WO2024099626A1 - Homopolymère de propylène - Google Patents

Homopolymère de propylène Download PDF

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Publication number
WO2024099626A1
WO2024099626A1 PCT/EP2023/075796 EP2023075796W WO2024099626A1 WO 2024099626 A1 WO2024099626 A1 WO 2024099626A1 EP 2023075796 W EP2023075796 W EP 2023075796W WO 2024099626 A1 WO2024099626 A1 WO 2024099626A1
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WO
WIPO (PCT)
Prior art keywords
propylene homopolymer
iso
measured
ranges
anyone
Prior art date
Application number
PCT/EP2023/075796
Other languages
English (en)
Inventor
Marco BOCCHINO
Claudio Cavalieri
Antonio RIEMMA
Alberta DE CAPUA
Eleonora Ciaccia
Davide TARTARI
Cristina COVA
Alessia DI CAPUA
Marco Ciarafoni
Giampaolo Pellegatti
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 WO2024099626A1 publication Critical patent/WO2024099626A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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

Definitions

  • the present disclosure relates to polypropylene homopolymer having high molecular weight and high melt strength.
  • Propylene homopolymer is widely used in the processing fields of injection, extrusion, tape casting and biaxial stretching due to the tailoring structure thereof
  • the common polypropylene molecular chain is of linear structure, which is unlike amorphous polymers, such as polystyrene PS with a region having property similar to the rubber elasticity in a wide temperature range.
  • polystyrene PS with a region having property similar to the rubber elasticity in a wide temperature range.
  • polypropylene cannot be thermoformed in a wide temperature range.
  • the softening point of polypropylene is close to its melt point.
  • the present disclosure is directed to a propylene homopolymer optionally containing up to 1.0 wt% of ethylene derived units characterized in that:
  • the fraction soluble in xylene at 25°C measured according to ISO 16 152 - 2005 is comprised between 6.0 wt% and 2.0wt%; -the isotactic pentads mmmm %, measured with C 13 NMR as reported in the examples section ranges from 96.5 mol% to 90.0 mol%;
  • melt strength measured according to ISO 16790-2005, at 250°C and applying an acceleration equal to 6 mm/s 2 is higher than 0.070 N.
  • the present disclosure is directed to a propylene homopolymer optionally containing up to 1.0 wt% of ethylene, preferably up to 0.6 wt% of ethylene derived units characterized in that:
  • melting points are present in the DSC thermogram measured according to ISO 11357- 3, with heating and cooling rate of 20°C/min; preferably the lower melting point ranges from 135°C to 150°C;
  • the higher melting point measured according to ISO 11357-3, with heating and cooling rate of 20°C/min, ranges from 155°C to 170°C; preferably from 157°C to 168°C;
  • the fraction soluble in xylene at 25°C measured according to ISO 16 152 - 2005 is comprised between 6.0 wt% and 2.0wt%; preferably comprised between 5.0 wt% and 2.5wt%; more preferably comprised between 4.0 wt% and 2.8wt%;
  • the isotactic pentads, mmmm %, measured with C 13 NMR as reported in the examples section ranges from 96.5 mol% to 90.0 mol%, .preferably from 96.0 mol% to 93.0 mol%; more preferably from 95.5 mol% to 93.5 mol%;
  • melt strength measured according to ISO 16790-2005 at 250°C and applying an acceleration equal to 6 mm/s 2 is higher than 0.070 N; preferably higher than 0.080 N; more preferably higher than 0.090 N.
  • the propylene homopolymer of the present disclosure is not nucleated.
  • the homopolymer of the present disclosure shows a value of melt strength lower than 0.30 N.
  • the homopolymer of the present disclosure shows a polydispersity index, PI, measured according to ISO 6721-10, comprised between 4.5 and 7.5; more preferably between 5.0 and 7.2; more preferably from 5.5 to 6.5.
  • the homopolymer of the present disclosure shows a tensile modulus ranging from 2100 MPa to 1100 MPa; preferably from 1800MPa, to 1200 Mpa.
  • the homopolymer of the present disclosure shows a charpy impact test at 23°C ranging from 4.0 kJ/m2 to 11.0 kJ/m2; preferably from 5.5 kJ/m2 to 9.0 kJ/m2.
  • the polypropylene homopolymer of the present disclosure is characterized by having an high melt strength and an high molecular weight. For this reason the homopolymer of the present disclosure can be used in blend with other polymers having a lower melt strength in order to increase the latter so that the resulting blend can be used for the production of foam products, biaxial stretching films, thermoforming products and blow molded products.
