WO2012076447A1 - Carton ondulé à base de polyoléfine - Google Patents

Carton ondulé à base de polyoléfine Download PDF

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Publication number
WO2012076447A1
WO2012076447A1 PCT/EP2011/071702 EP2011071702W WO2012076447A1 WO 2012076447 A1 WO2012076447 A1 WO 2012076447A1 EP 2011071702 W EP2011071702 W EP 2011071702W WO 2012076447 A1 WO2012076447 A1 WO 2012076447A1
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WO
WIPO (PCT)
Prior art keywords
xylene
soluble
corrugated
ranging
corrugated board
Prior art date
Application number
PCT/EP2011/071702
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English (en)
Inventor
Roberta Marzolla
Monica Galvan
Daniele Po
Original Assignee
Basell Poliolefine Italia S.R.L.
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 Basell Poliolefine Italia S.R.L. filed Critical Basell Poliolefine Italia S.R.L.
Publication of WO2012076447A1 publication Critical patent/WO2012076447A1/fr

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Classifications

    • 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
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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

Definitions

  • the present invention relates to corrugated board comprising a particular polypropylene- based composition said composition having particular features, to containers made of such corrugated boards and to a process for producing such corrugated boards.
  • Single-face and double-face corrugated board are well known material for packaging or other uses.
  • Plastic material have been widely used for this kind of application for example US 3,893,879 relates to a process for producing a plastic corrugated board.
  • crystalline polypropylene is mentioned.
  • US 5,842,315 relates to a corrugated board structure, wherein in particular the structure includes an upper layer of corrugated board formed by polyvinylchloride (PVC), polycarbonate (PC), polypropylene (PP) film or steel sheet, a bottom layer of PVC film 3, PP film, nylon film or wooden fiber skin and a middle layer of PU foam.
  • PVC polyvinylchloride
  • PC polycarbonate
  • PP polypropylene
  • corrugated board can be obtained by using polypropylene or polyethylene.
  • the polyolefin composition can be extruded at the highest speed possible
  • an object of the present invention is a corrugated board comprising a polyolefin composition comprising (per cent by weight):
  • c) from 5% to 30%, preferably from 9% to 25%, more preferably from 13% to 20% of ethylene homopolymer having a xylene soluble fraction at 25°C ranging from 2% to 30%, preferably from 3% to 20% even more preferably from 3% to 10%; the sum of a)+b) +c) being 100;
  • composition having a value of melt flow rate ranging from 0.5 to 30.0 g/10 min, preferably from 1.0 to 10.0 g/10 min, more preferably from 1.5 to 5.0 g/10.
  • the polyolefin composition to be used for the corrugated board of the present invention exhibits a flexural modulus value at least 1200 MPa, preferably it is comprised between 1200 MPa and 2000 MPa.
  • Propylene polymer (a) is selected from a propylene homopolymer and a copolymer of propylene containing at most 3 wt% of ethylene or a C4-C10 ⁇ -olefin or combination thereof. Particularly preferred is the propylene homopolymer.
  • melt flow rate of propylene polymer (a) typically ranges from 1.0 to 20.0 g/10 min, preferably from 2.0 to 15.0 g/10 min, more preferably from 3.0 to 10.0 g/10 min.
  • Elastomeric ethylene-propylene copolymer (b) can optionally comprises a diene.
  • the diene is typically in amounts ranging from 0.5 to 10 wt% with respect to the weight of copolymer (b).
  • the diene can be conjugated or not and it is preferably selected from butadiene, 1,4-hexadiene, 1,5-hexadiene, and ethylidene-norbornene-1.
  • the corrugated board object of the present invention is further endowed with an improved stress-whitening resistance. This effect improves among other things the aesthetic appearance of objects obtained by said material such as bags for example suitcases.
  • An other advantage of the corrugated board of the present invention is the surface appearance, that is improved. Furthermore when the described polyolefin composition is used for the production of the corrugated board object of the present invention it is possible to achieve high extrusion speeds.
  • the corrugated board object of the present invention can be obtained with processes commonly known in the art.
  • the corrugated boards according to the present invention can be any mono or multilayer corrugated board known in the art.
  • Fig 1 is an end elevational view of one layer of the corrugated board according to the present invention.
  • the layer comprises a top surface 1 and a bottom 2 and a corrugated sheet 3 between the two planar surfaces
  • Fig 2 is an end elevational view of a multilayer (3 layers in this case) corrugated board according to the present invention.
