WO2013150057A1 - High flow thermoplastic polyolefin with balanced mechanical performance and low shrinkage and clte - Google Patents
High flow thermoplastic polyolefin with balanced mechanical performance and low shrinkage and clte Download PDFInfo
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- WO2013150057A1 WO2013150057A1 PCT/EP2013/056997 EP2013056997W WO2013150057A1 WO 2013150057 A1 WO2013150057 A1 WO 2013150057A1 EP 2013056997 W EP2013056997 W EP 2013056997W WO 2013150057 A1 WO2013150057 A1 WO 2013150057A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
-
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/24—Crystallisation aids
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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
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
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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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
Definitions
- thermoplastic polyolefin (TPO) composition having a melt flow rate MFR 2 (230 °C) between 20 and 100 g/10 min measured according to ISO 1133, to the use of such thermoplastic polyolefin (TPO) composition for the production of injection moulded articles, e.g. automotive parts and to injection moulded articles prepared by using the thermoplastic polyolefin (TPO) composition.
- TPO thermoplastic polyolefin
- Polypropylene is the material of choice in many applications as it can be tailored to specific purposes needed.
- heterophasic polypropylenes i.e. thermoplastic polyolefins (TPOs)
- TPOs thermoplastic polyolefins
- the shrinkage and thermal expansion of a polymer are of great importance. While the shrinkage influences the processing of a part, especially in injection moulding, the coefficient of linear thermal expansion (CLTE) is important during the lifetime of the part. In particular, the coefficient of linear thermal expansion (CLTE) determines the minimum gap width between two adjacent parts, which are usually made from different materials. In order to avoid big gap widths and high stresses in the adjacent parts the coefficient of linear thermal expansion (CLTE) should thus be as low as possible.
- EP 1 477 525 Al relates to a polyolefin composition comprising a heterophasic propylene copolymer and a small amount of inorganic filler having an improved balance of thermal dimensional stability and impact strength at temperatures both above and below room temperature.
- WO 2010/006999 Al relates to polyolefin compositions comprising a heterophasic propylene copolymer, an inorganic filler, an ethylene/alpha-olefin elastomer and at least two different alpha-nucleating agents.
- US 5,854,328 A relates to a composition comprising a polyolefin elastomer and, preferably, talc.
- WO 2004/026957 Al relates to polyolefin compositions comprising high amounts of inorganic fillers.
- the described compositions have the disadvantage that the obtained materials may suffer from poor toughness, bad appearances and difficulties in processing. It should be further noted that the weight of the obtained parts considerably increases by the incorporation of such inorganic fillers. Furthermore, to minimize the need for filler incorporation the polymer itself should feature a high dimensional stability.
- the object of the present invention is to provide a polyolefin composition of low coefficient of linear thermal expansion (CLTE), low shrinkage and rather low weight, without compromising the mechanical properties of said composition.
- CLTE coefficient of linear thermal expansion
- thermoplastic polyolefin (TPO) composition having a melt flow rate MFR 2 (230 °C) between 20 and 100 g/10 min, measured according to ISO 1133, comprising
- a matrix phase comprising, preferably being, a propylene homopolymer (H-PP) and/or propylene copolymer (R-PP), and
- a dispersed phase (D) comprising, preferably being, an ethylene-Cs-Cg-a-olefin rubber copolymer (EOP),
- thermoplastic polyolefin composition (i) the xylene cold soluble (XCS) fraction of the thermoplastic polyolefin composition (TPO) has
- thermoplastic polyolefin (TPO) composition (ii) the ratio of the intrinsic viscosity (IV) of xylene cold insoluble (XCI) fraction to the intrinsic viscosity (IV) of the xylene cold soluble (XCS) fraction ([XCS]/[XCI]) of the thermoplastic polyolefin (TPO) composition is in the range of 0.75 to 1.35.
- thermoplastic polyolefin (TPO) composition in one preferred embodiment is a-nucleated.
- thermoplastic polyolefm (TPO) composition refers to a composition comprising (semi)crystalline polypropylene and an elastomer.
- TPO thermoplastic polyolefm
- the second which is commonly referred to as “reactor grade TPO” is made by first polymerizing propylene to a (semi)crystalline polypropylene and then polymerizing elastomer components, such as ethylene and propylene, in the presence of the (semi)crystalline polypropylene.
- the thermoplastic polyolefm (TPO) composition according to this invention comprises a propylene homopolymer (H-PP) or propylene copolymer (R-PP) as a polypropylene matrix and dispersed therein an ethylene-C 3 -Cg-a-olefin rubber copolymer (EOP).
- the matrix phase (M) contains (finely) dispersed inclusions being not part of the matrix phase (M) and said inclusions contain the ethylene-C 3 -Cg-a-olefin rubber copolymer (EOP).
- EOP ethylene-C 3 -Cg-a-olefin rubber copolymer
- inclusion indicates that the matrix and the inclusion form different phases within the thermoplastic polyolefm (TPO) composition, said inclusions are for instance visible by high resolution microscopy, like electron microscopy or scanning force microscopy.
- the xylene cold soluble (XCS) fraction can be seen as the rubber fraction, i.e. as the ethylene-C 3 -Cg-a-olefin rubber copolymer (EOP), whereas the xylene cold insoluble (XCI) fraction is dominated by the matrix phase (M). That is because the propylene homopolymer (H-PP) and/or the propylene copolymer (R-PP) which form the matrix phase (M) are (semi)crystalline and thus only little soluble in cold xylene. On the other hand the ethylene-C 3 -Cg-a-olefin rubber copolymer (EOP) is almost exclusively soluble in cold xylene.
- the matrix phase (M) is equally applicable for the xylene cold insoluble (XCI) fraction.
- the intrinsic viscosity (IV), melt flow rate MFR 2 and the propylene content of the matrix phase (M) and the cold insoluble (XCI) fraction are regarded to be the same throughout the invention if not otherwise indicated.
- the intrinsic viscosity (IV) and the ethylene content of the xylene cold soluble (XCS) fraction and the ethylene-C 3 -Cg-a-olefin rubber copolymer (EOP) are regarded also to be the same throughout the invention if not otherwise indicated.
- the matrix phase (M) must comprise a propylene homopolymer (H-PP) and/or a propylene copolymer (R-PP).
- the matrix phase (M) comprises a propylene homopolymer (H-PP). More preferably the main component of the matrix phase (M) is the propylene homopolymer (H-PP) and/or the propylene copolymer (R-PP).
- main component of the matrix phase (M) throughout this invention indicates that it makes up at least 50 wt- %, more preferably at least 75 wt.-%, yet more preferably of at least 90 wt.-%, still more preferably at least 95 wt.-%, like at least 99 wt.-%, of the matrix phase (M).
- the matrix phase is the propylene homopolymer (H-PP) and/or the propylene copolymer (R-PP).
- the dispersed phase (D) must comprise an ethylene-Cs-Cs-a-olefm rubber copolymer (EOP). More preferably the main component of the dispersed phase (D) is the ethylene-Cs-Cs-a-olefm rubber copolymer (EOP).
- the term "main component of the dispersed phase (D)" throughout this invention indicates that it makes up at least 50 wt.-%, more preferably at least 75 wt.-%, yet more preferably of at least 90 wt.-%, still more preferably at least 95 wt- %, like at least 99 wt.-% of the dispersed phase (D).
- the dispersed phase (D) is ethylene-Cs-Cs-a-olefm rubber copolymer (EOP).
