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WO2025056307A1 - Composition de polypropylène - Google Patents

Composition de polypropylène Download PDF

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Publication number
WO2025056307A1
WO2025056307A1 PCT/EP2024/073848 EP2024073848W WO2025056307A1 WO 2025056307 A1 WO2025056307 A1 WO 2025056307A1 EP 2024073848 W EP2024073848 W EP 2024073848W WO 2025056307 A1 WO2025056307 A1 WO 2025056307A1
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WO
WIPO (PCT)
Prior art keywords
polypropylene composition
xylene
composition according
anyone
measured
Prior art date
Legal status (The legal status 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 status listed.)
Pending
Application number
PCT/EP2024/073848
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English (en)
Inventor
Stefano Spataro
Alessia DI CAPUA
Marco Ciarafoni
Gianni Collina
Gianni Vitale
Fabrizio Piemontesi
Eleonora Ciaccia
Alessandro Mignogna
Giampiero Morini
Benedetta Gaddi
Ofelia Fusco
Piero Gessi
Lorenzo VERONESE
Leonardo BRUSTOLIN
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Basell Poliolefine Italia SRL
Original Assignee
Basell Poliolefine Italia SRL
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 SRL filed Critical Basell Poliolefine Italia SRL
Publication of WO2025056307A1 publication Critical patent/WO2025056307A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • 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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—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
    • 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
    • C08L2207/02—Heterophasic composition