  • the multilayer board comprises a top and a bottom planar layer 21 and 22, corrugated sheets 23 (one for each layer), and intermediate sheets 24 between two adjacent corrugated sheets 23.
  • composition of the present invention is obtained by means of a sequential copolymerization process.
  • Said process comprising at least three sequential polymerization stages with each subsequent polymerization being conducted in the presence of the polymeric material formed in the immediately preceding polymerization reaction, wherein the polymerization stage of propylene to the crystalline polymer (a) is carried out in at least one stage, than a copolymerization stage of mixtures of ethylene with propylene (and optionally a diene) to elastomeric polymer (b) and finally a polymerization stage of ethylene to polyethylene (c) are carried out.
  • the polymerisation stages may be carried out in the presence of a stereospecific Ziegler-Natta catalyst.
  • all the polymerisation stages are carried out in the presence of a catalyst comprising a trialkylaluminum compound, optionally an electron donor, and a solid catalyst component comprising a halide or halogen-alcoholate of Ti and an electron-donor compound supported on anhydrous magnesium chloride.
  • a catalyst comprising a trialkylaluminum compound, optionally an electron donor, and a solid catalyst component comprising a halide or halogen-alcoholate of Ti and an electron-donor compound supported on anhydrous magnesium chloride.
  • the polymerisation catalyst is a Ziegler-Natta catalyst comprising a solid catalyst component comprising:
  • the internal donor is preferably selected from the esters of mono or dicarboxylic organic acids such as benzoates, malonates, phthalates and certain succinates. They are described in US patent 4522930, European patent 45977 and international patent applications WO 00/63261 and WO 01/57099, for example. Particularly suited are the phthalic acid esters and succinate acids esters. Alkylphthalates are preferred, such as diisobutyl, dioctyl and diphenyl phthalate and benzyl-butyl phthalate. Among succinates, they are preferably selected from succinates of the formula (I):
  • radicals Ri and R 2 are a C 1 -C 20 linear or branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl or alkylaryl group, optionally containing heteroatoms;
  • the radicals R3 to 5, equal to or different from each other are hydrogen or a C 1 -C 20 linear or branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl or alkylaryl group, optionally containing heteroatoms, and the radicals R3 to 5 which are joined to the same carbon atom can be linked together to form a cycle; with the proviso that when R 3 to R 5 are contemporaneously hydrogen, 5 is a radical selected from primary branched, secondary or tertiary alkyl groups, cycloalkyl, aryl, arylalkyl or alkylaryl groups having from 3 to 20 carbon atoms;
  • radicals Ri and R 2 are a C 1 -C 20 linear or branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl or alkylaryl group, optionally containing heteroatoms and the radical R3 is a linear alkyl group having at least four carbon atoms optionally containing heteroatoms.
  • the Al-alkyl compounds used as co-catalysts comprise Al-trialkyls, such as Al-triethyl, Al- triisobutyl, Al-tri-n-butyl, and linear or cyclic Al-alkyl compounds containing two or more Al atoms bonded to each other by way of O or N atoms, or SO 4 or SO 3 groups.
  • the Al-alkyl compound is generally used in such a quantity that the Al/Ti ratio be from 1 to 1000.
  • External donor (c) can be of the same type or it can be different from the succinates of formula (I) or (II).
  • Suitable external electron-donor compounds include silicon compounds, ethers, esters such as phthalates, benzoates, succinates also having a different structure from those of formula (I) or (II), amines, heterocyclic compounds and particularly 2,2,6,6-tetramethylpiperidine, ketones and the 1,3-diethers of the general formula (III):
  • R 1 and R n are the same or different and are Ci-Ci 8 alkyl, C 3 -Ci 8 cycloalkyl or C 7 -Ci 8 aryl radicals; R in and R IV are the same or different and are C 1 -C 4 alkyl radicals; or the 1,3- diethers in which the carbon atom in position 2 belongs to a cyclic or polycyclic structure made up of 5, 6 or 7 carbon atoms and containing two or three unsaturations.
  • Preferred electron-donor compounds that can be used as external donors include aromatic silicon compounds containing at least one Si-OR bond, where R is a hydrocarbon radical.
  • a particularly preferred class of external donor compounds is that of silicon compounds of formula Ra 7 Rb 8 Si(OR 9 )c, where a and b are integer from 0 to 2, c is an integer from 1 to 3 and the sum (a+b+c) is 4; R 7 , R 8 , and R 9 , are Ci-Ci 8 hydrocarbon groups optionally containing heteroatoms.
  • Examples of such preferred silicon compounds are cyclohexyltrimethoxysilane, t- butyltrimethoxysilane, t-hexyltrimethoxysilane, cyclohexylmethyldimethoxysilane, 3,3,3- trifluoropropyl-2-ethylpiperidyl-dimethoxysilane, diphenyldimethoxysilane, methyl-t- butyldimethoxysilane, dicyclopentyldimethoxysilane, 2-ethylpiperidinyl-2-t- butyldimethoxysilane, (l, l, l-trifluoro-2-propyl)-methyldimethoxysilane and (l, l, l-trifluoro-2- propyl)-2-ethylpiperidinyldimethoxysilane.