- thermoplastic polyolefin (TPO) composition has superior properties compared to known compositions in this technical field.
- typically low intrinsic viscosity values have detrimental effect on mechanical performances.
- XCS xylene cold soluble
- EOP ethylene-C3-Cg-a-olefin rubber copolymer
- a xylene cold soluble (XCS) fraction in the range of 25 wt.-% to 45 wt.-%), based on the total weight of the thermoplastic polyolefin (TPO) composition, and keeping the amount of ethylene monomers of the ethylene-C3-Cg-a-olefin rubber copolymer (EOP) in the range of between 40 wt.-% and 60 wt.-% (i.e. ethylene content of xylene cold soluble (XCS) fraction in the range of 40 wt.-% and 60 wt- %), based on the total weight of the ethylene-C3- Cg-a-olefin rubber copolymer (EOP) (i.e.
- thermoplastic polyolefin (TPO) composition for the production of injection moulded articles, e.g. automotive parts is provided.
- an injection moulded article prepared by using said thermoplastic polyolefin (TPO) composition is provided.
- thermoplastic polyolefin (TPO) composition it is to be understood that these preferred embodiments or technical details also refer to the inventive use of the
- thermoplastic polyolefin (TPO) composition for the production of injection moulded articles, e.g. automotive parts and the inventive injection moulded article prepared by using the thermoplastic polyolefin (TPO) composition and vice versa (as far as applicable).
- TPO thermoplastic polyolefin
- the inventive thermoplastic polyolefin (TPO) composition comprises 55 wt- % to 75 wt.-%, based on the total weight of the composition, of a matrix phase (M)
- the thermoplastic polyolefin (TPO) composition of the inventive use comprises 55 wt- % to 75 wt- %, based on the total weight of the composition, of a matrix phase (M).
- the composition comprises 55 wt.-% to 70 wt.-% of a matrix phase (M) and/or 58 wt.-% to 75 wt.-% of a xylene cold insoluble (XCI) fraction.
- M matrix phase
- XCI xylene cold insoluble
- the matrix phase (M) is a propylene homopolymer.
- the matrix phase (M) and/or the xylene cold insoluble (XCI) has/have a melt flow rate MFR 2 (230 °C) of at least 50 g/10 min, preferably between 50 and 200 g/10 min, more preferably between 80 and 200 g/10 min and most preferably between 80 and 150 g/10 min, measured according to ISO 1133.
- the melt flow rate MFR 2 (230 °C) and the intrinsic viscosity (IV) are an indirect measure of the molecular weight and thus interrelated to each other, i.e. with increase of melt flow rate the intrinsic viscosity drops.
- the matrix phase (M) and/or the xylene cold insoluble (XCI) has/have an intrinsic viscosity (IV) measured according to ISO 1628 of below 1.5 dL/g, preferably between 0.7 and 1.5 dL/g, more preferably between 0.8 and 1.4 dL/g and most preferably between 0.9 and 1.3.
- the thermoplastic polyolefin (TPO) composition comprises 30 to 45 wt.-% of the ethylene-C3-Cg-a-olefin rubber copolymer (EOP) and/or 28 to 40 wt.-% of a xylene cold soluble (XCS) fraction.
- the weight percentages are based on the total weight of the thermoplastic polyolefin (TPO) composition.
- the ethylene-C3-Cg-a-olefin rubber copolymer (EOP) and/or the xylene cold solubles (XCS) has/have an ethylene content in the range of 40 wt.-% to 65 wt.-%, like in the range of 40 wt.-% to 60 wt.-%, preferably in the range of 40 wt.-% to 55 wt.-%, more preferably in the range of 45 wt.-% to 55 wt.-% and yet more preferably in the range of 45 wt.-% to 50 wt.-%, based on the total weight of the ethylene-C3-Cg-a-olefin rubber copolymer (EOP).
- EOP ethylene-C3-Cg-a-olefin rubber copolymer
- XCS xylene cold solubles
- the ethylene-C3-Cg-a-olefin rubber copolymer (EOP) is an ethylene-propylene or ethylene- 1 -octene copolymer rubber.
- the ethylene-C3-Cg-a-olefin rubber copolymer (EOP) is an ethylene- propylene copolymer rubber.
- the ethylene-C3-Cg-a-olefin rubber copolymer (EOP) and/or the xylene cold solubles (XCS) has/have an intrinsic viscosity (IV) measured according to ISO 1628 between 0.7 and 1.5 dL/g, preferably between 0.8 and 1.4 dL/g, and most preferably between 0.9 and 1.4 dL/g.
- the thermoplastic polyolefin (TPO) composition is free of inorganic filler, like filler selected from the group consisting of talc, wollastonite, mica, chalk and mixtures thereof.
- the composition has a melt flow rate MFR 2 (230 °C) between 30 and 100 g/10 min, preferably between 30 and 90 g/10 min and more preferably between 40 and 80 g/10 min, measured according to ISO 1133.
- the ratio of intrinsic viscosity (IV) of the matrix phase (M) to the intrinsic viscosity (IV) of the ethylene-Cs-Cg-a-olefin rubber copolymer (EOP) ([M]/[EOP]) and/or the ratio of the intrinsic viscosity (IV) of xylene cold insoluble (XCI) fraction to the intrinsic viscosity (IV) of the xylene cold soluble (XCS) fraction ([XCS]/[XCI]) is in the range of 0.75 to 1.35, like in the range of 0.75 to 1.30, more preferably is in the range of 0.0 to 1.30, yet more preferable in the range of 0.80 to 1.20.
- thermoplastic polyolefm (TPO) composition is a reactor grade thermoplastic polyolefm (rTPO) composition.
- thermoplastic polyolefm (TPO) composition shall be used in particular in the field of automotive applications. In this area there is a trend to larger articles. The problem of such articles is that high pressures are needed during manufacture. To reduce pressure, the melt flow of the used material should be rather low. Accordingly, the thermoplastic polyolefm (TPO) composition of the instant invention shall have a melt flow rate MFR 2 (230 °C) between 20 and 100 g/lOmin, measured according to ISO 1133.
- thermoplastic polyolefm (TPO) composition has a melt flow rate MFR 2 (230 °C) between 30 and 100 g/10 min, preferably between 30 and 90 g/10 min and more preferably between 40 and 80 g/10 min, measured according to ISO 1133.
- thermoplastic polyolefm (TPO) composition of the instant invention is featured by good mechanical properties. Accordingly, it is preferred that thermoplastic polyolefm (TPO) composition has flexural modulus of at least 850 MPa, more preferably of at least 970 MPa, yet more preferably in the range of 850 to 1,300 MPa, still more preferably in the range of 980 to 1,200 Pa.
- the measuring method of the flexural modulus is defined in the example section.
- thermoplastic polyolefin (TPO) composition has an Charpy impact strength at 23 °C of at least 5 kJ/m 2 , more preferably of at least 6 kJ/m 2 , yet more preferably in the range of 5 to 30 kJ/m 2 , still more preferably in the range of 6 to 20 kJ/m 2 , and/or has an impact strength at -20 °C of at least 2.2 kJ/m 2 , more preferably of at least 3.0 kJ/m 2 , yet more preferably in the range of 2.2 to 10 kJ/m 2 , still more preferably in the range of 3.0 to 9 kJ/m 2 .
- the measuring method of the impact strength is defined in the example section.
- thermoplastic polyolefin (TPO) composition has a coefficient of linear thermal expansion (CLTE) performed in a temperature range from -30 to +80°C of below 100 ⁇ / ⁇ , more preferably of below 96 ⁇ / ⁇ , still more preferably below 94 ⁇ / ⁇ and yet more preferably below 92 ⁇ / ⁇ .