  • the propylene homopolymers disclosed herein can be prepared by a process comprising polymerizing propylene optionally with ethylene, in the presence of Ziegler-Natta catalysts.
  • An essential component of said catalysts is a solid catalyst component comprising a titanium compound having at least one titanium-halogen bond, and an electron-donor compound, both supported on a magnesium halide in active form.
  • Another essential component co-catalyst is an organoaluminium compound, such as an aluminium alkyl compound.
  • An external donor is optionally added.
  • Catalysts having the above mentioned characteristics are well known in the patent literature; particularly advantageous are the catalysts described in US patent 4,399,054 and European patent 45977. Other examples can be found in US patent 4,472,524.
  • the solid catalyst components used in said catalysts comprise, as electron-donors (internal donors), compounds selected from the group consisting of ethers, ketones, lactones, compounds containing N, P and/or S atoms, and esters of mono- and dicarboxylic acids.
  • Particularly suitable electron- donor compounds are esters of phtalic acid and 1,3- diethers of formula:
  • RI and RII are the same or different and are Cl -Cl 8 alkyl, C3-C18 cycloalkyl or C7-C18 aryl radicals; RIII and RIV are the same or different and are C1-C4 alkyl radicals; or are 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, or of 5-n or 6-n' carbon atoms, and respectively n nitrogen atoms and n' heteroatoms selected from the group consisting of N, O, S and Si, where n is 1 or 2 and n' is 1, 2, or 3, said structure containing two or three unsaturations (cyclopolyenic structure), and optionally being condensed with other cyclic structures, or substituted with one or more substituents selected from the group consisting of linear or branched alkyl radicals; cycloalkyl, aryl, aralkyl, al
  • diethers are 2-methyl-2-isopropyl-l,3- dimethoxypropane, 2,2-diisobutyl-l,3-dimethoxypropane, 2-isopropyl-2-cyclopentyl-l,3- dimethoxypropane, 2-isopropyl-2-isoamyl- 1,3 -dimethoxypropane, 9,9-bis (methoxymethyl) fluorene.
  • Suitable electron-donor compounds are phthalic acid esters, such as diisobutyl, dioctyl, diphenyl and benzylbutyl phthalate.
  • a MgC12»nROH adduct (in particular in the form of spheroidal particles) wherein n is generally from 1 to 3 and ROH is ethanol, butanol or isobutanol, is reacted with an excess of TiC14 containing the electron-donor compound.
  • the reaction temperature is generally from 80 to 120° C.
  • the solid is then isolated and reacted once more with TiC14, in the presence or absence of the electron-donor compound, after which it is separated and washed with aliquots of a hydrocarbon until all chlorine ions have disappeared.
  • the titanium compound expressed as Ti, is generally present in an amount from 0.5 to 10% by weight.
  • the quantity of electron-donor compound which remains fixed on the solid catalyst component generally is 5 to 20% by moles with respect to the magnesium dihalide.
  • the titanium compounds which can be used for the preparation of the solid catalyst component, are the halides and the halogen alcoholates of titanium. Titanium tetrachloride is the preferred compound.
  • the Al-alkyl compounds used as co-catalysts comprise the 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 SO4 or SO3 groups.
  • 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 SO4 or SO3 groups.
  • the Al-alkyl compound is generally used in such a quantity that the Al/Ti ratio be from 1 to 1000.
  • the electron-donor compounds that can be used as external donors include aromatic acid esters such as alkyl benzoates, and in particular silicon compounds containing at least one Si- OR bond, where R is a hydrocarbon radical.
  • silicon compounds are (tert-butyl)2Si(OCH3)2, (cyclohexyl)(methyl)Si (OCH3)2, (cyclopentyl)2Si(OCH3)2 and (phenyl)2Si(OCH3)2 and (1,1,2- trimethylpropyl)Si(OCH3)3.
  • 1,3 -diethers having the formulae described above can also be used advantageously. If the internal donor is one of these diethers, the external donors can be omitted.
  • the component A) are preferably prepared by using catalysts containing a phthalate as internal donor and (cyclopentyl)2Si(OCH3)2 as outside donor, or the said 1,3-diethers as internal donors.