  • Particularly preferred specific examples of silicon compounds are (tert-butyl) 2 Si(OCH 3 )2, (cyclohexyl)(methyl) Si(OCH 3 ) 2 , (phenyl) 2 Si(OCH 3 ) 2 and (cyclopentyl) 2 Si(OCH 3 ) 2 .
  • electron donor compound (c) is used in such an amount to give a molar ratio between the organoaluminum compound and said electron donor compound (c) of from 0.1 to 500, more preferably from 1 to 300 and in particular from 3 to 100.
  • the solid catalyst component comprises, in addition to the above electron donors, Ti, Mg and halogen.
  • the catalyst component comprises a titanium compound, having at least a Ti-halogen bond, and the above mentioned electron donor compounds supported on a Mg halide.
  • the magnesium halide is preferably MgCl 2 in active form, which is widely known from the patent literature as a support for Ziegler-Natta catalysts. Patents USP 4,298,718 and USP 4,495,338 were the first to describe the use of these compounds in Ziegler-Natta catalysis.
  • magnesium dihalides in active form used as support or co-support in components of catalysts for the polymerisation of olefins are characterized by X-ray spectra in which the most intense diffraction line that appears in the spectrum of the non-active halide is diminished in intensity and is replaced by a halo whose maximum intensity is displaced towards lower angles relative to that of the more intense line.
  • the preferred titanium compounds are TiCl 4 and TiCl 3 ; furthermore, also Ti-haloalcoholates of formula Ti(OR)n-yXy can be used, where n is the valence of titanium, y is a number between 1 and n, X is halogen and R is a hydrocarbon radical having from 1 to 10 carbon atoms.
  • the preparation of the solid catalyst component can be carried out according to several methods, well known and described in the art.
  • the solid catalyst component can be prepared by reacting a titanium compound of formula Ti(OR)n-yXy, where n is the valence of titanium and y is a number between 1 and n, preferably TiCl 4 , with a magnesium chloride deriving from an adduct of formula MgCl 2 -pROH, where p is a number between 0.1 and 6, preferably from 2 to 3.5, and R is a hydrocarbon radical having 1-18 carbon atoms.
  • the adduct can be suitably prepared in spherical form by mixing alcohol and magnesium chloride in the presence of an inert hydrocarbon immiscible with the adduct, operating under stirring conditions at the melting temperature of the adduct (100-130° C). Then, the emulsion is quickly quenched, thereby causing the solidification of the adduct in form of spherical particles.
  • spherical adducts prepared according to this procedure are described in USP 4,399,054 and USP 4,469,648.
  • the so obtained adduct can be directly reacted with the Ti compound or it can be previously subjected to thermally controlled dealcoholation (80-130° C) so as to obtain an adduct in which the number of moles of alcohol is generally lower than 3, preferably between 0.1 and 2.5.
  • the reaction with the Ti compound can be carried out by suspending the adduct (dealcoholated or as such) in cold TiCl 4 (generally 0° C); the mixture is heated up to 80-130° C and kept at this temperature for 0.5-2 hours.
  • the treatment with TiCl 4 can be carried out one or more times.
  • the electron donor compound(s) can be added during the treatment with TiCl 4.
  • the final amount of the electron donor compound(s) is preferably such that the molar ratio with respect to the MgCl 2 is from 0.01 to 1, more preferably from 0.05 to 0.5.
  • the said catalyst components and catalysts are described in WO 00/63261 and WO 01/57099.
  • the catalysts may be precontacted with small quantities of olefin (prepolymerisation), maintaining the catalyst in suspension in a hydrocarbon solvent, and polymerising at temperatures from ambient to 60° C, thus producing a quantity of polymer from 0.5 to 3 times the weight of the catalyst.
  • the operation can also take place in liquid monomer, producing, in this case, a quantity of polymer 1000 times the weight of the catalyst.
  • the polyolefin compositions are obtained in spheroidal particle form, the particles having an average diameter from about 250 to 7,000 microns, a flowability of less than 30 seconds and a bulk density (compacted) greater than 0.4 g/ml.
  • the polymerisation stages may occur in liquid phase, in gas phase or liquid-gas phase.
  • the polymerisation of crystalline polymer (a) is carried out in liquid monomer (e.g. using liquid propylene as diluent), while the copolymerisation stages of elastomeric copolymer (b) and polyethylene (c) are carried out in gas phase.
  • all the three sequential polymerisation stages can be carried out in gas phase.
  • the reaction temperature in the polymerisation stage for the preparation of crystalline polymer (a) and in the preparation of elastomeric copolymer (b) and polyethylene (c) be the same or different, and is preferably from 40 to 100° C; more preferably, the reaction temperature ranges from 50 to 80° C in the preparation of polymer (a), and from 70 to 100° C for the preparation of polymer components (b) and (c).
