WO2011080221A2 - Procédé de préparation d'un mélange de polyoléfines chargé au carbonate de calcium - Google Patents

Procédé de préparation d'un mélange de polyoléfines chargé au carbonate de calcium Download PDF

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Publication number
WO2011080221A2
WO2011080221A2 PCT/EP2010/070672 EP2010070672W WO2011080221A2 WO 2011080221 A2 WO2011080221 A2 WO 2011080221A2 EP 2010070672 W EP2010070672 W EP 2010070672W WO 2011080221 A2 WO2011080221 A2 WO 2011080221A2
Authority
WO
WIPO (PCT)
Prior art keywords
mixture
compatibilizer
calcium carbonate
maleic anhydride
preparation
Prior art date
Application number
PCT/EP2010/070672
Other languages
English (en)
Other versions
WO2011080221A3 (fr
Inventor
Osman Ersoy
Mehmet Ali Oral
Original Assignee
Arcelik Anonim Sirketi
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 Arcelik Anonim Sirketi filed Critical Arcelik Anonim Sirketi
Priority to EP10796075A priority Critical patent/EP2519577A2/fr
Publication of WO2011080221A2 publication Critical patent/WO2011080221A2/fr
Publication of WO2011080221A3 publication Critical patent/WO2011080221A3/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/201—Pre-melted polymers
    • 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
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1535—Five-membered rings
    • C08K5/1539—Cyclic anhydrides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/24—Graft or block copolymers according to groups C08L51/00, C08L53/00 or C08L55/02; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified

