt flow rate MFR2 (230 °C /
• the propylene polymer (M) comprises, preferably consists of, a first propylene polymer fraction (M-A), a second propylene polymer fraction (M-B) and a third propylene polymer fraction (M-C), like a first propylene homopolymer fraction (M-A), a second propylene homopolymer fraction (M-B) and a third propylene polymer fraction (M-C).
• first propylene polymer fraction (M-A), the second propylene polymer fraction (M-B) and the third propylene polymer fraction (M-C), like the first propylene homopolymer fraction (M-A), the second propylene homopolymer fraction (M-B) and the third propylene polymer fraction (M-C) differ from each other by the melt flow rate MFR2 (230 °C /
• the first propylene polymer fraction (M-A) and the second propylene polymer fraction (M-B) preferably have a similar melt flow rate MFR2 (230 °C / 2.16 kg) measured according to ISO 1133. That is to say, the melt flow rate MFR2 (230 °C / 2.16 kg) measured according to ISO 1133 of the first propylene polymer fraction (M-A) and the second propylene polymer fraction (M-B) preferably do not differ more than 10 g/10min, more preferably not more than 5 g/10min, still more preferably not more than 2 g/10min.
• melt flow rate MFR2 (230 °C / 2.16 kg) measured according to ISO 1133 of the third propylene polymer fraction (M-C) differs from the MFR2 (230 °C /
• the propylene polymer (M) preferably comprises three propylene polymer fractions (M- A), (M-B) and (M-C), wherein
• the first propylene polymer fraction (M-A) has a melt flow rate MFR2 (230 °C / 2.16 kg) measured according to ISO 1133 in the range from 200.0 to 250.0 g/10min, preferably in the range from 204.0 to 240.0 g/10min, more preferably in the range from > 204.0 to 235.0 g/10min; and/or
• the second propylene polymer fraction (M-B) has a melt flow rate MFR2 (230 °C / 2.16 kg) measured according to ISO 1133 being lower than the melt flow rate MFR2 (230 °C / 2.16 kg) measured according to ISO 1133 of the first propylene polymer fraction (M-A) so that the mixture of (a) and (b) has a melt flow rate MFR2 (230 °C / 2.16 kg) measured according to ISO 1133 in the range from 150.0 to 210.0 g/10min, preferably in the range from 155.0 to ⁇ 204.0 g/10min, more preferably in the range from 165.0 to ⁇ 204.0 g/10min, and/or
• the third propylene polymer fraction (M-C) has a melt flow rate MFR2 (230 °C / 2.16 kg) measured according to ISO 1133 of the mixture of (a) and (b) so that the melt flow rate MFR2 (230 °C / 2.16 kg) measured according to ISO 1133 of the propylene polymer (M) is in the range from 50.0 to 80.0 g/10min, preferably in the range from 60.0 to 70.0 g/10min, more preferably in the range from 62.0 to 68.0 g/10min.
• the propylene polymer (M) comprises three propylene polymer fractions (M-A), (M-B) and (M-C), wherein
• the first propylene polymer fraction (M-A) has a melt flow rate MFR2 (230 °C / 2.16 kg) measured according to ISO 1133 in the range from 200.0 to 250.0 g/10min, preferably in the range from 204.0 to 240.0 g/10min, more preferably in the range from > 204.0 to 235.0 g/1 Omin; and
• each of the first propylene polymer fraction (M-A) and the second propylene polymer fraction (M-B) has a higher melt flow rate MFR2 than the third propylene polymer fraction (M-C).
• the heterophasic propylene copolymer (HECO) composition can be produced by blending the propylene polymer (M), the elastomeric ethylene-propylene copolymer (E) and the optional additives.
• the heterophasic propylene copolymer (HECO) composition is produced in a sequential step process, using reactors in serial configuration and operating at different reaction conditions. As a consequence, each fraction prepared in a specific reactor may have its own molecular weight distribution and/or comonomer content distribution.
• step (d) transferring the first propylene polymer fraction (M-A) and the second propylene polymer fraction (M-B) of step (c) into a third reactor (R3),
• step (g) polymerizing in the fourth reactor (R4) and in the presence of the first propylene polymer fraction (M-A), the second propylene polymer fraction (M-B) and the third propylene polymer fraction (M-C) obtained in step (e) propylene and ethylene to obtain the first elastomeric ethylene-propylene copolymer fraction (E-A), the first propylene polymer fraction (M-A), the second propylene polymer fraction (M-B), the third propylene polymer fraction (M-C) and the first elastomeric ethylene-propylene copolymer fraction (E-A) form the heterophasic propylene copolymer (HECO) composition.