Definitions

  • the present disclosure relates to a polypropylene copolymer composition with an improved combination of processability, stiffness and transparency. These compositions may be employed for the production of molded articles, in particular injection molded articles or thermoformed articles such as containers.
  • Injection molded parts such as food packaging and plastic cups place specific requirements on the polymeric materials employed to produce these articles.
  • Polypropylene-based polymers have many characteristics, which make them suitable for applications such as molded articles, but also pipes, fittings and foams.
  • polypropylene products of high stiffness are based on high molecular weight materials, which are often nucleated by adding nucleating agents, i.e. crystallization starts at a higher temperature and the crystallization speed is high
  • WO 2018/104092 relates to a polypropylene composition comprising:
  • polypropylene composition comprising:
  • melt flow rate MFR, measured according to ISO 1133 at 230 °C with a load of 2.16 kg, comprised between 12.0 g/10 min and 38.0 g/10 min;
  • polypropylene composition comprising:
  • copolymer is referred to polymers containing only two kinds of comonomers, such as propylene and ethylene.
  • the polypropylene composition of the present disclosure is not subjected to a chemical or physical visbreaking, i.e. the MFR is obtained with the polymerization process.
  • the polypropylene composition according to the present disclosure is preferably characterized by having one or more of the following properties: a) tensile modulus comprised between 1000 MPa and 700 MPa; preferably comprised between 920 MPa and 750 MPa; b) Charpy impact measured at 23°C higher than 35.0 kJ/m 2 ; preferably higher than 40 kJ/m 2 ; more preferably higher than 43.0 kJ/m 2 ; the highest value being 80 kJ/m 2 ; c) the elongation at break higher than 300 % preferably higher than 380 %, more preferably higher than 450 %; the higher value being 1000 %.
  • the polypropylene composition of the present disclosure is obtained with a polymerization process in two or more stages in which component A) is obtained in the first stages and then component B) is obtained in the second stages in the presence of component A), each stage can be in gas-phase, operating in one or more fluidized or mechanically agitated bed reactors, slurry phase using as diluent an inert hydrocarbon solvent, or bulk polymerization using the liquid monomer (for example propylene) as a reaction medium.
  • component B) is polymerized in a gas phase process in the presence of component A) [0012]
  • the polymerization is generally carried out at temperature 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 polypropylene composition herein disclosed is obtainable by a process comprising polymerizing propylene in the first stage (A) and copolymerizing propylene with ethylene in a second stage (B), in the presence in both stages of a solid catalyst component for the polymerization of olefins comprising a magnesium halide, a titanium compound having at least a Ti-halogen bond and at least an electron donor of formula (I) in which R 1 and R 2 are, independently, Ci-Cs alkyl groups, X is Si or C, R 3 and R 4 groups, independently, are selected from hydrogen, Ci-Cio hydrocarbon groups and halogens with the proviso that at least two R 3 are not hydrogen.
  • R 1 and R 2 are the same and are selected from C1-C4 linear or branched alkyl groups and more preferably from methyl groups.
  • R 4 groups are selected from hydrogen, C1-C4 linear or branched alkyl groups and halogens. More preferably, only one or two of R 4 groups are C1-C4 linear or branched alkyl groups or halogen.
  • Preferred alkyl groups are methyl, isopropyl or t-butyl, while preferred halogens are Cl and F.
  • the structures in which all R 4 groups are hydrogen are also preferred.
  • R 3 is a hydrocarbon group it is preferably selected from C1-C4 linear or branched alkyl groups and more preferably from methyl groups.
  • R 3 is a halogen it is preferably selected from Cl and F. More preferably it is F.
  • Another group of preferred structures are those in which X is carbon and R 3 is hydrogen or a halogen group preferably selected from Cl and F more preferably from F. Most preferred are the structures in which at least two of R 3 are selected from F and more preferably those in which all the R 3 groups are F.
  • the electron donor of formula (I) is 2-cyclohexyl-2-isopentyl-l,3- dim ethoxypropane; or 2-cyclohexyl-2-(3 ,3,3 -trifluoro -n-propyl)- 1 ,3 -dimethoxypropane.
  • the preparation of the solid catalyst component can be carried out according to several methods.
  • the solid catalyst component can be prepared by reacting a titanium compound of formula Ti(OR) q-y X y , where q is the valence of titanium and y is a number between 1 and q, preferably TiCk, with a magnesium chloride deriving from an adduct of formula MgCk’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, operating under stirring conditions at the melting temperature of the adduct (100-130°C).
  • the adduct is mixed with an inert hydrocarbon immiscible with the adduct thereby creating an emulsion which is quickly quenched 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 Ti compound or it can be previously subjected to thermal 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 TiCh (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 TiCh can be carried out one or more times.
  • the electron donor compound can be added in the desired ratios during the treatment with TiCk
  • Suitable external electron-donor compounds include silicon compounds, ethers, esters, amines, heterocyclic compounds and particularly 2,2,6,6-tetramethylpiperidine and ketones.
  • a preferred class of external donor compounds is that of silicon compounds of formula (R6)a(R7)bSi(ORs) c , where a and b are integers from 0 to 2, c is an integer from 1 to 4 and the sum (a+b+c) is 4; Re, Rz, and Rs, are alkyl, cycloalkyl or aryl radicals with 1-18 carbon atoms optionally containing heteroatoms.
  • Examples of such preferred silicon compounds are methylcyclohexyldimethoxysilane (C donor), diphenyldimethoxysilane, methyl-t-butyldimethoxysilane, dicyclopentyldimethoxysilane (D donor), diisopropyldimethoxysilane, (2-ethylpiperidinyl)t-butyldimethoxysilane, (2- ethylpiperidinyl)thexyldimethoxysilane, (3,3,3-trifluoro-n-propyl)-(2-ethylpiperidinyl)- dimethoxysilane, methyl(3,3,3-trifluoro-n-propyl)dimethoxysilane.
  • C donor methylcyclohexyldimethoxysilane
  • D donor dicyclopentyldimethoxysilane
  • diisopropyldimethoxysilane (2-eth
  • the silicon compounds in which a is 0, c is 3, R? is a branched alkyl or cycloalkyl group, optionally containing heteroatoms, and Rs is methyl are also preferred.
  • Examples of such preferred silicon compounds are cyclohexyltrimethoxysilane, t-butyltrimethoxysilane and thexyltrimethoxysilane.
  • the electron donor compound (iii) is used in such an amount to give a weight ratio between the organoaluminum compound and said electron donor compound (iii) of from 2.5 to 500, preferably from 3 to 300 and more preferably from 3.5 to 100.
  • the polymerization process can be carried out according to known techniques for example slurry polymerization using as diluent an inert hydrocarbon solvent, or bulk polymerization using the liquid monomer (for example propylene) as a reaction medium. Moreover, it is possible to carry out the polymerization process in gas-phase operating in one or more fluidized or mechanically agitated bed reactors.
  • the polymerization is generally carried out at temperature 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 polypropylene composition of the present disclosure can contain the additives that are commonly used in the art such as anti-oxidants, process stabilizers, slip agents, antistatic agents, antiblock agents, antifog agents and nucleating agents.
  • the sample is dissolved in tetrahydronaphthalene at 135 °C and then poured into a capillary viscometer.
  • the viscometer tube (Ubbelohde type) is surrounded by a cylindrical glass jacket; this setup allows for temperature control with a circulating thermostatic liquid.
  • the downward passage of the meniscus is timed by a photoelectric device.
  • the determination of oligomer content by solvent extraction consists of treating 5g of polypropylene sample with 10 ml of methylenedichloride (CH2CI2) in an ultrasonic bath at 25°C for 4 hours. 1 rm of the extracted solution is injected into a capillary column and analysed by using FID, without any filtration. For quantitative estimation of oligomer content a calibration based on external standard method has been applied. In particular, a series of hydrocarbons (Cl 2- C22-C28- C40) is used.
  • the melt flow rate MIL of the polymer was determined according to ISO 1133 (230°C, 2.16 Kg).
  • 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).
  • Flexural Modulus is measured according to ISO 178, and supplemental conditions according to ISO 1873-2.
  • Elongation at break Elongation at break measured according to ISO 527-2, and ISO 1873-2
  • HPT Head deflection temperature
  • the catalyst system has been produced according to the method described in PCT/EP2023/068696.
  • the catalyst used in example 1 is described in example 15 of
  • the solid catalyst component described above Before introducing it into the polymerization reactors, the solid catalyst component described above have been contacted with triethyl aluminum (TEAL) and di-cyclopentyldimethoxy silane (donor D) in a ratio reported on table 1. Then the resulting mixture is subjected to prepolymerization by maintaining it in suspension in liquid propylene at 20 °C for about 5 minutes before introducing it into the polymerization reactor.
  • TEAL triethyl aluminum
  • donor D di-cyclopentyldimethoxy silane
  • the polymerization run is conducted in continuous mode 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 two reactors are liquid phase reactors, and the third is a fluid bed gas phase reactor.
  • Component (A) is prepared in the first and second reactor, the first and second reactor have the same polymeriziton parameters, while component (B) is prepared in the third.
  • Hydrogen is used as molecular weight regulator.
  • the gas phase (propylene, ethylene and hydrogen) is continuously analyzed via gaschromatography.
  • Comparative example 3 is the commercial grade SG702 sold by Lyondellbasell. [0053] Examples 1 and 2 shows a better Charpy and elongation at break with respect to comparative example 3.