- CLTE coefficient of linear thermal expansion
- thermoplastic polyolefin (TPO) composition has a coefficient of linear thermal expansion (CLTE) performed in a temperature range from -30 to +80°C in the range of 70 to 100 ⁇ / ⁇ , more preferably in the range of 78 to 96 ⁇ / ⁇ , still more preferably in the range of 80 to 94 ⁇ / ⁇ and yet more preferably in the range of 82 to 92 ⁇ / ⁇ .
- CLTE coefficient of linear thermal expansion
- thermoplastic polyolefin (TPO) composition has a coefficient of linear thermal expansion (CLTE) performed in a temperature range from +23 to +80°C of below 110 ⁇ / ⁇ , more preferably of below 108 ⁇ / ⁇ , still more preferably below 106 ⁇ / ⁇ and most preferably below 104 ⁇ / ⁇ .
- CLTE coefficient of linear thermal expansion
- thermoplastic polyolefin (TPO) composition has a coefficient of linear thermal expansion (CLTE) performed in a temperature range from +23 to +80°C in the range of 80 to 110 ⁇ / ⁇ , yet more preferably in the range of 82 to 108 ⁇ / ⁇ , still more preferably in the range of 84 to 106 ⁇ / ⁇ and most preferably in the range of 86 to 104 ⁇ / ⁇ .
- CLTE coefficient of linear thermal expansion
- the thermoplastic polyolefin (TPO) composition has a shrinkage on 60x60x2 mm specimens performed across flow of below 1.0 %, more preferably of below 0.95 %, still more preferably below 0.9 % and most preferably below 0.85 %.
- the thermoplastic polyolefin (TPO) composition has a shrinkage on 60x60x2 mm specimens performed across flow in the range of 0.5 to 1.0 %, yet more preferably in the range of 0.55 to 0.95 %, still more preferably in the range of 0.6 to 0.9 % and most preferably in the range of 0.65 to 0.85 %.
- thermoplastic polyolefin (TPO) composition has a shrinkage on 60x60x2 mm specimens performed in flow of below 0.9 %, more preferably of below 0.85 %, still more preferably below 0.8 % and most preferably below 0.75 %.
- the thermoplastic polyolefin (TPO) composition has a shrinkage on 60x60x2 mm specimens performed in flow in the range of 0.5 to 0.9 %, yet more preferably in the range of 0.55 to 0.85 %, still more preferably in the range of 0.6 to 0.8 % and most preferably in the range of 0.65 to 0.75 %.
- thermoplastic polyolefin (TPO) composition of the present invention is considerably decreased compared to compositions comprising inorganic filler.
- thermoplastic polyolefin (TPO) composition is free of inorganic filler, like filler selected from the group consisting of talc, wollastonite, mica, chalk and mixtures thereof. Filler are typically added in mounts of at least 5 wt.-%.
- inorganic filler like filler selected from the group consisting of talc, wollastonite, mica, chalk and mixtures thereof. Filler are typically added in mounts of at least 5 wt.-%.
- thermoplastic polyolefin (TPO) composition is regarded to be "free of inorganic filler". More precisely the thermoplastic polyolefin (TPO) composition is "free of inorganic filler” if potential inorganic fillers are used in amounts in which they cannot act as an inorganic filler, i.e. as an additive improving the impact properties of the composition.
- thermoplastic polyolefin (TPO) composition is "free of inorganic filler” if potential inorganic fillers are used in amounts below 5 wt.-%, more preferably below 3 wt.-%.
- the thermoplastic polyolefin (TPO) composition is a-nucleated and thus may contain a ⁇ -nucleating agent.
- any ⁇ -nucleating agent can be used.
- suitable a-nucleating agents are selected from the group consisting of
- salts of monocarboxylic acids and polycarboxylic acids e.g. sodium benzoate or aluminum tert-butylbenzoate, and
- dibenzylidenesorbitol e.g. 1 ,3 : 2,4 dibenzylidenesorbitol
- Ci-Cg-alkyl- substituted dibenzylidenesorbitol derivatives such as methyldibenzylidenesorbitol, ethyldibenzylidenesorbitol or dimethyldibenzylidenesorbitol (e.g.
- salts of diesters of phosphoric acid e.g. sodium 2,2'-methylenebis (4, 6,-di-tert- butylphenyl) phosphate or aluminium-hydroxy-bis[2,2'-methylene-bis(4,6-di-t- butylphenyl)phosphate] ,
- a-nucleating agent is in particular selected from the group consisting of
- salts of monocarboxylic acids and polycarboxylic acids e.g. sodium benzoate or aluminum tert-butylbenzoate
- dibenzylidenesorbitol e.g. 1 ,3 : 2,4 dibenzylidenesorbitol
- Ci-Cg-alkyl- substituted dibenzylidenesorbitol derivatives such as methyldibenzylidenesorbitol, ethyldibenzylidenesorbitol or dimethyldibenzylidenesorbitol (e.g.
- salts of diesters of phosphoric acid e.g. sodium 2,2'-methylenebis (4, 6,-di-tert- butylphenyl) phosphate or aluminium-hydroxy-bis[2,2'-methylene-bis(4,6-di-t- butylphenyl)phosphate], like aluminium-hydroxy-bis[2,2'-methylene-bis(4,6-di-tert- butylphenyl)phosphate] and Li-myristate (NA21),
- thermoplastic polyolefin (TPO) composition is preferably up to 5.0 wt.-%, e.g. below 5.0 wt.-% or below 3.0 wt.-%.
- the thermoplastic polyolefin (TPO) composition contains from equal or below 0.0001 to equal or below 1.0 wt.-%, more preferably from 0.0005 to 1.0 wt.-%, yet more preferably from 0.01 to 1.0 wt.-%, of a ⁇ -nucleating agent, in particular selected from the group consisting of dibenzylidenesorbitol (e.g.
- 1,3 : 2,4 dibenzylidene sorbitol dibenzylidenesorbitol derivative, preferably dimethyldibenzylidenesorbitol (e.g. 1,3 : 2,4 di(methylbenzylidene) sorbitol), or substituted nonitol-derivatives, such as 1,2,3,-trideoxy- 4,6:5, 7-bis-0-[(4-propylphenyl)methylene]-nonitol, vinylcycloalkane polymer, vinylalkane polymer, and mixtures thereof.
- dimethyldibenzylidenesorbitol e.g. 1,3 : 2,4 di(methylbenzylidene) sorbitol
- substituted nonitol-derivatives such as 1,2,3,-trideoxy- 4,6:5, 7-bis-0-[(4-propylphenyl)methylene]-nonitol, vinylcycloalkane polymer, vinylalkane polymer, and
- thermoplastic polyolefin (TPO) composition contains a vinylcycloalkane, like vinylcyclohexane (VCH), polymer and/or vinylalkane polymer.
- VCH vinylcyclohexane
- the thermoplastic polyolefin (TPO) composition comprises equal or less than 150 ppm, preferably 30 to 150 ppm of the a nucleating agent.
- thermoplastic polyolefin (TPO) composition is preferably prepared by first polymerizing propylene to ((semi)crystalline) polypropylene which acts as the matrix phase (M) in the
- TPO thermoplastic polyolefin
- thermoplastic polyolefin (TPO) composition is preferably a reactor grade thermoplastic polyolefin (rTPO) composition.
