WO2017125459A1 - Composition contenant un copolymère d'éthylène - Google Patents

Composition contenant un copolymère d'éthylène Download PDF

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Publication number
WO2017125459A1
WO2017125459A1 PCT/EP2017/051020 EP2017051020W WO2017125459A1 WO 2017125459 A1 WO2017125459 A1 WO 2017125459A1 EP 2017051020 W EP2017051020 W EP 2017051020W WO 2017125459 A1 WO2017125459 A1 WO 2017125459A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyethylene
copolymer
calcium carbonate
polyethylene composition
composition according
Prior art date
Application number
PCT/EP2017/051020
Other languages
English (en)
Inventor
Mohammed Abdulaziz BIN RUSAYYIS
Original Assignee
Sabic Global Technologies B.V.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sabic Global Technologies B.V. filed Critical Sabic Global Technologies B.V.
Publication of WO2017125459A1 publication Critical patent/WO2017125459A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • 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
    • C08F2500/08—Low density, i.e. < 0.91 g/cm3
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

Definitions

  • composition comprising an ethylene copolymer
  • the present invention relates to a composition comprising an ethylene copolymer.
  • Compositions comprising an ethylene copolymer are used in many application fields for example in the production of pipes and films as well as in blow-molding and injection-molding applications.
  • Blow molding and injection molding may be used to make a wide variety of articles.
  • Blow molding is a molding process commonly used to produce for example household and industrial containers. In a blow molding process the polyethylene is melted and extruded into a mold and compressed air is used to inflate and shape the polymer into the desired form.
  • the injection molding process may be applied to produce caps and closures for example for containers of bottled water, juices and carbonated soft drinks, and furthermore articles used in transportation packaging such as crates, boxes, bins, pallets, pails and trays. These molding techniques are also applied to produce articles for houseware applications and packaging articles. Important properties of the polymer to be molded are its mechanical properties which, in turn, determine the properties of the final molded article.
  • ESCR environmental stress cracking resistance
  • ESCR is a key requirement for some applications such as caps and closures for carbonated soft drinks, detergents, and other chemicals.
  • the polyethylene composition according to the invention comprises a polyethylene copolymer having a density in the range between 910 and 960 kg/m 3 (according to ASTM D1505) and having an MFR 190/5 in the range between 0.1 and 120 g/10min (according to ASTM D1238 using a temperature of 190°C under a load 5kg) and calcium carbonate wherein the polyethylene copolymer has a bimodal or trimodal molar mass distribution.
  • polyethylene composition comprises between 1 and 25 % by weight of calcium carbonate (related to the total amount of polyethylene copolymer and calcium carbonate). Less than 1 % does not result in any improvement whereas an amount higher than 25% by weight influences mechanical properties.
  • the multimodal copolymers show better response to calcium carbonate compared to unimodal copolymers.
  • the copolymer may be a copolymer of ethylene and an alpha olefin selected from propylene, 1-butene, 1-hexene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene and cyclic olefins.
  • the copolymer is a copolymer of ethylene and 1-butene or 1-hexene.
  • the polyethylene copolymer has a density in the range from 930 to 960 kg/m 3 .
  • the polyethylene copolymer has an MFR 190/5 in the range between 1 and 20 g/10min. More preferably the copolymer has an MFR 190/5 in the range between 2 and 15 g/10min. MFR190/5 of the resin is determined according to ASTM D1238 using a temperature of 190°C under a load 5kg.
  • polyethylene composition comprises between 3 and 20 % by weight of calcium carbonate (related to the total amount of polyethylene copolymer and calcium carbonate).
  • the calcium carbonate has a mean particle size in the range between 0.5 ⁇ and 5 ⁇ .
  • More preferably calcium carbonate has a mean particle size of less than 2 ⁇ .
  • the mean particle size of the calcium carbonate is less than 1.5 ⁇ .
  • the calcium carbonate is surface treated with stearic acid. This treatment results in an improvement of the adhesion between the calcium carbonate particle and the polyethylene matrix which is important for the impact strength values.
  • Calcium carbonate available in the market may contain small amounts of impurities such as for example ⁇ 3% by weight magnesium carbonate.
  • the calcium carbonate can be dry-blended with the polyethylene copolymer resin and the blend can be fed into the extruder to be compounded.
  • the calcium carbonate is preferably added through a side gravimetric feeder so that the calcium carbonate particles are dispersed into the polymer while it is in the melt state in the extruder.
  • the polyethylene copolymer is preferably in a powder form.
  • the present invention results in an excellent combination of high ESCR and increased stiffness while good processability is maintained.
  • Other advantages of the present invention are improved stiffness of the product, down gauging, decreased cycle time in injection molding and a reduction of carbon footprint.
  • the polyethylene composition according to the invention is applied in the production of injection moulded articles that require high ESCR (with low molecular weight or high melt flow index for ease of processing in injection molding machines) such as for example caps and closures for chemicals, detergents, and carbonated soft drink in addition to injection molded containers.
