EP1597418B1 - Fibres de polypropylene - Google Patents
Fibres de polypropylene Download PDFInfo
- Publication number
- EP1597418B1 EP1597418B1 EP04709618A EP04709618A EP1597418B1 EP 1597418 B1 EP1597418 B1 EP 1597418B1 EP 04709618 A EP04709618 A EP 04709618A EP 04709618 A EP04709618 A EP 04709618A EP 1597418 B1 EP1597418 B1 EP 1597418B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- copolymer
- ethylene
- propylene
- heterophasic
- fibres
- 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.)
- Expired - Lifetime
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- -1 Polypropylene Polymers 0.000 title description 6
- 229920001155 polypropylene Polymers 0.000 title description 3
- 239000004743 Polypropylene Substances 0.000 title description 2
- 229920001577 copolymer Polymers 0.000 claims abstract description 54
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 54
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 39
- 239000005977 Ethylene Substances 0.000 claims description 39
- 239000000835 fiber Substances 0.000 claims description 33
- 229920001971 elastomer Polymers 0.000 claims description 16
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 16
- 239000005060 rubber Substances 0.000 claims description 16
- 229920005604 random copolymer Polymers 0.000 claims description 12
- 239000011159 matrix material Substances 0.000 claims description 11
- 229920000181 Ethylene propylene rubber Polymers 0.000 claims description 9
- 239000004711 α-olefin Substances 0.000 claims description 7
- 239000004745 nonwoven fabric Substances 0.000 claims description 4
- 239000002759 woven fabric Substances 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 description 29
- 238000000034 method Methods 0.000 description 23
- 239000003054 catalyst Substances 0.000 description 17
- 239000004744 fabric Substances 0.000 description 12
- 238000009987 spinning Methods 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229920001384 propylene homopolymer Polymers 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 230000000707 stereoselective effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- JWCYDYZLEAQGJJ-UHFFFAOYSA-N dicyclopentyl(dimethoxy)silane Chemical compound C1CCCC1[Si](OC)(OC)C1CCCC1 JWCYDYZLEAQGJJ-UHFFFAOYSA-N 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000000518 rheometry Methods 0.000 description 2
- 238000002076 thermal analysis method Methods 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001595 flow curve Methods 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000004750 melt-blown nonwoven Substances 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Images
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 novel fibres comprising propylene copolymers. More particularly, the invention relates to fibres comprising heterophasic propylene copolymers, especially heterophasic propylene copolymers containing a propylene random copolymer and an ethylene rubber copolymer.
- polypropylene is widely used in many fibre and fabric applications. However, it is generally deficient in applications that require high softness. Such applications include nonwoven fabrics for disposable garments or diapers and also for furniture applications. For soft-end use fibre and fabric applications random copolymers have come into use since they can be processed into fibres and fabrics that exhibit improved softness and drape characteristics compared to fibres and fabrics made from propylene homopolymers.
- the propylene copolymers are described as being an "alloy" from a random propylene copolymer having an ethylene content of 1-5 wt% and a bipolymer having an ethylene content of 10-30 wt%.
- the propylene copolymer alloy is further described as having a single T g peak, this being an indication as to the miscibility of the random copolymer and the bipolymer.
- the miscibility of the random copolymer and the bipolymer is disclosed to be a prerequisite for spinnability.
- fibres from propylene copolymers which fibres shall be characterised by excellent softness.
- the fibres shall be producible in an economical process, i.e. with high production speeds and without causing processing problems.
- the fibres of the present invention are characterised by a heterophasic propylene copolymer having at least two discernible T g peaks. Nevertheless, as will be further shown below, these heterophasic propylene copolymers are perfectly spinnable with high uptake speeds and the produced fibres are characterised by excellent softness.
- the ethylene content may range from 20 - 80 wt% preferably from 20 - 50 wt%, Accordingly, the C 3 -C 8 ⁇ -olefin content may range from 80 - 20 wt%, preferably from 80 - 50 wt%, According to a preferred embodiment the ethylene rubber copolymer is an ethylene propylene rubber (EPR).
- EPR's are more cost-effective than ethylene rubbers with higher ⁇ -olefins and they can either be synthesised in the second step of a two-step process, where the first step synthesises the matrix polymer or they can be mixed with the matrix polymer in a separate melt blending step.
- the heterophasic propylene copolymer contains 2 -15 wt%, preferably 5 -12 wt% of the ethylene rubber copolymer. These concentration ranges for the ethylene rubber are preferred, because fibres from heterophasic propylene copolymer with the above amounts of ethylene rubber copolymer offer the best compromise as to spinnability and mechanical properties, which both in general decrease with higher rubber contents, and softness, which generally increases with higher rubber content.
- the heterophasic propylene copolymer has an MFR of from 0.1 - 50 g/10 min, preferably 2.5 - 30 g/10 min. While in general a wide range of MFR's, e.g.
- the heterophasic propylene copolymer has an MFR of from 200 - 2000 g/10 min.
- the production of melt blown nonwoven fabrics of this invention requires MFR's in the range of from 200 - 2000 g/10 min.