  • the pressure of the polymerisation stage to prepare polymer (a), if carried out in liquid monomer, is the one which competes with the vapor pressure of the liquid propylene at the operating temperature used, and it may be modified by the vapor pressure of the small quantity of inert diluent used to feed the catalyst mixture, by the overpressure of optional monomers and by the hydrogen used as molecular weight regulator.
  • the polymerisation pressure preferably ranges from 33 to 43 bar, if done in liquid phase, and from 5 to 30 bar if done in gas phase.
  • the residence times relative to the two stages depend on the desired ratio between polymers (a) and (b) and (c), and can usually range from 15 minutes to 8 hours.
  • Conventional molecular weight regulators known in the art such as chain transfer agents (e.g. hydrogen or ZnEt 2 ), may be used.
  • additives, fillers and pigments commonly used in olefin polymers, may be added, such as nucleating agents, extension oils, mineral fillers, and other organic and inorganic pigments.
  • inorganic fillers such as talc, calcium carbonate and mineral fillers, also brings about an improvement to some mechanical properties, such as flexural modulus and HDT. Talc can also have a nucleating effect.
  • the nucleating agents are added to the compositions of the present invention in quantities ranging from 0.05 to 2% by weight, more preferably from 0.1 to 1% by weight, with respect to the total weight, for example, however the absence of nucleating agent is preferred.
  • the resistance to whitening is determined by subjecting small disc, which have a 4 cm diameter and prepared by injection moulding, prepared from the polymer being tested to the impact of a ram having a 76 g weight. Both the minimum height (h) up to the maximum height allowed by the apparatus necessary to obtain whitening, and the width (diameter) of the whitened area are recorded.
  • the polymerization was carried out in the presence of a catalyst system in a series of three reactors equipped with devices to transfer the product from one reactor to the one
  • the solid catalyst component described above was contacted at 12° C for 24 minutes with aluminium triethyl (TEAL) and dicyclopentyldimethoxysilane (DCPMS) as outside-electron- donor component.
  • TEAL aluminium triethyl
  • DCPMS dicyclopentyldimethoxysilane
  • the catalyst system is then subjected to prepolymerization by maintaining it in suspension in liquid propylene at 20° C for about 5 minutes before introducing it into the first
  • the polymerisation run is conducted in continuous in a series of three reactors equipped with devices to transfer the product from one reactor to the one immediately next to it.
  • the first reactor is a liquid phase reactor
  • the second and third reactors are fluid bed gas phase reactors.
  • Polymer (a) is prepared in the first reactor, while polymers (b) and (c) are prepared in the second and third reactor, respectively.
  • Hydrogen is used as molecular weight regulator.
  • the gas phase (propylene, ethylene and hydrogen) is continuously analysed via gas- chromatography.
  • the polymer particles are introduced in a twin screw extruder (Werner-type extruder), wherein they are mixed with 635 ppm of Irganox 1010, 635 ppm of Irgafos 168, 2450 ppm of distearyl thio-diproprionate and 270 ppm of synthetic hydrotalcite.
  • Irganox 1010 is pentaerytrityl tetrakis 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propanoate, while Irgafos 168 is tris (2,4-di-tert-butylphenyl) phosphite, both marketed by Ciba-Geigy. Particles are extruded under nitrogen atmosphere in a twin screw extruder, at a rotation speed of 250 rpm and a melt temperature of 200-250° C.
  • the polymerization has been carried out by using the same catalyst system and the same polymerization reactors of examples 1 and 2 excepting that the third gas phase reactor has not been used. Temperature and pressure are maintained constant throughout the course of the reaction. Hydrogen is used as molecular weight regulator.
  • the gas phase (propylene, ethylene and hydrogen) is continuously analysed via gas- chromatography. At the end of the run the powder is discharged and dried under a nitrogen flow. The polymerization parameters are reported on table la
  • the polymer particles are introduced in a twin screw extruder (Werner-type extruder), wherein they are mixed with 635 ppm of Irganox 1010, 635 ppm of Irgafos 168, 2450 ppm of distearyl thio-diproprionate and 270 ppm of synthetic hydrotalcite.
  • Irganox 1010 is pentaerytrityl tetrakis 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propanoate, while Irgafos 168 is tris (2,4-di-tert-butylphenyl) phosphite, both marketed by Ciba-Geigy.
  • the polymer particles are extruded under nitrogen atmosphere in a twin screw. The characteristics of the polymers have been reported in table 2