  • the polymerization is generally carried out at temperatures of from 20 to 120°C, preferably of from 40 to 80°C.
  • the operating pressure is generally between 0.5 and 5 MPa, preferably between 1 and 4 MPa.
  • the operating pressure is generally between 1 and 8 MPa, preferably between 1.5 and 5 MPa.
  • Hydrogen is typically used as a molecular weight regulator.
  • the polymerization can be in gas phase or in slurry or in solution. In one or more reactors. Preferably the polymerization is carried put in two slurry reactors operating in series.
  • the propylene homopolymer optionally containing up to 1.0 wt% of ethylene derived units of the present disclosure can be used for obtaining fibers, film, molded articles and foamed articles.
  • Xylene Solubles fraction has been measured according to ISO 16 152 - 2005; with solution volume of 250 ml, precipitation at 25°C for 20 minutes, 10 of which with the solution in agitation (magnetic stirrer), and drying at 70°.
  • Tm melting points of the polymers
  • the weighted sample was sealed into aluminium pans and heated to 200°C at 20°C/minute.
  • the sample was kept at 200°C for 2 minutes to allow a complete melting of all the crystallites, then cooled to 5°C at 20°C/minute.
  • the sample was heated for the second run time to 200°C at 20°C/min. In this second heating run, the peak temperature (Tp,m) was taken as the melting temperature.
  • the weight percentage of ethylene content was evaluated using the following equation: 100 * E% mol * MWE
  • the tacticity of Propylene sequences was calculated as mm content from the ratio of the PPP mmTpp (28.90-29.65 ppm) and the whole Tpp (29.80-28.37 ppm).
  • the sample is dissolved by tetrahydronaphthalene at 135 °C and then it is poured into the capillary viscometer.
  • the viscometer tube (Ubbelohde type) is surrounded by a cylindrical glass jacket; this setup allows temperature control with a circulating thermostated liquid.
  • the downward passage of the meniscus is timed by a photoelectric device.
  • the passage of the meniscus in front of the upper lamp starts the counter which has a quartz crystal oscillator.
  • the meniscus stops the counter as it passes the lower lamp and the efflux time is registered: this is converted into a value of intrinsic viscosity through Huggins' equation, provided that the flow time of the pure solvent is known at the same experimental conditions (same viscometer and same temperature).
  • One single polymer solution is used to determine IV]
  • the melt strength is measured according to ISO 16790-2005, by Haul-off Melt Strength Meter produced by Geottfert MaschinenstoffPruefmaschinen, Germany.
  • This system measures the extensional properties of polymer melts by drawing a vertical melt strand at a constant pull-off speed or with a linear or exponentially accelerating velocity.
  • the HAUL-OFF system measures the force needed to elongate the strand, and calculates elongation stress, draw ratio and apparent elongation rate and viscosity.
  • Polymer is melt and plasticized through a capillary rheometer, then is extruded from a hole die with a 1 mm of diameter, 30 mm of length and 180° inlet angle. The test is performed at 250°C.
  • the distance from the capillary outlet to the center of the transducer pulley is 150 mm.
  • the monofilament is stretched at each temperature test applying an acceleration equal to 6 mm/s 2 and, passing through an angular transducer, its tension is measured.
  • the draw ratio (dimensionless value) and force (cN) values are recorded as the final result in addition to the entire curve.
  • the value of the melt strength is the maximum force value of the curve.
  • the solid catalyst used in the following examples was prepared according to the Example 10 of the International Patent Application WO 00/63261.
  • Triethylaluminium (TEAL) was used as co-catalyst and dicyclopentyldimethoxysilane as external donor, with the weight ratios indicated in Table 1.
  • the polymerization run is carried out in continuous mode in a series of two reactors equipped with devices to transfer the product from one reactor to the one immediately next to it.
  • the two reactors are liquid phase loop reactors.
  • Propylene is the main solvent, hydrogen is used as molecular weight regulator.
  • the gas phase is continuously analyzed via gas-chromatography.
  • Comparative example 2 is HP556E a propylene homopolymer sold by LyondellBasell.

