EP2699718B1 - Terpolymere auf propylenbasis für fasern - Google Patents

Terpolymere auf propylenbasis für fasern Download PDF

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Publication number
EP2699718B1
EP2699718B1 EP12714727.0A EP12714727A EP2699718B1 EP 2699718 B1 EP2699718 B1 EP 2699718B1 EP 12714727 A EP12714727 A EP 12714727A EP 2699718 B1 EP2699718 B1 EP 2699718B1
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Prior art keywords
fibers
terpolymer
hexene
propylene
ethylene
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English (en)
French (fr)
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EP2699718A1 (de
Inventor
Roberta Marzolla
Monica Galvan
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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
    • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/30—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising olefins as the major constituent
    • 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
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
    • D01F6/06—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins from polypropylene
    • 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
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/06—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyolefin as constituent

Definitions

  • the present invention relates to fibers, including fibrils and cut filaments (staple fibers), made of propylene/ethylene/alpha-olefins terpolymers particularly fit for their production.
  • fibers made of propylene/ethylene/1-hexene terpolymers are particularly fit for their production.
  • it relates to fibers made of propylene/ethylene/1-hexene terpolymers.
  • the fibers of the present invention are particularly adequate for use in applications where a good balance of tenacity and elongation at break is required.
  • the fibers of the present invention are specifically suitable for the manufacture of spunbonded non-woven fabrics.
  • Fibers comprising copolymers of propylene with a low content of 1-hexene are known in the art.
  • US patent No. 6,365,682 relates to propylene based terpolymers useful for the preparation of films.
  • Terpolymers having an ethylene content ranging from 0.9 to 3 wt% and an alpha olefin content ranging from 1 to 15 wt% are indicated as particularly suitable. Only terpolymers of propylene/ethylene and 1-butene are exemplified.
  • US 4,211,819 relates to heat-melt adhesive propylene polymer fibers which can be produced with a superior spinnability.
  • the fibers comprise a resin consisting of (A) 50-100% by weight of a crystalline propylene terpolymer consisting of specified amounts of propylene, butene-1 and ethylene, and (B) 0-50% by weight of a substantially noncrystalline etylene-propylene random copolymer.
  • the terpolymer contains certain amount of propylene homopolymer.
  • WO 98/29586 relates to a heat-fusible composite fiber comprising a sheath component of a crystalline propylene copolymer resin having a low melting point and a core component of a crystalline polypropylene resin having a higher melting point.
  • a sheath component of a crystalline propylene copolymer resin having a low melting point and a core component of a crystalline polypropylene resin having a higher melting point.
  • relation (1) is Tm>158-6*(C2+0.8 ⁇ ); more preferably Tm>159-6*(C2+0.8a).
  • the crystallization temperature ranges from 70°C to 100°C, preferably from 80°C to 95°C; more preferably from 85°C to 95°C.
  • the polydispersity index (PI) ranges from 2.0 to 7.0, preferably from 3.0 to 6.5, more preferably from 3.5 to 6.0.
  • the visbreaking process can be carried out by treating the precursor terpolymer of the present invention with appropriate amounts, preferably from 0.001 to 0.20 wt%, more preferably from 0.04 to 0.10 wt%, of free radical initiators according to processes well-known in the art.
  • the visbreaking process is carried out by contacting under high shear conditions the polymeric material with at least one free radical initiator at a temperature equal to or higher that the decomposition temperature of the free radical initiator.
  • Preferred free radical initiators are peroxides having a decomposition temperature ranging from 150° to 250°C, such as di-tert-butyl peroxide, dicumyl peroxide, the 2,5-dimethyl-2,5-di (tert-butylperoxy)hexyne, and 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane (traded by Akzo under the name Luperox 101 or Trigonox 101).
  • the terpolymers of the present invention have a stereoregularity of isotactic type of the propylenic sequences this is clear by the low value of xylene extractables at 25°C that is preferably lower than 15%, more preferably lower than 12%.