• HECO heterophasic propylene copolymer
• the third reactor (R3) and fourth reactor (R4) are preferably gas phase reactors (GPR).
• the first reactor (R1) and second reactor (R2) are slurry reactors (SR), like a loop reactors (LR), whereas the third reactor (R3) and the fourth reactor (R4) are gas phase reactors (GPR).
• SR slurry reactors
• R3 and R4 gas phase reactors
• GPR gas phase reactors
• at least three, preferably four polymerization reactors, namely two slurry reactors (SR), like two loop reactors (LR1) and (LR2), and two gas phase reactors (GPR-1) and (GPR-2) connected in series are used. If needed prior to the first slurry reactor (SR) a pre-polymerization reactor is placed.
• a further suitable slurry-gas phase process is the Spheripol ® process of Basell.
• the conditions for the first reactor (R1) i.e. the slurry reactor (SR), like a loop reactor (LR), of step (a) may be as follows: the temperature is within the range of 50 °C to 110 °C, preferably between 60 °C and 100 °C, more preferably between 68 and 95 °C, the pressure is within the range of 20 bar to 80 bar, preferably between 40 bar to 70 bar, hydrogen can be added for controlling the molar mass in a manner known per se.
• the first reactor (R1) i.e. the slurry reactor (SR), like a loop reactor (LR)
• the pressure is within the range of 20 bar to 80 bar, preferably between 40 bar to 70 bar
• hydrogen can be added for controlling the molar mass in a manner known per se.
• step (c) the reaction mixture from step (a) is transferred to the second reactor (R2), i.e. gas phase reactor (GPR-1), i.e. to step (c), whereby the conditions in step (c) 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, hydrogen can be added for controlling the molar mass in a manner known per se.
• the second reactor i.e. gas phase reactor (GPR-1)
• GPR-1 gas phase reactor
• the residence time can vary in the three reactor zones.
• the residence time in bulk reactor, e.g. loop is in the range 0.1 to 2.5 hours, e.g. 0.15 to 1.5 hours and the residence time in gas phase reactor will generally be 0.2 to 6.0 hours, like 0.5 to 4.0 hours.
• 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 reactors (GPR).
• R1 first reactor
• SR slurry reactor
• LR loop reactor
• GPR gas phase reactors
• the process comprises also a prepolymerization with the catalyst system, as described in detail below, comprising a Ziegler-Natta procatalyst, an external donor and optionally a cocatalyst.
• the catalyst system as described in detail below, comprising a Ziegler-Natta procatalyst, an external donor and optionally a cocatalyst.
• the prepolymerization is conducted as bulk slurry polymerization in liquid propylene, i.e. the liquid phase mainly comprises propylene, with minor amount of other reactants and optionally inert components dissolved therein.
• the prepolymerization reaction is typically conducted at a temperature of 10 to 60 °C, preferably from 15 to 50 °C, and more preferably from 20 to 45 °C.
• the catalyst components are preferably all introduced to the prepolymerization step.
• the solid catalyst component (i) and the cocatalyst (ii) can be fed separately it is possible that only a part of the cocatalyst is introduced into the prepolymerization stage and the remaining part into subsequent polymerization stages. Also in such cases it is necessary to introduce so much cocatalyst into the prepolymerization stage that a sufficient polymerization reaction is obtained therein.
• heterophasic propylene copolymer (HECO) composition is obtained by a multistage polymerization process, as described above, in the presence of a catalyst system comprising as component (i) a Ziegler-Natta procatalyst which contains a trans-esterification product of a lower alcohol and a phthalic ester.
• the procatalyst used according to the invention for preparing the heterophasic propylene copolymer (HECO) composition is prepared by a) reacting a spray crystallized or emulsion solidified adduct of MgCh and a C1-C2 alcohol with TiCU b) reacting the product of stage a) with a dialkylphthalate of formula (I) wherein R 1’ and R 2’ are independently at least a C5 alkyl under conditions where a transesterification between said Ci to C2 alcohol and said dialkylphthalate of formula (I) takes place to form the internal donor c) washing the product of stage b) or d) optionally reacting the product of step c) with additional TiCU
• the procatalyst is produced as defined for example in the patent applications WO 87/07620, WO 92/19653, WO 92/19658 and EP 0 491 566.
• the content of these documents is herein included by reference.
• Ethanol is preferably used as alcohol.
• the adduct which is first melted and then spray crystallized or emulsion solidified, is used as catalyst carrier.