Definitions

  • the present invention relates to a mixture obtained by combining
  • polyolefin materials with filler materials such as calcium carbonate, etc.
  • Filled polyolefin materials are used in various fields, in the production of washing machines, for example in the production of different elements such as cuve, detergent dispenser, pump body and receptacle.
  • Polyolefin for example polypropylene (PP) material is preferred since it has high chemical resistance and good mechanical strength values and it is cheap.
  • filler materials and strengtheners such as talc, calcium carbonate, a cheaper material with more suitable features for utilization purposes can be produced.
  • One of the ways to increase the mechanical strength of calcium carbonate filled PP material is to form a chemical bond between the calcium carbonate filler and the polypropylene matrix.
  • tensile force when a tensile force is applied to the calcium carbonate filled PP composite material, tensile force transfer between the polymeric matrix and the calsite is only provided by the physical relation (friction forces) between the calcium carbonate and the polypropylene matrix.
  • the tensile force reaches a certain value, gaps occur between the calcium carbonate and the polymeric matrix due to the polymeric matrix lengthening by stretching, and friction forces providing the tension transfer significantly decrease due to these gaps.
  • One of the ways to increase the mechanical strength values of the calcium carbonate filled PP material is to form a chemical intereaction between the calcium carbonate and the PP matrix. Decreasing filler surface energy by means of modification with substances with low molecular weight (such as calcium stearate, silane, phosphorus based materials), saturating oligomeric polymers to the filler surface are amongst the most widely known and used methods. However, although mechanical strength values are provided to be increased by applying these methods, due to the low molecular weights of the chemicals applied onto the surfaces of the filler particles, adherens of the polymeric matrix on to the filler surface is weak..
  • substances with low molecular weight such as calcium stearate, silane, phosphorus based materials
  • Filler materials are loaded into the polypropylene raw material at process temperatures higher than the melting point during the production in order to obtain a homogeneous mixture.
  • degredation starts at the organic portion of the mixture after the free radicals are formed due to the effect of the heat and high shear forces, and these radicals react with oxygen, other chemicals and main polymer chain in the environment. Further steps of the degradation causes chain-breaking and/or decrease in the molecular weight, thus causes decrease in mechanical strength values, color distortion and detoriation of fluidity characteristics.
  • chemical stabilizers are required to be added into the mixture during the process of polymeric mixture
  • Filled polyolefin materials are subjected to heat, water vapor and
  • Chemicals applied in order to form a chemical bond between the surface of the calcium carbonate and the PP matrix generally comprise free radicals. Interaction between chemicals which provide stabilization and which can be added to the formulation in order to eliminate the harmful effects of the free radicals which occur as a result of the chain-breakings which can occur due to the high shear forces during the mixture
  • the aim of the present invention is the realization of a polyolefin based mixture strengthened with a filler material and the chemical stability of which is increased.
  • the mixture realized in order to attain the aim of the present invention, explicated in the first claim and the respective claims thereof comprises a homopolymer, a filler material and at least one compatibilizer.
  • the mixture is obtained according to a mixture preparation method comprising the steps of melting the homopolymer and the compatibilizer by mixing both at temperatures higher than the melting points thereof and adding filler material to this melted mixture.
  • a chemical bond is formed between the calcium carbonate filler material and the polymer matrix and increase in mechanical strength values is provided.
  • polypropylene are loaded into the double screw extruder and after a homogeneous mixture is provided by melting the compatibilizer and the polypropylene in the double screw extruder, the calcium carbonate is added to this mixture as filler material. After the intereaction between the compatibilizer and the calcium carbonate surfaces is completed, stabilizers are added to the mixture. Thus, intereaction of the stabilizers with the compatibilizer is prevented.
  • the mixture prepared according to the mixture preparation method of the present invention comprises a homopolymer or a copolymer, a filler material and at least one compatibilizer.
  • the mixture is obtained according to a mixture preparation method
  • a semicrystalline isotactic propylene is used as the homopolymer.
  • Calcium carbonate is preferably used as the filler material.
  • a compatibilizer comprising maleic anhydrate is used as the compatibilizer. In the preferred embodiment of the present invention, percentage by weight of the maleic anhydrate is between 0.01 -10%. Afterwards, stabilizers are also added to the mixture in order to protect this mixture obtained against degradation that can occur at the production and operating conditions.
  • antioxidants [0021] In the preferred embodiment of the present invention, antioxidant
  • stabilizers are used as the stabilizer, which deactivate the radicals
  • thiosynergist thermal stabilizer which shows synergistic interaction and which provides long term thermal stabilization (LTTS) when used together with the antioxidant stabilizer.
  • the maleic anhydrite filled (grafted) stabilizer and the homopolymer, preferably polypropylene are mixed at a temperature higher than the melting points of both materials.
  • the mixing process is performed in the double screw extruder which can be heated and cooled to a temperature degree higher than the melting points of the polypropylene and the compatibilizer, and which has one or more than one temperature-controlled mixing receptacle and
  • the temperature of the mixture comprising polypropylene and maleic anhydride grafted compatibilizer loaded into the mixing receptacle of the double screw extruder is increased to 180-220°C range.
  • melting of the polypropylene and also the ring opening reaction at the maleic anhydride portion of the compatibilizer are provided. Consequently, free radicals form by means of the ring opening reaction at the maleic anhydride.
  • These opened radicals form a chemical bond with Ca +2 and CO3 "2 ions on the calcium carbonate that will be added to the mixture later.
  • the mechanical strength of the mixture is increased by forming a chemical bond between the calcium carbonate and the polypropylene.
  • extruder is realized by increasing the temperature in the mixing receptacle and by means of the arrangement of the smasher/mixer screw blocks.
  • the polypropylene and the maleic anhydride grafted compatibilizer are melted by means of the force transmitted onto the mixture by means of the smasher/mixer screw blocks rather than by means of increasing the mixing receptacle temperature.
  • Smasher/mixer screw blocks are arranged such as to increase the temperature to the degree required for the complete melting of the polypropylene and formation of the ring opening reaction in the compatibilizer comprising maleic anhydrate.
  • An arrangement having at least seven 30° stagger angles, at least four 60° stagger angles and at least six 90° stagger angles is an exemplary arrangement.
  • the double screw extruder comprises a backward conveying screw element located just after the smasher/mixer screw blocks in order to be sure that the polymeric mixture melts homogeneously and ring opening mechanism is completed.
  • Backward conveying screw element provides the pressure and the temperature of the polymer melt to increase and also prevents the not-melt polypropylene and compatibilizer granules from being conveyed further by filtering them.
  • the not-melt granules are conveyed backwards to the smasher/mixer screw blocks by means of the backward conveying screw element.
  • the double screw extruder comprises a side stuffer unit in order that calcium carbonate addition can be performed at the end of the backward
  • the double screw extruder furthermore comprises a wide pitch, deep threaded, forward conveying screw.
  • initial efficiency of calcium carbonate thus production capacity is increased.
  • ions on calcium carbonate surfaces and free radicals in the mixture and forming as a result of the ring opening reaction chemically bond with each other.
  • the temperature of the mixture is brought to 150-170°C, preferably to 165°C.
  • free radicals of the maleic anhydrate grafted polymer chemically bonding to the calcium carbonate surfaces breaking off from the filler surface and entering into ring closing reaction is minimized.
  • Antioxidant stabilizer is a mixture of a main phenolic antioxidant as the hydrogen donor and a phosphate based secondary antioxidant as the hydroperoxyde decomposer.
  • a main phenolic antioxidant as the hydrogen donor
  • a phosphate based secondary antioxidant as the hydroperoxyde decomposer.
  • the mixture comprises calcium stearate which increases the effectiveness of the stabilizer, which has acid binding properties and which reduces the friction between the mixture and the mixers at temperatures higher than the melting point of the polymer.
  • the compatibilizer in another embodiment of the present invention, the compatibilizer
  • maleic anhydride grafted homopolymer increases the tensile strength and flexural strength, it also decreases the percentage elongation value during tension and bending and makes the material brittle.
  • the compatibilizer in another embodiment of the present invention, the compatibilizer
  • maleic anhydride grafted copolymer PP (MA-g-CPP). Usage of maleic anhydride grafted copolymer increases tensile, bending and impact strengths.
  • the compatibilizer in another embodiment of the present invention, the compatibilizer
  • MA-g-SEBS maleic anhydride grafted styrene ethylene butadiene styrene
  • the compatibilizer in another embodiment of the present invention, the compatibilizer
  • MA-g-EPDM maleic anhydride grafted ethylene propylene diene terpolymer
  • maleic anhydrate grafted to an elastomeric polymer such as maleic anhydride grafted styrene ethylene butadiene styrene or maleic anhydride grafted ethylene propylene diene terpolymer increases the impact strength and elongation during tension and bending, and decreases tension/bending modulus and tensile and bending strength.
  • maleic anhydride grafted homopolymer or copolymer polypropylene is mixed with maleic anhydride grafted styrene ethylene butadiene styrene or maleic anhydride grafted ethlene propylene diene terpoylmer proportionally.
  • tensile and bending strengths, and also impact and tensile/bending percentage elongation values increase synergistically.
  • the first mixture (K1 ) used in the experiments comprises polypropylene, calcium carbonate, maleic anhydrate grafted polypropylene, antioxidant and lubricant.
  • the mixture is prepared by mixing the polypropylene, maleic anhydrate grafted polypropylene and calcium carbonate at the same time.
  • D2 a chemical bond is provided between polypropylene and maleic anhydrate grafted polypropylene by melting the polypropylene and the maleic anhydrate grafted polypropylene and mixing them, then calcium carbonate is added to this mixture, and finally the stabilizer and the lubricant are added, in other words the mixture is prepared according to the mixture preparation method of the present invention.
  • the second mixture (K2) comprises polypropylene, calcium carbonate and maleic anhydrate grafted polypropylene, and the rate of maleic anhydrate in the maleic anhydrate grafted polypropylene is more than in the first mixture.
  • the third mixture (K3) comprises polypropylene, calcium carbonate and maleic anhydrate grafted styrene ethylene butadiene styrene.
  • the fourth experiment (D4) the mixture is again prepared according to the mixture preparation method of the present invention.
  • the fourth and the fifth mixtures (K4, K5) comprise polypropylene, calcium carbonate, maleic anhydrate grafted polypropylene and maleic anhydrate grafted styrene ethylene butadiene styrene. While in the fourth mixture (K4) maleic anhydrate grafted polypropylene is more, in the fifth mixture (K5) maleic anhydrate grafted styrene ethylene butadiene styrene is more.
  • the rate of the components used in the mixtures and the results of the experiments are shown in Table 1.
  • polypropylene and the calcium carbonate is realized by using the ring opening reaction feature of the compatibilizer comprising maleic anhydride.
  • the compatibilizer comprising maleic anhydride.