Abstract

Cette invention concerne un carton ondulé à base d'une composition de polyoléfine comprenant (en pourcentage en poids) : a) de 50 à 85 % d'un polymère de propylène ayant une fraction soluble dans le xylène mesurée à 25°C inférieure à 3 % ; b) de 5 à 20 % d'un copolymère d'éthylène et de propylène, ledit copolymère ayant une quantité de motifs récurrents dérivés de l'éthylène allant de 30 à 60 %, et étant partiellement soluble dans le xylène à 25°C ; la fraction polymère soluble dans le xylène à 25°C ayant une valeur de viscosité intrinsèque allant de 2,0 à 4,0 dl/g ; et c) de 5 à 30 % d'un homopolymère d'éthylène ayant une fraction soluble dans le xylène à 25°C allant de 5 à 30 % ; la somme de a) +b) +c) étant de 100 ; ladite composition ayant une valeur d'écoulement à chaud allant de 0,5 à 30,0 g/10 mn.
PCT/EP2011/071702 2010-12-07 2011-12-05 Carton ondulé à base de polyoléfine WO2012076447A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP10193904 2010-12-07
EP10193904.9 2010-12-07
US42164710P 2010-12-10 2010-12-10
US61/421,647 2010-12-10

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WO2012076447A1 true WO2012076447A1 (fr) 2012-06-14

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Citations (13)