- the polypropylene for the matrix phase (M) is not particularly restricted and can be a propylene homopolymer (H-PP), a propylene copolymer (R-PP) or a mixture thereof, like a mixture of a propylene homopolymer (H-PP) and a propylene copolymer (R-PP).
- the matrix phase (M) is a propylene homopolymer (H-PP).
- homopolymer as used in the instant invention relates to a polypropylene that consists substantially, i.e. of at least 97 wt%, preferably of at least 98 wt%, more preferably of at least 99 wt%, still more preferably of at least 99.8 wt% of propylene units. In a preferred embodiment of the present invention, only propylene units in the propylene homopolymer are detectable.
- the propylene homopolymer (H-PP) is preferably featured by low amounts of xylene cold soluble. Accordingly it is preferred that the propylene homopolymer (H-PP) has a xylene soluble fraction of below 4.0 wt.-%, more preferably below 3.0 wt.-%, still more preferably below 2.0 wt.-%.
- the same values apply for the matrix phase (M) if it is constituted by a propylene homopolymer (H-PP) only.
- propylene copolymer and the terms elastomer, rubber, like rubber copolymer, define different embodiments.
- a "propylene copolymer”, just as the propylene homopolymer, is a (semi)crystalline polymer and thus contains rather low amounts of xylene cold solubles (XCS) whereas the elastomer or the rubber, like the rubber copolymer, according to this invention contains considerable amounts of xylene cold solubles (XCS).
- XCS xylene cold solubles
- the xylene cold soluble (XCS) content of the "propylene copolymer” is not more than 15 wt.-%, more preferably is not more than 10 wt.-%, whereas the xylene cold soluble (XCS) content of the elastomer or of the rubber, like of the rubber copolymer, is at least 20 wt.-%, more preferably is at least 30 wt.-%.
- the propylene copolymer (R-PP) has a xylene cold soluble (XCS) content of not more than 10 wt.-%, more preferably of not more than 8.0 wt.-%, like in the range of 3.0 to 8.0 wt.-%.
- XCS xylene cold soluble
- the matrix phase (M) if it is constituted by a propylene copolymer (R-PP) only.
- the matrix phase (M) is a mixture of a propylene homopolymer (H-PP) and a propylene copolymer (R-PP) the xylene cold soluble (XCS) may in the range of 2.0 to 7.0 wt.-%.
- the propylene matrix phase (M) comprises a propylene copolymer or is a mixture of propylene homopolymer and propylene copolymer
- the propylene copolymer comprises monomers copolymerizable with propylene, for example comonomers such as ethylene and C4 to C12 ⁇ -olefins, in particular ethylene and C4 to C10 a-olefins, e.g. 1-butene or 1-hexene.
- the comonomer content in the propylene matrix is in such a case preferably relatively low, i.e. up to 4.0 wt.-%, more preferably 0.1 to 3.0 wt.-%, still more preferably 0.2 to 2.0 wt.-%.
- the matrix phase (M), i.e. the propylene homopolymer and/or the propylene copolymer, and/or the xylene cold insoluble (XCI) fraction may have a melt flow rate (MFR 2 measured under a load of 2.16 kg at 230 °C according to ISO 1133) of at least 50 g/10 min.
- MFR 2 melt flow rate measured under a load of 2.16 kg at 230 °C according to ISO 1133
- the propylene homo- or copolymer matrix phase (M) has an MFR 2 between 50 and 200 g/10 min, more preferably between 80 and 200 g/10 min and most preferably between 80 and 150 g/10 min, measured according to ISO 1133.
- the propylene homo- or copolymer matrix phase (M) can be unimodal or multimodal, like bimodal. However, it is preferred that the propylene homo- or copolymer matrix phase (M) is unimodal.
- the matrix phase (M) When the matrix phase (M) is unimodal with respect to the molecular weight distribution, it may be prepared in a single stage process e.g. a slurry or gas phase process in a slurry or gas phase reactor. Preferably, the unimodal matrix phase (M) is polymerized as a slurry polymerization. Alternatively, the unimodal matrix may be produced in a multistage process using at each stage process conditions which result in similar polymer properties.
- matrix phase (M) comprises two or more different propylene polymers these may be polymers with different monomer make up and/or with different molecular weight distributions. These components may have identical or differing monomer compositions and tacticities.
- the matrix phase (M) may therefore be prepared by various processes, for example, in a single stage or multiple stages, by such polymerization methods as slurry polymerization, gas phase polymerization, bulk polymerization, solution polymerization or a combination therefrom.
- Preparation of the matrix phase (M) may also include the use of a catalyst known to those of skill in the art, such as a metallocene catalyst or a Ziegler-Natta catalyst.
- a catalyst known to those of skill in the art, such as a metallocene catalyst or a Ziegler-Natta catalyst.
- the matrix phase (M) is present in the thermoplastic polyolefin (TPO) composition in an amount of 50 to 70 wt.-%, based on the total weight of the thermoplastic polyolefin (TPO) composition.
- the thermoplastic polyolefin (TPO) composition comprises the matrix phase (M) in an amount of 55 to 70 wt.-%, based on the total weight of the thermoplastic polyolefin (TPO) composition.
- the matrix phase (M) is present in the thermoplastic polyolefm (TPO) composition in an amount of 60 to 70 wt.-%, preferably in an amount of 62.5 to 70 wt.-% and most preferably in an amount of 65 to 70 wt.-%, based on the total weight of the thermoplastic polyolefm (TPO) composition.
- the amount of xylene cold insoluble (XCI) fraction trends to be higher than the matrix phase (M) in the thermoplastic polyolefm (TPO) composition.
- the xylene cold insoluble (XCI) fraction of the thermoplastic polyolefm (TPO) composition is in the range of 55 to 80 wt.-%, more preferably in the range of 60 to 75 wt.-%, yet more preferably in the range of 63 to 71 wt.-%.
- the matrix phase (M) and/or the xylene cold insoluble (XCI) fraction has/have an intrinsic viscosity (IV; according to ISO 1628 with decalin as solvent) of below 1.5 dL/g, preferably between 0.7 and 1.5 dL/g, more preferably between 0.8 and 1.4 dL/g, more preferable between 0.9 and 1.3 dL/g and most preferably between 1 and 1.2 dL/g.
- IV intrinsic viscosity
- thermoplastic polyolefm (TPO) composition according to the invention further comprises a dispersed phase (D) comprising, preferably being, an ethylene-C 3 -Cg-a-olefin rubber copolymer (EOP).
- D dispersed phase
- EOP ethylene-C 3 -Cg-a-olefin rubber copolymer
- Important aspect of the present invention is that the ethylene-C 3 -Cg-a-olefin rubber copolymer (EOP) and thus the xylene cold soluble (XCS) fraction are present in the thermoplastic polyolefm (TPO) composition in rather high amounts. It has been observed that with low amounts of the ethylene-C 3 -Cg-a-olefin rubber copolymer (EOP), i.e. of the xylene cold soluble (XCS) fraction, the desired improvement in the coefficient of linear thermal expansion (CLTE) and/or shrinkage cannot be achieved.
- EOP ethylene-C 3 -Cg-a-olefin rubber copolymer
- XCS xylene cold soluble
- the thermoplastic polyolefm (TPO) composition comprises the ethylene-C 3 -Cg-a-olefin rubber copolymer (EOP) in an amount of 30 to 50 wt.-%, based on the total weight of the thermoplastic polyolefin (TPO) composition.