  • high ESCR with low molecular weight or high melt flow index for ease of processing in injection molding machines
  • caps and closures for chemicals, detergents, and carbonated soft drink in addition to injection molded containers.
  • the polyethylene composition according to the invention may also be applied in technical application fields such as for example the production of pipes, electrical conduits and blow molded household and industrial containers for example those used for liquid detergents and engine oils.
  • the catalysts can be divided in three different subclasses including Ziegler Natta catalysts, Phillips catalysts and single site catalysts.
  • Suitable catalysts for the production of polyethylene according to the invention include Ziegler Natta catalysts, chromium based catalysts and single site metallocene catalysts.
  • the process and the catalyst have to form a well-balanced system.
  • the catalyst is crucial for the polymerisation reaction of multimodal polyethylene. By cooperation of process and catalyst a definite polymer structure is produced.
  • the polyethylene copolymer is prepared with a Ziegler Natta catalyst.
  • the ethylene copolymer according to the invention may comprise additives such as for example pigments, a UV stabilizer for example a sterically hindered amine, fillers, minerals, lubricants and/or other stabilisers.
  • additives such as for example pigments, a UV stabilizer for example a sterically hindered amine, fillers, minerals, lubricants and/or other stabilisers.
  • EP2199335 discloses a flame retardant composition
  • a flame retardant composition comprising an ethylene copolymer comprising polar comonomer units such as for example alkyl (meth)acrylates, (meth) acrylic acids and vinyl acetate, a silicone group containing compound, an inorganic filler material and an ethylene homo or copolymer.
  • the amount of CaCC is 35% by weight.
  • the flame retardant composition according to EP2199335 is used in wire and cable applications.
  • the polyethylene according to EP2199335 has no bimodal or trimodal molar mass distribution.
  • EP1512719 discloses a flame retardant composition
  • a flame retardant composition comprising an ethylene copolymer comprising polar comonomer units such as for example alkyl (meth)acrylates, (meth) acrylic acids and vinyl acetate, a silicone group containing compound and an inorganic filler for example calcium carbonate.
  • the amount of CaCC is 35% by weight.
  • the polyethylene according to EP1512719 has no bimodal or trimodal molar mass distribution.
  • the polyethylene composition according to the present invention does not comprise an ethylene copolymer comprising polar comonomer units such as for example alkyl
  • the polyethylene composition according to the present invention does not comprise a silicone group containing compound.
  • US20120123006 discloses a compressed crosslinked expansion molded article as part of a footwear member wherein the foaming process consists of foaming a composition comprising a mixture comprising an ethylene -alpha copolymer obtained with a metallocene catalyst and ethylene vinyl acetate and amongst others calcium carbonate.
  • the copolymer has a specific melt tension value for foam processes.
  • US20120123006 has no bimodal or trimodal molar mass distribution.
  • the polyethylene composition according to the present invention is not crosslinked.
  • the polyethylene composition according to the present invention is not suitable to be foamed.
  • EP1 146077 discloses the use of sodium benzoate as a possibility of improving ESCR of polymers to be applied in moulded articles.
  • melt flow rate is determined according to ASTM D1238 and is indicated in g/10 min. MFR is determined at 190 °C for polyethylene and determined at a loading of 5.00 kg (MFR5).
  • ESCR test was performed according to the Bent Strip method described in ASTM D 1693.
  • stiffness is determined as Young's modulus as measured by ATSM D 16993.
  • PE 1 is a polyethylene homopolymer having a density of 961 kg/m 3 with an MFR5 of 0.1 g/10 min.
  • PE 2 is a polyethylene copolymer having a density of 953 kg/m 3 with an MFR5 of 6.3 g/10 min.
  • PE 3 is a polyethylene copolymer having a density of 949 kg/m 3 with an MFR5 of 0.23 g/10 min.
  • the PE-CaC03 compositions were produced by compounding polyethylene with the stabilizers (to stabilize the polymer melt and to protect it from thermal degradation in the extruder as well as from oxidative degradation after the compounding step and calcium carbonate in different dosage percentages.
  • the calcium carbonate used is surface treated with stearic acid and has a 0.7 ⁇ mean particle size (supplied by Omya; Hydrocarb 95 T).
  • the dosage percentages are shown in Table 1.
  • the compounding was performed by using a co-rotating twin screw extruder Krauss Maffei ZE25AX560-4TX1-UG10 (L/D 56).
  • the extrusion conditions were as follows: Melt temperature 230 °C, torque 62%, screw speed 200 rpm, and output 15 kg/h.
  • Irganox 1010, Irgafos 168, Ca stearate and Zn stearate are supplied by BASF.
  • ESCR performance of polyethylene copolymers is improved when CaC03 is added. This improvement is directly proportional to the CaC03 dosage level.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition de polyéthylène comprenant un copolymère de polyéthylène ayant une densité dans la plage de 910 à 960 kg/m3 (selon ASTM D1505) et ayant une valeur MFR190/5 dans la plage de 0,1 à 120 g/10 min (selon ASTM D1238 à une température de 190 °C sous une charge de 5 kg) et un carbonate de calcium, où le copolymère de polyéthylène a une distribution des poids molaires bimodale ou trimodale.
PCT/EP2017/051020 2016-01-21 2017-01-19 Composition contenant un copolymère d'éthylène WO2017125459A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP16152234.7 2016-01-21
EP16152234 2016-01-21
US201662405273P 2016-10-07 2016-10-07
US62405273 2016-10-07