  • the terpolymers to be used for the fiber of the present invention show a high melting point is linked to the specifc polymerization process used fot their preparation that is described below: in fact, with that process it is possible to obtain a terpolymer that is multimodalized in composition, i.e. the resulting terpolymer contains various fractions having a low content of comonomers, said fractions being responsible of the high melting point, and other fractions having a quite high comonomer content.
  • the fiber according to the present invention typically exhibits a value of tenacity higher than 25 cN/tex; preferably higher than 30 cN/tex, more preferably higher than 33 cN/tex, and a value of elongation at break typically higher than 180%, preferably higher than 200%.
  • the fibers according to the present invention have a titre ranging from 1 to 8 dtex, preferably 1.5 to 4 dtex, more preferably from 2 to 3 dtex.
  • the fibres of the present invention can contain formulations of stabilizers suited for obtaining a skin-core structure (skin-core stabilization), or a highly stabilizing formulation. In the latter case, a superior resistance to aging is achieved for durable nonwovens.
  • the terpolymer used in the present invention can be prepared by polymerisation in one or more polymerisation steps. Such polymerisation can be carried out 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
  • An external donor is optionally added.
  • the catalysts generally used in the process of the invention are capable of producing polypropylene with a value of xylene insolubility at ambient temperature greater than 90%, preferably greater than 95%.
  • 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 phthalic acid and 1,3-diethers of the following formula: wherein R 1 and R 11 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 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
  • Ethers of this type are described in published European patent applications 361493 and 728769 .
  • diethers are 2-methyl-2-isopropyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclopentyl-1,3-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.
  • the preparation of the above mentioned catalyst component is carried out according to various methods.
  • a MgCl 2 ⁇ 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 TiCl 4 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 TiCl 4 , 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 SO 4 or SO 3 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 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.
  • 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) 2 Si(OCH 3 ) 2 , (cyclohexyl)(methyl)Si (OCH 3 ) 2 , (cyclopentyl) 2 Si(OCH 3 ) 2 and (phenyl) 2 Si(OCH 3 ) 2 and (1,1,2-trimethylpropyl)Si(OCH 3 ) 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 terpolymers are preferably prepared by using catalysts containing a phthalate as internal donor and (cyclopentyl) 2 Si(OCH 3 ) 2 as outside donor, or the said 1,3-diethers as internal donors.
  • the said propylene-ethylene-hexene-1 polymers can be produced with a polymerization process illustrated in European patent application 1 012 195 .
  • the said process comprises feeding the monomers to said polymerisation zones in the presence of catalyst under reaction conditions and collecting the polymer product from the said polymerisation zones.
  • the growing polymer particles flow upward through one (first) of the said polymerisation zones (riser) under fast fluidisation conditions, leave the said riser and enter another (second) polymerisation zone (downcomer) through which they flow downward in a densified form under the action of gravity, leave the said downcomer and are reintroduced into the riser, thus establishing a circulation of polymer between the riser and the downcomer.
  • the condition of fast fluidization in the riser is established by feeding a gas mixture comprising the relevant monomers to the said riser. It is preferable that the feeding of the gas mixture is effected below the point of reintroduction of the polymer into the said riser by the use, where appropriate, of gas distributor means.
  • the velocity of transport gas into the riser is higher than the transport velocity under the operating conditions, preferably from 2 to 15 m/s.
  • the polymer and the gaseous mixture leaving the riser are conveyed to a solid/gas separation zone.
  • the solid/gas separation can be effected by using conventional separation means. From the separation zone, the polymer enters the downcomer.
  • the gaseous mixture leaving the separation zone is compressed, cooled and transferred, if appropriate with the addition of make-up monomers and/or molecular weight regulators, to the riser.
  • the transfer can be effected by means of a recycle line for the gaseous mixture.
  • control of the polymer circulating between the two polymerisation zones can be effected by metering the amount of polymer leaving the downcomer using means suitable for controlling the flow of solids, such as mechanical valves.
  • the operating parameters are those that are usual in olefin polymerisation process, for example between 50 to 120° C.