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Publication number Priority date Publication date Assignee Title
US3893879A (en) 1971-10-22 1975-07-08 Mitsui Toatsu Chemicals Process for producing a plastic corrugated board and apparatus therefor
US4298718A (en) 1968-11-25 1981-11-03 Montecatini Edison S.P.A. Catalysts for the polymerization of olefins
EP0045977A2 (fr) 1980-08-13 1982-02-17 Montedison S.p.A. Composants et catalyseurs pour la polymérisation d'oléfines
US4399054A (en) 1978-08-22 1983-08-16 Montedison S.P.A. Catalyst components and catalysts for the polymerization of alpha-olefins
US4469648A (en) 1978-06-13 1984-09-04 Montedison S.P.A. Process for preparing spheroidally shaped products, solid at room temperature
US4472524A (en) 1982-02-12 1984-09-18 Montedison S.P.A. Components and catalysts for the polymerization of olefins
US4495338A (en) 1968-11-21 1985-01-22 Montecatini Edison S.P.A. Components of catalysts for the polymerization of olefins
US4507348A (en) * 1980-08-29 1985-03-26 Mitsui Petrochemical Industries Corrugated board-like sheet made of synthetic resin
US4522930A (en) 1982-02-12 1985-06-11 Montedison S.P.A. Components and catalysts for the polymerization of olefins
US5842315A (en) 1997-03-24 1998-12-01 Tung Yik Trading Co., Ltd. Corrugated board structure
WO2000063261A1 (fr) 1999-04-15 2000-10-26 Basell Technology Company B.V. Constituants et catalyseurs de polymerisation d'olefines
WO2001057099A1 (fr) 2000-02-02 2001-08-09 Basell Technology Company B.V. Composants et catalyseurs destines a la polymerisation d'olefines
EP1849826A1 (fr) * 2006-04-26 2007-10-31 Borealis Technology Oy Article en transparentes polyoléfiniques soumis a un traitement thermique

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4495338A (en) 1968-11-21 1985-01-22 Montecatini Edison S.P.A. Components of catalysts for the polymerization of olefins
US4298718A (en) 1968-11-25 1981-11-03 Montecatini Edison S.P.A. Catalysts for the polymerization of olefins
US3893879A (en) 1971-10-22 1975-07-08 Mitsui Toatsu Chemicals Process for producing a plastic corrugated board and apparatus therefor
US4469648A (en) 1978-06-13 1984-09-04 Montedison S.P.A. Process for preparing spheroidally shaped products, solid at room temperature
US4399054A (en) 1978-08-22 1983-08-16 Montedison S.P.A. Catalyst components and catalysts for the polymerization of alpha-olefins
EP0045977A2 (fr) 1980-08-13 1982-02-17 Montedison S.p.A. Composants et catalyseurs pour la polymérisation d'oléfines
US4507348A (en) * 1980-08-29 1985-03-26 Mitsui Petrochemical Industries Corrugated board-like sheet made of synthetic resin
US4472524A (en) 1982-02-12 1984-09-18 Montedison S.P.A. Components and catalysts for the polymerization of olefins
US4522930A (en) 1982-02-12 1985-06-11 Montedison S.P.A. Components and catalysts for the polymerization of olefins
US5842315A (en) 1997-03-24 1998-12-01 Tung Yik Trading Co., Ltd. Corrugated board structure
WO2000063261A1 (fr) 1999-04-15 2000-10-26 Basell Technology Company B.V. Constituants et catalyseurs de polymerisation d'olefines
WO2001057099A1 (fr) 2000-02-02 2001-08-09 Basell Technology Company B.V. Composants et catalyseurs destines a la polymerisation d'olefines
EP1849826A1 (fr) * 2006-04-26 2007-10-31 Borealis Technology Oy Article en transparentes polyoléfiniques soumis a un traitement thermique

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
RAIJA AHVENAINEN; THEA SIPILINEN-MALM; RAIJA-LIISA HEINIO; ANNUKKA LEPPNEN: "Packaging materials in microwave ovens", PACKAGING TECHNOLOGY AND SCIENCE, vol. 5, no. 6, November 1992 (1992-11-01), pages 291 - 294

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