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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)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

La présente invention concerne un procédé de préparation de mélanges qui permet de préparer un mélange comprenant un homopolymère, un matériau de charge et un agent de compatibilité. Le mélange est obtenu selon un procédé de préparation de mélanges comprenant les étapes consistant à faire fondre l'homopolymère et l'agent de compatibilité en les mélangeant à des températures supérieures à leurs points de fusion respectifs et à ajouter le matériau de charge au mélange fondu ainsi obtenu.
PCT/EP2010/070672 2009-12-31 2010-12-23 Procédé de préparation d'un mélange de polyoléfines chargé au carbonate de calcium WO2011080221A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP10796075A EP2519577A2 (fr) 2009-12-31 2010-12-23 Procédé de préparation d'un mélange de polyoléfines chargé au carbonate de calcium

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
TR200910098 2009-12-31
TRA2009/10098 2009-12-31

Publications (2)

Publication Number Publication Date
WO2011080221A2 true WO2011080221A2 (fr) 2011-07-07
WO2011080221A3 WO2011080221A3 (fr) 2011-09-29

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EP (1) EP2519577A2 (fr)
WO (1) WO2011080221A2 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1134422A (en) 1965-04-09 1968-11-20 Stamicarbon Process for the preparation of filled thermoplastic materials
US4120844A (en) 1977-03-09 1978-10-17 Ford Motor Company Molded calcium carbonate filled propylene resin composites
US5969027A (en) 1994-12-07 1999-10-19 Ferro Corporation Polymer blend comprising polypropylene
US6642290B1 (en) 2002-04-12 2003-11-04 Milliken & Company Highly nucleated syndiotactic polypropylene

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7501174B2 (en) * 2007-03-01 2009-03-10 Prs Mediterranean Ltd. High performance geosynthetic article
DE102007031967A1 (de) * 2007-07-10 2009-01-15 Clariant International Limited Baumaterialien auf Polyolefin-Basis

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1134422A (en) 1965-04-09 1968-11-20 Stamicarbon Process for the preparation of filled thermoplastic materials
US4120844A (en) 1977-03-09 1978-10-17 Ford Motor Company Molded calcium carbonate filled propylene resin composites
US5969027A (en) 1994-12-07 1999-10-19 Ferro Corporation Polymer blend comprising polypropylene
US6642290B1 (en) 2002-04-12 2003-11-04 Milliken & Company Highly nucleated syndiotactic polypropylene

Also Published As

Publication number Publication date
EP2519577A2 (fr) 2012-11-07
WO2011080221A3 (fr) 2011-09-29

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