  • This first stage process can be carried out under operating pressures of between 0.5 and 10 MPa, preferably between 1.5 to 6 MPa.
  • one or more inert gases are maintained in the polymerisation zones, in such quantities that the sum of the partial pressure of the inert gases is preferably between 5 and 80% of the total pressure of the gases.
  • the inert gas can be nitrogen or propane, for example.
  • the various catalysts are fed up to the riser at any point of the said riser. However, they can also be fed at any point of the downcomer.
  • the catalyst can be in any physical state, therefore catalysts in either solid or liquid state can be used.
  • the terpolymer of the present invention may be blended with additives commonly employed in the art, such as antioxidants, light stabilizers, heat stabilizers, nucleating agents, colorants and fillers.
  • Fibers or filaments comprising the terpolymer of the invention may be prepared using processes and apparatuses well known in the art, i.e. by melt-spinning the terpolymer in conventional devices suitable for producing single or composite fibers or filaments.
  • the composite fibers or filaments may have a "sheath-core structure".
  • fibers or filaments having a sheath-core structure is meant herein fibers or filaments having an axially extending interface and comprising at least two components, i.e. at least an inner core and at least an outer sheath, said at least two components comprising different polymeric materials and being joined along the axially extending interface.
  • sheath thickness may be uniform or the sheath thickness may not be uniform around the circumference of a fiber or filament cross-section.
  • Said fibers or filaments having sheath-core structure can be produced using conventional melt-spin equipments having concentric annular dies.
  • the terpolymer of the invention may be conveniently used to for the outer sheath of fibers or filaments having a sheath-core structure.
  • the inner core may comprise any polymeric material commonly used for spunbonding applications, depending on the desired end properties of the composite fibers or filaments.
  • the sheath-core fibers or filaments comprise 50-90 wt%, more preferably 65-80 wt%, of polymeric material forming the core-layer and 10-50 wt%, more preferably 20-35 wt%, of the copolymer of propylene and 1-pentene of the invention forming the outer sheathlayer.
  • sheath-core fibers or filaments comprising 70 wt% of polymeric-material forming the core layer and 30 wt% of the terpolymer of the invention forming the outer sheath.
  • Another object of the present invention is a spunbonded non-woven fabric comprising the fibers of the invention, such fabric.
  • a further object of the present invention is a process for manufacturing the spunbonded non-woven fabric according to the invention, wherein a terpolymer as described in claim 1 is subjected to spunbonding.
  • the 13 C NMR spectrum is acquired using the following parameters: Spectral width (SW) 60 ppm Spectrum centre (O1) 30 ppm Decoupling sequence WALTZ 65_64pl Pulse program (1) ZGPG Pulse Length (P1) (2) ⁇ for 90° Total number of points (TD) 32K Relaxation Delay (2) 15s Number of transients (3) 1500
  • a copolymer is prepared by polymerising propylene, ethylene and hexene-1 in the presence of a catalyst under continuous conditions in a plant comprising a polymerisation apparatus as described in EP 1 012 195 .
  • the catalyst is sent to the polymerisation apparatus that comprises two interconnected cylindrical reactors, riser and downcomer. Fast fluidisation conditions are established in the riser by recycling gas from the gas-solid separator.
  • the gas composition in the two reactor legs has been differentiated by using the "barrier" feed according to what described in EP 1 012 195 .
  • This stream is propylene fed in the larger upper part of the downcomer.
  • the catalyst employed comprises a catalyst component prepared by analogy with example 5 of EP-A-728 769 but using microspheroidal MgCl 2 ⁇ 1.7C 2 H 5 OH instead of MgCl 2 ⁇ 2.1C 2 H 5 OH.
  • Such catalyst component is used with dicyclopentyl dimethoxy silane (DCPMS) as external donor and with triethylaluminium (TEA).
  • DCPMS dicyclopentyl dimethoxy silane
  • TEA triethylaluminium
  • the polymer particles exiting the reactor are subjected to a steam treatment to remove the reactive monomers and volatile substances and then dried.
  • the main operative conditions and characteristics of the produced polymers are indicated in Tables 1-3.
  • a copolymer is prepared by operating as in example 1, except that the "barrier" feed was not used.
  • the maximum spinning speed gives indication of the spinnability of the propylene polymer 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)
  • Artificial Filaments (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Claims (7)