- the ethylene-C 3 -Cg-a-olefin rubber copolymer (EOP) is present in the thermoplastic polyolefin (TPO) composition in an amount of 30 to 45 wt.-%, based on the total weight of the thermoplastic polyolefin (TPO) composition.
- the ethylene-C3-Cg-a-olefin rubber copolymer (EOP) is present in the thermoplastic polyolefin (TPO) composition in an amount of 30 to 40 wt.-%, preferably in an amount of 30 to 37.5 wt.-% and most preferably in an amount of 30 to 35 wt.-%, based on the total weight of the thermoplastic polyolefin (TPO) composition.
- the amount of xylene cold soluble fraction (XCS) fraction trends to be lower than the ethylene-C3-Cg-a-olefin rubber copolymer (EOP) in the thermoplastic polyolefin (TPO) composition.
- the xylene cold soluble fraction (XCS) fraction of the thermoplastic polyolefin (TPO) composition is in the range of 20 to 45 wt.-%, more preferably in the range of 25 to 40 wt.-%, yet more preferably in the range of 29 to 37 wt.-%.
- the weight ratio of the ethylene-C 3 -Cg-a-olefin rubber copolymer (EOP) to the r matrix phase (M) [(EOP)/(M)] is below 1.0, more preferably below 0.9, still more preferably in the range of 0.3 to below 1.0, yet more preferably in the range of 0.4 to 0.9, still yet more preferably in the range of 0.4 to 0.8.
- the weight ratio of ethylene-C 3 -Cg-a-olefin rubber copolymer (EOP) to the matrix phase (M) [(EOP)/(M)] is in the range of 0.4 to 0.8 or in the range of 0.4 to 0.7.
- EOP ethylene-C 3 -Cg-a-olefin rubber copolymer
- XCS xylene cold soluble fraction
- the ethylene-C 3 -Cg-a-olefin rubber copolymer (EOP) and/or the xylene cold soluble fraction (XCS) contain(s) between 40 wt.-% to 65 wt.-%, like between 40 wt.-% to 60 wt.-%, ethylene, based on the total weight of the ethylene-C 3 -Cg-a- olefin rubber copolymer (EOP) and the xylene cold soluble fraction (XCS), respectively.
- the ethylene-C3-Cg-a-olefin rubber copolymer (EOP) and/or the xylene cold soluble fraction (XCS) has/have an ethylene content in the range of 40 wt.-% to 55 wt.-%, preferably in the range of 45 wt.-% to 55 wt.-% and more preferably in the range of 45 wt.-% to 50 wt.-%, based on the total weight of the ethylene-C3-Cg-a-olefin rubber copolymer (EOP) and the xylene cold soluble fraction (XCS), respectively.
- EOP ethylene-C3-Cg-a-olefin rubber copolymer
- XCS xylene cold soluble fraction
- the content of the a-olefin comonomer having 3 to 8 C- atoms ranges from 35 wt.-% to 60 wt.-%, like 40 wt.-% to 60 wt.-%, more preferably in the range of 45 wt.-% to 60 wt.-%, preferably in the range of 45 wt.-% to 55 wt.-%, based on the total weight of the ethylene-C3-Cg-a-olefin rubber copolymer (EOP), i.e. the xylene cold soluble fraction (XCS).
- EOP ethylene-C3-Cg-a-olefin rubber copolymer
- the comonomers are selected from the group consisting of propylene, 1 -butene, 1 - hexene, 4-methyl-l -pentane and 1 -octene. More preferably propylene, 1 -butene, 1 -hexene or 1 -octene is used as comonomer for the ethylene-C3-Cg-a-olefin rubber copolymer (EOP).
- EOP ethylene-C3-Cg-a-olefin rubber copolymer
- EPR ethylene- propylene rubber
- the ethylene-C3-Cg-a-olefin rubber copolymer (EOP) has a balanced weight average molecular weight. Small particles are formed in case the matrix and the elastomeric phase have similar molecular weight. Small particles are generally preferred, because this improves the overall properties of the thermoplastic polyolefin (TPO) composition. However, in the instant invention the matrix has by trend a high melt flow rate and thus a rather low weight average molecular weight. Accordingly, also the ethylene-C3-Cg-a-olefin rubber copolymer (EOP) should have a low weight average molecular weight in order to obtain small particles.
- IV intrinsic viscosity
- EOP ethylene-C 3 -Cg-a-olefin rubber copolymer
- XCS xylene cold soluble
- the ethylene-C 3 -Cg-a-olefin rubber copolymer (EOP) and/or the xylene cold soluble (XCS) fraction has/have an intrinsic viscosity (IV) between 0.7 and 1.5 dL/g, preferably between 0.8 and 1.5 dL/g, more preferable between 0.9 and 1.4 dL/g.
- thermoplastic polyolefin (TPO) composition comprises the matrix phase (M) and the ethylene-C 3 -Cg-a-olefin rubber copolymer (EOP) such that a specific ratio of intrinsic viscosity is reached. More precisely, the ratio of intrinsic viscosity (IV) of the matrix phase (M) to the intrinsic viscosity (IV) of the ethylene-C 3 -Cg-a-olefin rubber copolymer (EOP) ([M]/[EOP]) in the thermoplastic polyolefin (TPO) composition shall be in the range of 0.75 to 1.35, like in the range of 0.75 to 1.30.
- the ratio of intrinsic viscosity (IV) of the matrix phase (M) to the intrinsic viscosity (IV) of the ethylene-C 3 -Cg-a-olefin rubber copolymer (EOP) in the thermoplastic polyolefin (TPO) composition is in the range of 0.80 to 1.20, preferable in the range of 0.90 to 1.20.
- the ratio of the intrinsic viscosity (IV) of xylene cold insoluble (XCI) fraction to the intrinsic viscosity (IV) of the xylene cold soluble (XCS) fraction ([XCS]/[XCI]) of the thermoplastic polyolefin (TPO) composition is in the range of 0.75 to 1.35, like in the range of 0.75 to 1.30, more preferably in the range of 0.80 to 1.20, yet more preferable in the range of 0.90 to 1.20.
- the ethylene-C 3 -Cg-a-olefin rubber copolymer (EOP) may be prepared using titanium, vanadium or metallocene based catalysts capable of readily polymerizing rubbers under typical process conditions by known polymerization processes such as solution, suspension and gas-phase polymerization.
- the manner in which the thermoplastic polyolefin (TPO) composition comprising the propylene homo- or copolymer matrix phase (M) and the ethylene-C3-Cg-a-olefin rubber copolymer (EOP) as disperse phase are produced is not critical to the present invention. They can be produced by conventional melt blending of the individual components, i.e.
- thermoplastic polyolefin (TPO) composition are produced by "reactor blending" by a multistage polymerization process such as bulk polymerization, gas phase polymerization, slurry polymerization, solution polymerization or combinations thereof using conventional catalysts. Those processes are well known to one skilled in the art.
- the thermoplastic polyolefin (TPO) composition is a reactor grade thermoplastic polyolefin (rTPO) composition.
- a preferred process is a combination of bulk slurry loop reactor(s) and gas phase reactor(s).
- the propylene homopolymer (H-PP) and/or propylene copolymer (R-PP) of the matrix phase (M) can be prepared either in one or two loop reactors or in a combination of loop and gas phase reactor.
- the polymer produced in this way is transferred into another reactor and the disperse phase (D) comprising, preferably being, the ethylene-C3-Cg-a-olefin rubber copolymer (EOP), is polymerized.
