EP2463413B1 - Fibres de polyoléfine - Google Patents

Fibres de polyoléfine Download PDF

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Publication number
EP2463413B1
EP2463413B1 EP20110191869 EP11191869A EP2463413B1 EP 2463413 B1 EP2463413 B1 EP 2463413B1 EP 20110191869 EP20110191869 EP 20110191869 EP 11191869 A EP11191869 A EP 11191869A EP 2463413 B1 EP2463413 B1 EP 2463413B1
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Prior art keywords
xylene
ethylene
propylene
ranging
copolymer
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EP20110191869
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German (de)
English (en)
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EP2463413A1 (fr
Inventor
Monica Galvan
Gabriella Sartori
Roberta Marzolla
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Basell Poliolefine Italia SRL
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Basell Poliolefine Italia SRL
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Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins

Definitions

  • the present invention relates to fibres comprising a polyolefin composition.
  • fibres are also included the manufactured products similar to fibres, such as fibrils and cut filaments (staple fibres).
  • the fibres of the present invention are particularly fit for use in applications where a good balance of tenacity and elongation at break is required.
  • the fibres of the present invention are suitable for the manufacture of spunbonded non-woven fabrics.
  • WO 2006/125720 relates to a polypropylene composition comprising (per cent by weight):
  • WO 2006/067023 relates to a polypropylene composition comprising (per cent by weight):
  • compositions of WO 2006/125720 and of WO 2006/067023 typically have a value of melt flow rate ranging from 0.50 to 10 g/10 min and from 10 to 30 g/10 min, respectively, which values are well below the melt flow rates of the compositions comprised in the fibres of the present invention.
  • Polyolefin fibres are generally known in the prior art.
  • EP 1264017 relates to multicomponent fibres and non-woven fabrics and fabric laminates which comprise the multicomponent fibres.
  • a continuous filament spunbond fabric is produced from a blend comprising 76% isotactic polypropylene, 20% propylene copolymer, and 4% polyethylene, which values are different from those of the polyolefin composition comprised in the fibres of the invention.
  • the composition has a content of component (b) plus component (c) in amounts comprised between 15 wt% and 25 wt%, preferably from 20 wt% and 25 wt%.
  • the composition of the present invention exhibits a flexural modulus value of at least 1200 MPa, preferably at least 1300 MPa, even more preferably the flexural modulus is comprised between 1400 MPa and 1700 MPa.
  • the fibres of the invention typically with a titre of 2.3 dtex exhibit a value of tenacity at least equal to or higher than 8 cN/tex, preferably higher than 9 cN/tex, and a value of elongation at break at least equal to or higher than 350%, preferably equal to or higher than 400%.
  • the fibres according to the present invention have a titre ranging from 1 to 4 dtex, preferably from 1.5 to 2.5 dtex.
  • the fibres of the present invention can be efficiently spun at speeds that are typically higher than 2000 m/min, preferably higher than 2500 m/min.
  • the fibres of the present invention also exhibit an elastic recovery at 10% of at least 5%, preferably of at least 7%.
  • Crystalline propylene polymer (a) is selected from a propylene homopolymer and a copolymer of propylene containing at most 3 wt% of ethylene or a C 4 -C 10 ⁇ -olefin or combination thereof. Particularly preferred is the propylene homopolymer.
  • crystalline propylene polymer (a) has a polydispersity index ranging from 4 to 10, preferably from 5 to 10.
  • the melt flow rate of crystalline propylene polymer (a) preferably ranges from 130 to 250 g/10 min, preferably from 140 to 220 g/10 min, more preferably from 150 to 210 g/10 min.
  • the intrinsic viscosity of the soluble fraction in xylene at 25° C of the ethylene-propylene copolymer (b) is comprised between 1.5 and 4 dl/g; preferably between 2 and 3.5 dl/g; more preferably between 2.5 and 3.5 dl/g (calculated on the sum of xylene soluble fraction of a+b).
  • the composition of the present invention is obtained by means of a sequential copolymerization process.
  • the present invention is further directed to a process for the preparation of the polyolefin compositions as reported above, 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 trialkylaluminium 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 trialkylaluminium 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.
  • succinates they are preferably selected from succinates of the formula (I): wherein the radicals R 1 and R 2 , equal to or different from each other, are a C 1 -C 20 linear or branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl or alkylaryl group, optionally containing heteroatoms; the radicals R 3 to R 6 , 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 R 3 to R 6 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, R 6 is a radical selected from primary branched, secondary or tertiary alkyl groups, cycloalkyl, aryl,
  • 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): wherein R 1 and R II are the same or different and are C 1 -C 18 alkyl, C 3 -C 18 cycloalkyl or C 7 -C 18 aryl radicals; R III 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.
  • Ethers of this type are described in published European patent applications 361493 and 728769 .
  • 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 R a 7 R b 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 C 1 -C 18 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, (1,1,1-trifluoro-2-propyl)-methyldimethoxysilane and (1,1,1-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 partcular 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 25° C 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.
  • the fibres of the invention are suitable for the manufacture of spunbonded non-woven fabrics.
  • the particulars are given in the following examples, which are given to illustrate, without limiting, the present invention.
  • the 13 C NMR spectra were acquired on a Bruker DPX-400 (100.61 Mhz, 90° pulse, 12s delay between pulses). About 3000 transients were stored for each spectrum; mmmm pentad peak (21.8 ppm) was used as reference.
  • microstructure analysis was carried out as described in literature ( Polymer, 1984, 25, 1640, by Inoue Y. et Al. and Polymer, 1994, 35, 339, by Chujo R. et Al.).
  • Elastic recovery is the percentage value of the maximum deformation (220 mm, corresponding to 10% deformation with respect to the initial cross head distance of 200 mm) minus the percent of residual deformation as above defined.
  • 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 immediately next to it.
  • 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 subj ected to prepolymerization by maintaining it in suspension in liquid propylene at 20° C for about 5 minutes before introducing it into the first polymerization reactor.
  • 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 gaschromatography.
  • the propylene compositions were added with the following additives: calcium stearate 500 ppm, Irganox B215 1500 ppm.
  • the maximum spinning speed gives indication of the spinnability of the polyolefin composition of the invention.
  • the value corresponds to the highest spinning rate that can be maintained for 30 minutes with no filament break.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Claims (6)