  1. Faser umfassend ein Terpolymer, das Propylen, Ethylen und 1-Hexen enthält, wobei
    (i) der Gehalt an von Ethylen abgeleiteten Einheiten im Bereich von 0,5 Gew.-% bis 5,0 Gew.-% liegt;
    (ii) der Gehalt an von 1-Hexen abgeleiteten Einheiten im Bereich von 1,0 Gew.-% bis 5,0 Gew.-% liegt;
    (iii) die Menge, als Gew.-%, von 1-Hexen (α), die Menge, als Gew.-%, von Ethylen (C2) und der Schmelzpunkt (Tm) des Terpolymers der folgenden Beziehung (1) entsprechen: Tm > 157 - 6 * C ⁢ 2 + 0 , 8 ⁢ α
    Figure imgb0011
    (iv) die Schmelzfließrate (MFR) (ISO 1133 230 °C, 2,16 kg) im Bereich von 10 bis 100 g/10 min liegt.
  2. Faser nach Anspruch 1, wobei in dem Terpolymer der Gehalt an von Ethylen abgeleiteten Einheiten im Bereich von 1,0 Gew.-% bis 3,0 Gew.-% liegt; und der Gehalt an von 1-Hexen abgeleiteten Einheiten im Bereich von 2,0 Gew.-% bis 4,0 Gew.-% liegt.
  3. Faser nach einem der Ansprüche 1 - 2, wobei in dem Terpolymer die Beziehung (1) Folgendes ist: Tm > 158 - 6 * C ⁢ 2 + 0 , 8 ⁢ α
    Figure imgb0012
  4. Faser nach einem der Ansprüche 1 - 3, wobei das Terpolymer eine Kristallisationstemperatur im Bereich von 70 °C bis 100 °C aufweist.
  5. Faser nach einem der Ansprüche 1 - 4, die eine Mantel-Kern-Struktur aufweist.
  6. Spinngebundener Vliesstoff umfassend die Fasern nach einem der Ansprüche 1 - 5.
  7. Verfahren für die Herstellung des spinngebundenen Vliesstoffs nach Anspruch 6, wobei ein Terpolymer, wie es in einem der Ansprüche 1 - 4 beschrieben ist, Spinnbondieren unterworfen wird.
EP12714727.0A 2011-04-21 2012-04-20 Terpolymere auf propylenbasis für fasern Active EP2699718B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP12714727.0A EP2699718B1 (de) 2011-04-21 2012-04-20 Terpolymere auf propylenbasis für fasern

Applications Claiming Priority (4)

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US201161477885P 2011-04-21 2011-04-21
EP11163357 2011-04-21
PCT/EP2012/057229 WO2012143485A1 (en) 2011-04-21 2012-04-20 Propylene-based terpolymers for fibers
EP12714727.0A EP2699718B1 (de) 2011-04-21 2012-04-20 Terpolymere auf propylenbasis für fasern

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EP2699718A1 EP2699718A1 (de) 2014-02-26
EP2699718B1 true EP2699718B1 (de) 2015-03-04

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020058462A1 (en) * 2018-09-21 2020-03-26 Borealis Ag Polypropylene composition for melt spun fiber applications

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JP6293378B2 (ja) * 2014-12-03 2018-03-14 バーゼル・ポリオレフィン・イタリア・ソチエタ・ア・レスポンサビリタ・リミタータ 容器用プロピレン系三元重合体

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Publication number Priority date Publication date Assignee Title
WO2020058462A1 (en) * 2018-09-21 2020-03-26 Borealis Ag Polypropylene composition for melt spun fiber applications

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WO2012143485A1 (en) 2012-10-26

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