- EOP ethylene-C3-Cg-a-olefin rubber copolymer
- this step is done in a gas phase polymerization.
- thermoplastic polyolefin (TPO) composition is any stereospecific catalyst for propylene polymerization which is capable of polymerizing and copolymerizing propylene and comonomers at a temperature of 40 to 1 10 °C and at a pressure from 10 to 100 bar.
- Ziegler-Natta as well as metallocene catalysts are suitable catalysts.
- One skilled in the art is aware of the various possibilities to produce such thermoplastic polyolefin (TPO) compositions and will simply find out a suitable procedure to produce suitable thermoplastic polyolefin (TPO) compositions which are used in the present invention.
- the first reactor (Rl) is preferably a slurry reactor (SR) and can be any continuous or simple stirred batch tank reactor or loop reactor operating in bulk or slurry.
- Bulk means a polymerization in a reaction medium that comprises of at least 60 % (w/w) monomer.
- the slurry reactor (SR) is preferably a (bulk) loop reactor (LR).
- the second reactor (R2) and optional further reactor are preferably gas phase reactors
- gas phase reactors can be any mechanically mixed or fluid bed reactors.
- gas phase reactors Preferably the gas phase reactors (GPR) comprise a mechanically agitated fluid bed reactor with gas velocities of at least 0.2 m/sec.
- the gas phase reactor is a fluidized bed type reactor preferably with a mechanical stirrer.
- the first reactor (Rl) is a slurry reactor (SR), like loop reactor (LR), whereas the second reactor (R2) and any further reactor are gas phase reactors (GPR).
- SR slurry reactor
- GPR gas phase reactors
- a preferred multistage process is a "loop-gas phase"-process, such as developed by Borealis A/S, Denmark (known as BORSTAR® technology) described e.g. in patent literature, such as in EP 0 887 379, WO 92/12182 WO 2004/000899, WO 2004/111095, WO 99/24478, WO 99/24479 or in WO 00/68315.
- a further suitable slurry-gas phase process is the Spheripol ® process of Basell.
- thermoplastic polyolefin (TPO) As defined above the conditions for the first reactor (Rl), 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 40 °C to 110 °C, preferably between 60 °C and 100 °C, like 68 to 90 °C
- the pressure is within the range of 20 bar to 80 bar, preferably between 40 bar to 70 bar
- reaction mixture is transferred to the second reactor (R2), i.e. gas phase reactor (GPR-1), whereby the conditions are preferably as follows:
- the temperature is within the range of 50 °C to 130 °C, preferably between 60 °C and 100 °C,
- the pressure is within the range of 5 bar to 50 bar, preferably between 15 bar to 35 bar,
- hydrogen can be added for controlling the molar mass in a manner known per se.
- the condition in any further reactor is similar to the second reactor (R2).
- the residence time can vary in the three reactor zones.
- the residence time the first reactor (Rl), i.e. the slurry reactor (SR), like a loop reactor (LR), is in the range 0.2 to 4 hours, e.g. 0.3 to 1.5 hours and the residence time in the gas phase reactor(s) 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 (Rl), 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).
- Rl 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 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 0 to 50 °C, preferably from 10 to 45 °C, and more preferably from 15 to 40 °C.
- the pressure in the prepolymerization reactor is not critical but must be sufficiently high to maintain the reaction mixture in liquid phase.
- the pressure may be from 20 to 100 bar, for example 30 to 70 bar.
- the catalyst components are preferably all introduced to the prepolymerization step.
- hydrogen may be added into the prepolymerization stage to control the molecular weight of the prepolymer as is known in the art.
- antistatic additive may be used to prevent the particles from adhering to each other or to the walls of the reactor.
- thermoplastic polyolefin (TPO) is preferably obtained by a sequential polymerization process, as described above, in the presence of a catalyst system comprising a Ziegler-Natta catalyst and optionally an external donor, preferably a catalyst system comprising three components, namely as component (i) a Ziegler-Natta procatalyst, and optionally as component (ii) an organometallic cocatalyst and as component (iii) an external donor represented by formula (Ilia) or (Illb), preferably represented by formula (Ilia).
- the procatalyst used according to the invention is prepared by
- R 1 and R 2 are independently at least a C 5 alkyl
- step d) optionally reacting the product of step c) with additional T1CI4.
- 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.
- the adduct which is first melted and then spray crystallized or emulsion solidified, is used as catalyst carrier. In the next step the spray crystallized or emulsion solidified adduct of the formula
- MgCl 2 *nROH wherein R is methyl or ethyl, preferably ethyl, and n is 1 to 6, is contacting with T1CI 4 to form a titanised carrier, followed by the steps of
- dialkylphthalate of formula (I) selected from the group consisting of propylhexylphthalate (PrHP), dioctylphthalate (DOP), di-iso- decylphthalate (DIDP), and ditridecylphthalate (DTDP), yet more preferably the dialkylphthalate of formula (I) is a dioctylphthalate (DOP), like di-iso-octylphthalate or diethylhexylphthalate, in particular diethylhexylphthalate,
- DOP dioctylphthalate
- R 1 and R 2 being methyl or ethyl, preferably ethyl
- dialkylphthalat of formula (II) being the internal donor and • recovering said transesterification product as the procatalyst composition
- the adduct of the formula MgCl 2 *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.
- This crystallized adduct is preferably used as the catalyst carrier and reacted to the procatalyst useful in the present invention as described in WO 92/19658 and WO 92/19653.
- the procatalyst used according to the invention contains 2.5 wt.-% of titanium at the most, preferably 2.2% wt.-% at the most and more preferably 2.0 wt.-% at the most.
- Its donor content is preferably between 4 to 12 wt.-% and more preferably between 6 and 10 w -%.
- 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).
- 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 (Illb).
- 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. It is in particular preferred that R 5 is selected from the group consisting of iso-propyl, iso- butyl, iso-pentyl, tert. -butyl, tert.-amyl, neopentyl, cyclopentyl, cyclohexyl,
- R x and R y can be the same or different a represent a hydrocarbon group having 1 to 12 carbon atoms.
- R x and R y are independently selected from the group consisting of linear aliphatic hydrocarbon group having 1 to 12 carbon atoms, branched aliphatic hydrocarbon group having 1 to 12 carbon atoms and cyclic aliphatic hydrocarbon group having 1 to 12 carbon atoms. It is in particular preferred that R x and R y are independently selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, octyl, decanyl, iso-propyl, iso-butyl, iso- pentyl, tert. -butyl, tert.-amyl, neopentyl, cyclopentyl, cyclohexyl, methylcyclopentyl and cycloheptyl.
- 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 of formula (Illb) is diethylaminotriethoxysilane.
- the external donor is selected from the group consisting of
- diethylaminotriethoxysilane Si(OCH 2 CH 3 ) 3 (N(CH 2 CH 3 ) 2 )]
- dicyclopentyl dimethoxy silane Si(OCH 3 ) 2 (cyclo-pentyl) 2
- diisopropyl dimethoxy silane Si(OCH 3 )2(CH(CH 3 )2)2] and mixtures thereof.
- the Ziegler-Natta procatalyst is modified by polymerizing a vinyl compound in the presence of the catalyst system, comprising the special Ziegler-Natta procatalyst (component (i)), the external donor (component (iii)) and optionally the cocatalyst (component (ii)), wherein the vinyl compound has the formula:
- thermoplastic polyolefm (TPO) composition wherein R 3 and R 4 together form a 5- or 6-membered saturated, unsaturated or aromatic ring or independently represent an alkyl group comprising 1 to 4 carbon atoms.