• the adduct of the formula MgCl2*nROH, wherein R is methyl or ethyl and n is 1 to 6, is in a preferred embodiment melted and then the melt is preferably injected by a gas into a cooled solvent or a cooled gas, whereby the adduct is crystallized into a morphologically advantageous form, as for example described in WO 87/07620.
• the procatalyst used according to the invention has been produced by using ethanol as the alcohol and dioctylphthalate (DOP) as dialkylphthalate of formula (I), yielding diethyl phthalate (DEP) as the internal donor compound.
• DOP dioctylphthalate
• DEP diethyl phthalate
• the catalyst used according to the invention is the catalyst as described in the example section; especially with the use of dioctylphthalate as dialkylphthalate of formula (I).
• the catalyst system used preferably comprises in addition to the special Ziegler-Natta procatalyst an organometallic cocatalyst as component (ii).
• the cocatalyst from the group consisting of trialkylaluminium, like triethylaluminium (TEA), dialkyl aluminium chloride and alkyl aluminium sesquichloride.
• TAA triethylaluminium
• dialkyl aluminium chloride dialkyl aluminium chloride
• alkyl aluminium sesquichloride alkyl aluminium sesquichloride.
• Component (iii) of the catalysts system used is an external donor represented by formula (Ilia) or (lllb).
• Formula (Ilia) is defined by
• R 5 represents a branched-alkyl group having 3 to 12 carbon atoms, preferably a branched-alkyl group having 3 to 6 carbon atoms, or a cyclo-alkyl having 4 to 12 carbon atoms, preferably a cyclo-alkyl having 5 to 8 carbon atoms.
• R x and R y can be the same or different a represent a hydrocarbon group having 1 to 12 carbon atoms.
• both R x and R y are the same, yet more preferably both R x and R y are an ethyl group.
• the external donor is dicyclopentyl dimethoxy silane [Si(OCH3) 2 (cyclo- pentyl) 2 ] (Donor D).
• the polymerized vinyl compound can act as an a- nucleating agent.
• the polymerized vinyl compound is the first a-nucleating agent (NU1).
• heterophasic propylene copolymer (HECO) composition of the present invention is preferably used for the production of articles, more preferably of molded articles, yet more preferably of injection molded articles or compression molded articles. Even more preferred is the use for the production of parts of car seats, paint pails, strollers, baby walkers, toys, heavy duty pails or transport packagings and the like.
• the current invention also provides articles, more preferably molded articles, like injection molded articles or compression molded articles, comprising, preferably comprising at least 60 wt.-%, more preferably at least 80 wt.-%, yet more preferably at least 95 wt.-%, like consisting of, the inventive heterophasic propylene copolymer (HECO) composition.
• HECO heterophasic propylene copolymer
• the present invention is especially directed to parts of car seats, paint pails, strollers, baby walkers, toys, heavy duty pails or transport packagings and the like, comprising, preferably comprising at least 60 wt.-%, more preferably at least 80 wt.-%, yet more preferably at least 95 wt.-%, like consisting of, the inventive heterophasic propylene copolymer (HECO) composition.
• HECO heterophasic propylene copolymer
• the present invention is also directed to the use of the polypropylene composition (C) as defined herein for the preparation of such an article.
• the present invention will now be described in further detail by the examples provided below.
• MFR 5 (190 °C) is measured according to ISO 1133 (190 °C, 5.0 kg load).
• w(PP1) is the weight fraction of the first polypropylene fraction (PP1), i.e. the product of the first reactor (R1)
• w(PP2) is the weight fraction of the second polypropylene fraction (PP2), i.e. of the polymer produced in the second reactor (R2)
• C(PP1) is the comonomer content [in wt.-%] of the first polypropylene fraction (PP1), i.e. of the product of the first reactor (R1),
• C(R2) is the comonomer content [in wt.-%] of the product obtained in the second reactor (R2), i.e. the mixture of the first polypropylene fraction (PP1) and the second polypropylene fraction (PP2),
• C(PP2) is the calculated comonomer content [in wt.-%] of the second polypropylene
• PP2 wherein w(PP1) is the weight fraction of the first polypropylene fraction (PP1), i.e. the product of the first reactor (R1), w(PP2) is the weight fraction of the second polypropylene fraction (PP2), i.e. of the polymer produced in the second reactor (R2),
• XS(PP1) is the xylene cold soluble (XCS) content [in wt.-%] of the first polypropylene fraction (PP1), i.e. of the product of the first reactor (R1), XS(R2) is the xylene cold soluble (XCS) content [in wt.-%] of the product obtained in the second reactor (R2), i.e. the mixture of the first polypropylene fraction (PP1) and the second polypropylene fraction (PP2),
• XS(PP2) is the calculated xylene cold soluble (XCS) content [in wt.-%] of the second polypropylene fraction (PP2).