  1. Fibre comprenant une composition polyoléfinique, ladite composition comprenant (pour cent en poids) :
    a) 50% à 85% d'un polymère de propylène, présentant une quantité de pentades isotactiques (mmmm), mesurée par 13C-RMN sur la fraction insoluble dans le xylène à 25°C, supérieure à 97,5% en mole ;
    b) 5% à 20% d'un copolymère d'éthylène et de propylène, le copolymère présentant une quantité d'unités récurrentes dérivées d'éthylène dans la plage de 30 à 50% et étant partiellement soluble dans le xylène à 25°C ; la fraction polymère soluble dans le xylène à 25°C présentant une valeur de viscosité intrinsèque dans la plage de 1,5 à 4 dl/g ; et
    c) 5% à 30% d'homopolymère d'éthylène ; la somme a) + b) + c) valant 100 ;
    ladite composition présentant une valeur d'indice de fluidité à chaud dans la plage de 20 à 150 g/10 min.
  2. Fibre selon la revendication 1, la composition polyoléfinique comprenant (pour cent en poids) :
    a) 70% à 84% d'un polymère cristallin de propylène, présentant une quantité de pentades isotactiques (mmmm), mesurée par 13C-RMN sur la fraction insoluble dans le xylène à 25°C, supérieure à 97,5% en mole ;
    b) 8% à 15% d'un copolymère d'éthylène et de propylène, le copolymère présentant une quantité d'unités récurrentes dérivées d'éthylène dans la plage de 30 à 50% et étant partiellement soluble dans le xylène à 25°C ; la fraction polymère soluble dans le xylène à 25°C présentant une valeur de viscosité intrinsèque dans la plage de 1,5 à 4 dl/g ; et
    c) 8% à 14% d'homopolymère d'éthylène,
  3. Fibre selon les revendications 1 ou 2, la composition polyoléfinique comprenant 72% en poids à 82% en poids du polymère de propylène (a), 9% en poids à 14% en poids du copolymère (b) et 9% en poids à 13% en poids du polyéthylène (c).
  4. Fibre selon l'une quelconque des revendications 1-3, la composition présentant une teneur en composant (b) plus composant (c) en des quantités comprises entre 20% en poids et 25% en poids.
  5. Fibre selon l'une quelconque des revendications 1-4, la composition présentant une valeur de l'indice de fluidité à chaud dans la plage de 40 à 90 g/10 min.
  6. Tissu non tissé filé-lié comprenant les fibres selon l'une quelconque des revendications 1-5.
EP20110191869 2010-12-07 2011-12-05 Fibres de polyoléfine Active EP2463413B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP20110191869 EP2463413B1 (fr) 2010-12-07 2011-12-05 Fibres de polyoléfine