Publications (1)

Publication Number Publication Date
WO2017125459A1 true WO2017125459A1 (fr) 2017-07-27

Family

ID=55229566

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2017/051020 WO2017125459A1 (fr) 2016-01-21 2017-01-19 Composition contenant un copolymère d'éthylène

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Country Link
WO (1) WO2017125459A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1146077A1 (fr) * 2000-04-13 2001-10-17 Borealis Technology Oy Composition de polymère HDPE
EP1375584A1 (fr) * 2002-06-20 2004-01-02 Borealis Technology Oy Feuilles perméables
EP2199335A1 (fr) * 2008-12-22 2010-06-23 Borealis AG Composition ignifuge avec des propriétés mécaniques améliorées
US20120123006A1 (en) * 2009-05-29 2012-05-17 Sumitomo Chemical Company, Limited Resin composition for crosslinking/foam molding, crosslinked molded foam, member for footwear, and footwear

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1146077A1 (fr) * 2000-04-13 2001-10-17 Borealis Technology Oy Composition de polymère HDPE
EP1375584A1 (fr) * 2002-06-20 2004-01-02 Borealis Technology Oy Feuilles perméables
EP2199335A1 (fr) * 2008-12-22 2010-06-23 Borealis AG Composition ignifuge avec des propriétés mécaniques améliorées
US20120123006A1 (en) * 2009-05-29 2012-05-17 Sumitomo Chemical Company, Limited Resin composition for crosslinking/foam molding, crosslinked molded foam, member for footwear, and footwear

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