- the so modified catalyst is used for the preparation of the thermoplastic polyolefm (TPO) composition according to this invention to accomplish a-nucleation of the thermoplastic polyolefm (TPO) composition (BNT -technology).
- the current invention also provides injection molded articles, like (automotive) articles, comprising at least to 60 wt.-%, more preferably at least 80 wt.-%, yet more preferably at least 95 wt.-%, like consisting, of the inventive thermoplastic polyolefm (TPO) composition.
- inventive thermoplastic polyolefm (TPO) composition is especially directed to automotive articles, especially to car interiors and exteriors, like bumpers, side trims, step assists, body panels, spoilers, dashboards, interior trims and the like, comprising at least to 60 wt.-%, more preferably at least 80 wt.-%, yet more preferably at least 95 wt.-%, like consisting, of the inventive thermoplastic polyolefin (TPO) composition.
- TPO thermoplastic polyolefin
- thermoplastic polyolefin (TPO) is produced in a sequential polymerization process, i.e. in a first and optional second reactor the matrix phase (M) is produced and in a subsequent step the rubber copolymer (EOP) obtaining thereby the thermoplastic polyolefin (TPO):
- w(M) is the weight fraction [in wt.-%] of the matrix phase (M),
- w(EPO) is the weight fraction [in wt.-%] of the rubber copolymer (EOP),
- C(M) is the comonomer content [in wt.-%] of the matrix phase (M),
- C(TPO) is the comonomer content [in wt.-%] of the thermoplastic polyolefin (TPO),
- C(EOP) is the calculated comonomer content [in wt.-%] of the rubber copolymer
- w(M) is the weight fraction [in wt.-%] of the matrix phase (M)
- w(EOP) is the weight fraction [in wt.-%] of the rubber copolymer (EOP)
- XS(M) is the xylene cold soluble (XCS) content [in wt.-%] of the matrix phase (M),
- XS(TPO) is the xylene cold soluble (XCS) content [in wt.-%] of the thermoplastic polyolefm (TPO),
- XS(EOP) is the calculated xylene cold soluble (XCS) content [in wt.-%] of the rubber copolymer (EOP).
- w(M) is the weight fraction [in wt.-%] of the matrix phase (M),
- w(EOP) is the weight fraction [in wt.-%] of the rubber copolymer (EOP),
- MFR(M) is the melt flow rate MFR 2 (230 °C) [in g/lOmin] of the matrix phase (M),
- MFR(TPO) is the melt flow rate MFR 2 (230 °C) [in g/1 Omin] of the thermoplastic
- TPO polyolefm
- MFR(EOP) is the calculated melt flow rate MFR 2 (230 °C) [in g/lOmin] of the rubber copolymer (EOP).
- the comonomer content is determined by quantitative Fourier transform infrared spectroscopy (FTIR) after basic assignment calibrated via quantitative 13 C nuclear magnetic resonance (NMR) spectroscopy in a manner well known in the art. Thin films are pressed to a thickness of 250 ⁇ and spectra recorded in transmission mode.
- FTIR quantitative Fourier transform infrared spectroscopy
- NMR quantitative 13 C nuclear magnetic resonance
- the ethylene content of a polypropylene-co-ethylene copolymer is determined using the baseline corrected peak area of the quantitative bands found at 720-722 and 730-
- MFR 2 (230 °C) was measured according to ISO 1133 (230 °C, 2.16 kg load).
- MFR 2 (190 °C) was measured according to ISO 1133 (190 °C, 2.16 kg load).
- Intrinsic viscosity was measured according to DIN ISO 1628/1, October 1999 (in Decalin at 135 °C).
- Flexural Modulus, Flexural Strength and Stain at strength were determined in 3 -point- bending at 23°C according to ISO 178 on 80x10x4 mm 3 test bars injection moulded in line with EN ISO 1873-2.
- Charpy impact test The charpy notched impact strength (Charpy NIS) was measured according to ISO 179 2C / DIN 53453 at 23 °C and -20 °C, using injection molded bar test specimens of 80x10x4 mm prepared in accordance with ISO 294-1 : 1996
- Coefficient of linear thermal expansion The coefficient of linear thermal expansion (CLTE) was determined in accordance with ISO 11359-2: 1999 on 10 mm long pieces cut from the same injection molded specimens as used for the flexural modulus determination. The measurement was performed in a temperature range from -30 to +80°C at a heating rate of 1 °C/min. Additionally, the measurement was performed in a temperature range from +23 to +80°C at a heating rate of 1 °C/min.
- Shrinkage The shrinkage was measured according to an internal standard using 60x60x2 mm injection molded plaques. Measurements were performed after injection and conditioning at room temperature for at least 96h in the flow direction and perpendicular to the flow direction. Following conditions were used for injection molding: injection time: 3s, melt temperature: 240 °C, mold temperature: 50 °C, hold pressure: from 73 to 23 bars in 10 steps, hold time: 10 s, cooling time: 20 s.
- Examples IE1 and IE2 were accomplished on a 21.3 L autoclave equipped with control valves for dosing the reactor with monomers, hydrogen and for flashing.
- the dosage of monomers and hydrogen into the reactor was monitored by flow controllers and also by monitoring the mass of their respective reservoirs.
- the temperature of the reactors was controlled via cooling/heating of water in the double jacket around the reactors including sensors in both the top and bottom of the reactor.
- Helical stirrers with magnetic coupling were used for effective mixing inside the reactor and the stirring rates could be varied during the course of the reaction. The entire process was programmed ahead of time, executed and monitored by work station computers outside of the reactor cabins.
- the catalyst used in the polymerization process for examples IE1 and IE2 has been produced as follows: First, 0.1 mol of MgC ⁇ x 3 EtOH was suspended under inert conditions in 250 ml of decane in a reactor at atmospheric pressure. The solution was cooled to the temperature of -15°C and 300 ml of cold TiCLi was added while maintaining the temperature at said level. Then, the temperature of the slurry was increased slowly to 20 °C. At this temperature, 0.02 mol of dioctylphthalate (DOP) was added to the slurry. After the addition of the phthalate, the temperature was raised to 135 °C during 90 minutes and the slurry was allowed to stand for 60 minutes.
- DOP dioctylphthalate
- the reactor is initially purged with propylene and then filled with 5250g of propylene and 6 litres of Hydrogen for the pre-polymerisation.
- the catalyst as described in the previous paragraph was mixed with a solution of TEAL and U-donor at a set ratio for 5 minutes before being added to the reactor.
- the catalyst loading vessel is then flushed with 250g propylene to ensure all of the catalyst mixture is added to the reactor.
- the reactor then undergoes prepolymerisation at 23°C for 6 minutes while stirring at 350 rpm.
- the reactor is heated up to 85°C to initiate bulk conditions. While in transition the desired amount of hydrogen is added to the reactor via a flow controller. Hydrogen is always added in bulk and not added continuously during the reaction. Once the desired reactor conditioners are reached, the reactor is held at a constant pressure by dosing with propylene. This transition time to reach the bulk conditions was typically -19 minutes. After the specified bulk residence time, the reactor is purged to 0.5 bar with a stirring speed of 100 rpmto continue to a gas phase step.
- the transition to the final gas phase began.
- the stirring rate of the reactor was increased to 350 rpm and the reactor was dosed with propylene, ethylene and hydrogen as the temperature and pressure were increased to 85°C and 21 bar, respectively.
- the transition time between loop and GPR1 was typically between 8 to 10 minutes.