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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

L'invention concerne une composition de polypropylène comprenant : • A) de 65,5 % en poids à 82,5 % en poids d'un homopolymère de propylène ; • B) de 17,5 % en poids à 34,5 % en poids d'un copolymère de propylène-éthylène ayant une teneur en unités dérivées de l'éthylène allant de 40,6 % en poids à 47,4 % en poids, ladite composition de polypropylène ayant : • i) une fraction soluble dans le xylène à 25 °C allant de 24,0 % en poids à 32,3 % ; • ii) la teneur en unités dérivées de l'éthylène sur la fraction soluble dans le xylène à 25 °C allant de 34,6 % en poids à 42,0 % en poids, mesurée par RMN 13C ; • (iii) un indice de fluidité, MFR, mesuré selon la norme ISO 1133 à 230 °C avec une charge de 2,16 kg, compris entre 14,0 g/10 min et 38,0 g/10 min ; • (iv) la viscosité intrinsèque, mesurée dans du tétrahydronaphtalène à 135 °C, de la fraction soluble dans le xylène à 25° C allant de 2,2 dl/g à 3,5 dl/g, la somme des quantités A) et B) étant de 100 % en poids.
PCT/EP2024/073848 2023-09-12 2024-08-26 Composition de polypropylène Pending WO2025056307A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP23196962 2023-09-12
EP23196962.7 2023-09-12

Publications (1)

Publication Number Publication Date
WO2025056307A1 true WO2025056307A1 (fr) 2025-03-20

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Citations (6)

* 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
US4469648A (en) 1978-06-13 1984-09-04 Montedison S.P.A. Process for preparing spheroidally shaped products, solid at room temperature
WO2006037705A1 (fr) * 2004-10-04 2006-04-13 Basell Poliolefine Italia S.R.L. Compositions polyolefiniques elastomeres
WO2017085195A1 (fr) * 2015-11-17 2017-05-26 Borealis Ag Composition de tpo à écoulement élevé présentant un excellent impact à température basse
WO2017178191A1 (fr) * 2016-04-14 2017-10-19 Basell Poliolefine Italia S.R.L. Compositions de polypropylène
WO2018104092A1 (fr) 2016-12-05 2018-06-14 Basell Poliolefine Italia S.R.L. Copolymères de propylène hétérophasique

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
WO2006037705A1 (fr) * 2004-10-04 2006-04-13 Basell Poliolefine Italia S.R.L. Compositions polyolefiniques elastomeres
WO2017085195A1 (fr) * 2015-11-17 2017-05-26 Borealis Ag Composition de tpo à écoulement élevé présentant un excellent impact à température basse
WO2017178191A1 (fr) * 2016-04-14 2017-10-19 Basell Poliolefine Italia S.R.L. Compositions de polypropylène
WO2018104092A1 (fr) 2016-12-05 2018-06-14 Basell Poliolefine Italia S.R.L. Copolymères de propylène hétérophasique

Non-Patent Citations (2)

* 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. 1977, no. 10, pages 536
HUGGINS, M.L., J. AM. CHEM. SOC., vol. 64, 1942, pages 2716

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