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP10193988 2010-12-07
EP20110191869 EP2463413B1 (fr) 2010-12-07 2011-12-05 Fibres de polyoléfine

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EP2463413A1 EP2463413A1 (fr) 2012-06-13
EP2463413B1 true EP2463413B1 (fr) 2014-01-29

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ES2685921T3 (es) 2013-03-12 2018-10-15 Fitesa Nonwoven, Inc. Tela no tejida extensible

Family Cites Families (16)

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Publication number Priority date Publication date Assignee Title
DK133012C (da) 1968-11-21 1976-08-09 Montedison Spa Katalysator til polymerisation af alkener
YU35844B (en) 1968-11-25 1981-08-31 Montedison Spa Process for obtaining catalysts for the polymerization of olefines
IT1096661B (it) 1978-06-13 1985-08-26 Montedison Spa Procedimento per la preparazione di prodotti in forma sferoidale solidi a temperatura ambiente
IT1098272B (it) 1978-08-22 1985-09-07 Montedison Spa Componenti,di catalizzatori e catalizzatori per la polimerizzazione delle alfa-olefine
IT1209255B (it) 1980-08-13 1989-07-16 Montedison Spa Catalizzatori per la polimerizzazione di olefine.
IT1190681B (it) 1982-02-12 1988-02-24 Montedison Spa Componenti e catalizzatori per la polimerizzazione di olefine
IT1190683B (it) 1982-02-12 1988-02-24 Montedison Spa Componenti e catalizzatori per la polimerizzazione di olefine
IT1227260B (it) 1988-09-30 1991-03-28 Himont Inc Dieteri utilizzabili nella preparazione di catalizzatori ziegler-natta
US6420285B1 (en) * 1994-11-23 2002-07-16 Bba Nonwovens Simpsonville, Inc. Multicomponent fibers and fabrics made using the same
IL117114A (en) 1995-02-21 2000-02-17 Montell North America Inc Components and catalysts for the polymerization ofolefins
HUP0103083A3 (en) 1999-04-15 2003-01-28 Basell Technology Co Bv Components and catalysts for the polymerization of olefins
WO2001057099A1 (fr) 2000-02-02 2001-08-09 Basell Technology Company B.V. Composants et catalyseurs destines a la polymerisation d'olefines
WO2006063905A1 (fr) * 2004-12-13 2006-06-22 Basell Poliolefine Italia S.R.L. Composition de polyolefines, fibres et tissus non-tisses
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CN101180357B (zh) 2005-05-27 2011-10-19 巴塞尔聚烯烃意大利有限责任公司 具有良好抗致白性的聚烯烃组合物
US8728960B2 (en) * 2007-01-19 2014-05-20 Exxonmobil Chemical Patents Inc. Spunbond fibers and fabrics from polyolefin blends

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