- the comonomers were added to maintain a desired gas ratio.
- the pressure was held constant at 21 bar by dosing with ethylene/propylene at the appropriate gas ratio.
- the amount of polymer being produced could be monitored by measuring the amount of propylene and ethylene added during the course of the reaction. After a desired split level was reached, the reactor followed the termination procedure outlined below.
- the stirring speed is reduced to 100 rpm and the gas mixture purged from the reactor to 0 barg.
- Residual gases are removed from the reactor (as well as the polymer particles) by treating the reactor with several vacuum cycles. This cycle involves put the reactor under vacuum for several minutes, filling up to ambient pressures with nitrogen and then repeating the process several times. The product is then safely removed from the reactor.
- the analytics of the prepared samples can be gathered from Table 1.
- CE2 with a MFR 2 (230 °C) of 32 g/lOmin corresponds to CEl, further comprising 16 wt-% of the commercial high density polyethylene product MG 9601 of Borealis AG having a MFR 2 (190 °C/2.16kg) of 31 g/lOmin and a density of 960 kg/m 3 .
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Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
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MX2014011604A MX352811B (en) | 2012-04-05 | 2013-04-03 | High flow thermoplastic polyolefin with balanced mechanical performance and low shrinkage and clte. |
ES13714630.4T ES2610902T3 (en) | 2012-04-05 | 2013-04-03 | High flow thermoplastic polyolefins with balanced mechanical performance and low shrinkage and CLTE |
EP13714630.4A EP2834300B1 (en) | 2012-04-05 | 2013-04-03 | High flow thermoplastic polyolefin with balanced mechanical performance and low shrinkage and clte |
KR1020147028973A KR101512279B1 (en) | 2012-04-05 | 2013-04-03 | High flow thermoplastic polyolefin with balanced mechanical performance and low shrinkage and clte |
BR112014024253-4A BR112014024253B1 (en) | 2012-04-05 | 2013-04-03 | thermoplastic polyolefin composition, use of said composition and injection molded article |
CN201380018150.9A CN104204069B (en) | 2012-04-05 | 2013-04-03 | The high fluidity TPO that mechanical performance and low-shrinkage and low coefficient of linear thermal expansion equalize |
US14/388,964 US9120922B2 (en) | 2012-04-05 | 2013-04-03 | High flow thermoplastic polyolefin with balanced mechanical performance and low shrinkage and CLTE |
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EP12163287 | 2012-04-05 | ||
EP12163287.1 | 2012-04-05 |
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WO2013150057A1 true WO2013150057A1 (en) | 2013-10-10 |
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PCT/EP2013/056997 WO2013150057A1 (en) | 2012-04-05 | 2013-04-03 | High flow thermoplastic polyolefin with balanced mechanical performance and low shrinkage and clte |
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US (1) | US9120922B2 (en) |
EP (1) | EP2834300B1 (en) |
KR (1) | KR101512279B1 (en) |
CN (1) | CN104204069B (en) |
BR (1) | BR112014024253B1 (en) |
ES (1) | ES2610902T3 (en) |
MX (1) | MX352811B (en) |
WO (1) | WO2013150057A1 (en) |
Cited By (6)
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EP3170864A1 (en) | 2015-11-17 | 2017-05-24 | Borealis AG | High flow tpo composition with excellent balance in mechanical properties for automotive interior |
WO2017085195A1 (en) | 2015-11-17 | 2017-05-26 | Borealis Ag | High flow tpo composition with excellent low temperature impact |
WO2017129721A1 (en) * | 2016-01-29 | 2017-08-03 | Borealis Ag | Heterophasic propylene copolymer with low shrinkage |
WO2017210081A1 (en) * | 2016-05-31 | 2017-12-07 | Dow Global Technologies Llc | Thermoplastic polyolefin blends including ethylene rich polymers |
EP3450472A1 (en) * | 2017-08-28 | 2019-03-06 | Borealis AG | Polypropylene composition with low shrinkage at wide application temperature range |
US10557027B2 (en) | 2015-11-17 | 2020-02-11 | Borealis Ag | High flow TPO composition with excellent tensile strain at break and low powder stickiness |
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US10479849B2 (en) * | 2015-11-02 | 2019-11-19 | Braskem America, Inc. | Low emission propylene-based polymer resins |
SG11201810592WA (en) | 2016-05-31 | 2018-12-28 | Dow Global Technologies Llc | Thermoplastic polyolefin blends having improved low temperature impact performance |
BR112018074449B1 (en) * | 2016-07-25 | 2022-12-27 | Borealis Ag | COMPOSITION, ARTICLE, USE OF A PEROXIDE, AND PROCESS FOR PREPARING THE COMPOSITION |
CN109563324B (en) * | 2016-08-03 | 2021-06-18 | 住友化学株式会社 | Heterophasic propylene polymeric material |
CN111527141B (en) * | 2017-12-22 | 2024-03-15 | 博禄塑料(上海)有限公司 | Soft polyolefin composition |
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- 2013-04-03 MX MX2014011604A patent/MX352811B/en active IP Right Grant
- 2013-04-03 EP EP13714630.4A patent/EP2834300B1/en not_active Revoked
- 2013-04-03 US US14/388,964 patent/US9120922B2/en active Active
- 2013-04-03 WO PCT/EP2013/056997 patent/WO2013150057A1/en active Application Filing
- 2013-04-03 ES ES13714630.4T patent/ES2610902T3/en active Active
- 2013-04-03 KR KR1020147028973A patent/KR101512279B1/en not_active IP Right Cessation
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US10472509B2 (en) | 2015-11-17 | 2019-11-12 | Borealis Ag | High flow TPO composition with excellent balance in mechanical properties for automotive interior |
WO2017085195A1 (en) | 2015-11-17 | 2017-05-26 | Borealis Ag | High flow tpo composition with excellent low temperature impact |
EP3170864A1 (en) | 2015-11-17 | 2017-05-24 | Borealis AG | High flow tpo composition with excellent balance in mechanical properties for automotive interior |
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US10557027B2 (en) | 2015-11-17 | 2020-02-11 | Borealis Ag | High flow TPO composition with excellent tensile strain at break and low powder stickiness |
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CN111032707A (en) * | 2017-08-28 | 2020-04-17 | 博里利斯股份公司 | Polypropylene composition with low shrinkage at wide application temperature range |
EP3450472A1 (en) * | 2017-08-28 | 2019-03-06 | Borealis AG | Polypropylene composition with low shrinkage at wide application temperature range |
CN111032707B (en) * | 2017-08-28 | 2022-03-25 | 博里利斯股份公司 | Polypropylene composition with low shrinkage at wide application temperature range |
US11578198B2 (en) | 2017-08-28 | 2023-02-14 | Borealis Ag | Polypropylene composition with low shrinkage at wide application temperature range |
Also Published As
Publication number | Publication date |
---|---|
MX352811B (en) | 2017-12-08 |
US20150057408A1 (en) | 2015-02-26 |
EP2834300B1 (en) | 2016-10-26 |
ES2610902T3 (en) | 2017-05-04 |
CN104204069A (en) | 2014-12-10 |
CN104204069B (en) | 2016-08-24 |
KR101512279B1 (en) | 2015-04-14 |
MX2014011604A (en) | 2015-04-08 |
US9120922B2 (en) | 2015-09-01 |
KR20140130236A (en) | 2014-11-07 |
BR112014024253B1 (en) | 2020-12-29 |
EP2834300A1 (en) | 2015-02-11 |
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