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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)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Homopolymère de propylène contenant éventuellement jusqu'à 1,0 % en poids d'unités dérivées de l'éthylène, caractérisé en ce que : - deux points de fusion sont présents ; - le point de fusion supérieur est compris entre 155 °C et 170 °C ; - la fraction soluble dans le xylène à 25 °C est comprise entre 6,0 % en poids et 2,0 % en poids ; - le % des pentades isotactiques mmmm est compris entre 96,5 % en moles et 90,0 % en moles ; - la viscosité intrinsèque (IV) mesurée dans le tétrahydronaphtalène à 135 °C va de 5,5 à 12,0 dl/g ; - la résistance à l'état fondu est supérieure à 0,70 N.
PCT/EP2023/075796 2022-11-07 2023-09-19 Homopolymère de propylène WO2024099626A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP22205915 2022-11-07
EP22205915.6 2022-11-07

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WO2024099626A1 true WO2024099626A1 (fr) 2024-05-16

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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US4472524A (en) 1982-02-12 1984-09-18 Montedison S.P.A. Components and catalysts for the polymerization of olefins
EP0361493A1 (fr) 1988-09-30 1990-04-04 Himont Incorporated Diéthers utilisables dans la préparation des catalyseurs Ziegler-Natta et leur préparation
EP0728769A1 (fr) 1995-02-21 1996-08-28 Montell North America Inc. Composants et catalyseurs pour la polymérisation d'oléfines
WO2000063261A1 (fr) 1999-04-15 2000-10-26 Basell Technology Company B.V. Constituants et catalyseurs de polymerisation d'olefines
US10023667B2 (en) * 2012-06-27 2018-07-17 Total Research & Technology Feluy Propylene homopolymer for high-tenacity fibers and nonwovens
EP2995641B1 (fr) * 2014-09-11 2019-12-25 Borealis AG Composition de polypropylène pour un film de condensateur
EP2984112B1 (fr) * 2013-04-09 2020-06-03 Borealis AG Processus de fabrication de polypropylène
WO2021167850A1 (fr) * 2020-02-17 2021-08-26 Exxonmobil Chemical Patents Inc. Compositions de polymère à base de propylène ayant une queue de masse moléculaire élevée

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US4472524A (en) 1982-02-12 1984-09-18 Montedison S.P.A. Components and catalysts for the polymerization of olefins
EP0361493A1 (fr) 1988-09-30 1990-04-04 Himont Incorporated Diéthers utilisables dans la préparation des catalyseurs Ziegler-Natta et leur préparation
EP0728769A1 (fr) 1995-02-21 1996-08-28 Montell North America Inc. Composants et catalyseurs pour la polymérisation d'oléfines
WO2000063261A1 (fr) 1999-04-15 2000-10-26 Basell Technology Company B.V. Constituants et catalyseurs de polymerisation d'olefines
US10023667B2 (en) * 2012-06-27 2018-07-17 Total Research & Technology Feluy Propylene homopolymer for high-tenacity fibers and nonwovens
EP2984112B1 (fr) * 2013-04-09 2020-06-03 Borealis AG Processus de fabrication de polypropylène
EP2995641B1 (fr) * 2014-09-11 2019-12-25 Borealis AG Composition de polypropylène pour un film de condensateur
WO2021167850A1 (fr) * 2020-02-17 2021-08-26 Exxonmobil Chemical Patents Inc. Compositions de polymère à base de propylène ayant une queue de masse moléculaire élevée

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
C. J. CARMANR. A. HARRINGTONC. E. WILKES: "Monomer Sequence Distribution in Ethylene-Propylene Rubber Measured by 13C NMR. 3. Use of Reaction Probability Mode", MACROMOLECULES, vol. 10, 1977, pages 536

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