• MFR(PP1) is the melt flow rate MFR2 (230 °C) [in g/10min] of the first polypropylene fraction (PP1), i.e. of the product of the first reactor (R1)
• MFR(R2) is the melt flow rate MFR2 (230 °C) [in g/10min] of the product obtained in the second reactor (R2), i.e. the mixture of the first polypropylene fraction (PP1) and the second polypropylene fraction (PP2),
• MFR(PP2) is the calculated melt flow rate MFR2 (230 °C) [in g/10min] of the second polypropylene fraction (PP2).
• C(R3) is the comonomer content [in wt.-%] of the product obtained in the third reactor (R3), i.e. the mixture of the first polypropylene fraction (PP1), the second polypropylene fraction (PP2), and the third polypropylene fraction (PP3), C(PP3) is the calculated comonomer content [in wt.-%] of the third polypropylene fraction (PP3).
• w(R2) is the weight fraction of the second reactor (R2), i.e. the mixture of the first polypropylene fraction (PP1) and the second polypropylene fraction (PP2)
• w(PP3) is the weight fraction of the third polypropylene fraction (PP3), i.e. of the polymer produced in the third reactor (R3)
• XS(R2) is the xylene cold soluble (XCS) content [in wt.-%] of the product of the second reactor (R2), i.e. of the mixture of the first polypropylene fraction (PP1) and second polypropylene fraction (PP2),
• XS(R3) is the xylene cold soluble (XCS) content [in wt.-%] of the product obtained in the third reactor (R3), i.e. the mixture of the first polypropylene fraction (PP1), the second polypropylene fraction (PP2), and the third polypropylene fraction (PP3),
• XS(PP3) is the calculated xylene cold soluble (XCS) content [in wt.-%] of the third polypropylene fraction (PP3).
• MFR(R2) is the melt flow rate MFR2 (230 °C) [in g/10min] of the product of the second reactor (R2), i.e. of the mixture of the first polypropylene fraction (PP1) and second polypropylene fraction (PP2),
• MFR(R3) is the melt flow rate MFR2 (230 °C) [in g/10min] of the product obtained in the third reactor (R3), i.e. the mixture of the first polypropylene fraction (PP1), the second polypropylene fraction (PP2), and the third polypropylene fraction (PP3),
• MFR(PP3) is the calculated melt flow rate MFR2 (230 °C) [in g/10min] of the third polypropylene fraction (PP3). Quantification of microstructure by NMR spectroscopy
• Quantitative nuclear-magnetic resonance (NMR) spectroscopy was used to quantify the comonomer content and comonomer sequence distribution of the polymers.
• Quantitative 13 C ⁇ 1 H ⁇ NMR spectra were recorded in the solution-state using a Bruker Advance III 400 NMR spectrometer operating at 400.15 and 100.62 MHz for 1 H and 13 C respectively. All spectra were recorded using a 13 C optimised 10 mm extended temperature probehead at 125°C using nitrogen gas for all pneumatics.
• Quantitative 13 C ⁇ 1 H ⁇ NMR spectra were processed, integrated and relevant quantitative properties determined from the integrals using proprietary computer programs. All chemical shifts were indirectly referenced to the central methylene group of the ethylene block (EEE) at 30.00 ppm using the chemical shift of the solvent. This approach allowed comparable referencing even when this structural unit was not present. Characteristic signals corresponding to the incorporation of ethylene were observed Cheng, H. N., Macromolecules 17 (1984), 1950).
• the tacticity distribution was quantified through integration of the methyl region between 23.6-19.7 ppm correcting for any sites not related to the stereo sequences of interest (Busico, V., Cipullo, R., Prog. Polym. Sci. 26 (2001) 443; Busico, V., Cipullo, R., Monaco, G., Vacatello, M., Segre, A.L., Macromoleucles 30 (1997) 6251). Specifically the influence of regio defects and comonomer on the quantification of the tacticity distribution was corrected for by subtraction of representative regio defect and comonomer integrals from the specific integral regions of the stereo sequences.
• the isotacticity was determined at the pentad level and reported as the percentage of isotactic pentad (mmmm) sequences with respect to all pentad sequences:
• [mmmm] % 100 * ( mmmm / sum of all pentads)
• the amount of 2,1 erythro regio defects was quantified using the average integral of the two characteristic methyl sites at 17.7 and 17.2 ppm:

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