- Heterophasic propylene copolymers having the desired MFR's may be obtained by vis-breaking the low-MFR polymer with e.g. peroxides, or they may be available directly from the polymerisation process by suitable choice of conditions.
- the fibres of the invention comprise a heterophasic propylene copolymer having an overall ethylene content of from 1.0 -15.0 wt%.
- the heterophasic propylene copolymers of which the fibres of the invention are comprised preferably show two T g temperatures.
- the first of these glass transition temperatures preferably is in the range of from -15 to +5°C, more preferably around 0°C.
- This first T g temperature usually is attributed to the matrix phase and is influenced by the comonomer content of the matrix phase. In the case of ethylene as comonomer it is lower with higher ethylene contents.
- the second of these glass transition temperatures preferably is in the range of from -35 to -65°C, more preferably from -40 to -60°C and most preferably around -50°C.
- the second T g usually is attributed to the rubber copolymer of the disperse phase and it is influenced by its molecular weight and its ethylene content.
- a particularly preferred embodiment refers to a fibre comprising a heterophasic propylene copolymer which contains 80 - 95 wt% of a matrix phase comprising a propylene random copolymer with from 1.0 -15.0 wt% of ethylene and 5 - 20 wt% of a disperse phase comprising an ethylene propylene rubber with from 20 - 40 wt% of ethylene and 80-60 wt% of propylene, the heterophasic propylene copolymer having an overall ethylene content of from 4.0 -12.0 wt% and two distinct T g peaks. Fibres made from these heterophasic propylene copolymer are characterised by superior softness, and contrary to the disclosure of US 6,218,010 , the heterophasic propylene copolymer has two T g peaks.
- the invention also refers to articles comprising fibres according to the invention.
- fabric articles include, but are not limited to: nonwoven fabrics for hygiene applications such as diapers, medical gowns and masks; woven fabrics for upholstery and clothing; ropes, twines, carpets.
- the heterophasic propylene copolymers may be used to produce fibres of the following types; continuous fibre, bulked continuous fibre, staple fibre, monofilament fibre, stretch tape, strapping; and nonwoven fabrics which are spunbonded, meltblown, or produced from staple fibre.
- the heterophasic propylene copolymers may be produced by multistage process polymerisation of propylene and ethylene and/or an ⁇ -olefin such as bulk polymerisation, gas phase polymerisation, slurry polymerisation, solution polymerisation or combinations thereof using conventional catalysts.
- Those processes are well known to one skilled in the art.
- a preferred process is a combination of bulk slurry loop reactor(s) and gas phase reactor(s).
- the matrix polymer can be made either in loop reactors or in a combination of loop and gas phase reactor.
- the polymer produced in this way is transferred into another reactor and the disperse phase is polymerised.
- this polymerisation step is done in a gas phase polymerisation.
- a suitable catalyst for the polymerisation of the heterophasic copolymer is any stereospecific catalyst for propylene polymerisation which is capable of polymerising and copolymerising propylene and comonomers at a temperature of 40 to 110°C and at a pressure from 10 to 100 bar.
- Ziegler Natta catalysts as well as metallocene catalysts are suitable catalysts.
- One skilled in the art is aware of the various possibilities to produce such heterophasic systems and will simply find out a suitable procedure to produce suitable heterophasic polymer systems which are used in the present invention.
- the heterophasic propylene copolymer may also be produced by mixing and melt blending a propylene random copolymer with an ethylene rubber copolymer.
- a heterophasic propylene copolymer prepared as explained above, may be subjected to a controlled rheology (CR) process well known in the art, whereby the copolymer is visbroken into a resin having a narrower molecular weight distribution and lower average molecular weight in order to facilitate fibre spinning.
- the molecular weight (MW) of the visbroken heterophasic copolymer determines the level of melt viscosity and the ultimate desirable physical properties of the fibre.
- the MFR of the visbroken copolymer as determined by the MFR test (ISO 1133) may vary within a wide range from fractional to about 2000 g/10 minutes.
- the CR process is preferably carried out by using organic peroxides, such as 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane).
- organic peroxides such as 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane.
- the compounds used in the CR process are added to the polymer and the polymer is , for example, visbroken during the extrusion step.
- the CR process may also convert the polymer granules to pellets for easier feeding into the fibre spinning extruder.
- Additives such as stabilizers, pigments, fillers, antioxidants, ultra-violet screening agents, nucleating agents, certain processing oils and the like may optionally be added; however, this should not be considered a limitation of the present invention.
- the heterophasic copolymer is then drawn to a fine diameter fibre by one of several well known in the art modifications of the basic melt-extrusion fibre process.
- This process consists of the steps of (1) continuously feeding the heterophasic copolymer to a melting screw extruder; (2) At the end of the screw, a spinning pump meters the melted polymer through a filter to a spinneret where the melted polymer is extruded under pressure through capillaries, typically at a rate of about 0.3-1.0 grams per hole per minute; the capillaries, depending upon the desired fibre product, may vary widely in number, size and shape; (3) solidifying the fibres by transferring the heat to a surrounding medium; and (4) winding of the solidified fibres onto packages.
- Further processing typically includes orienting the fibres by drawing them to many times their original length. Also, a variety of thermal and texturing treatments well known in the art may be employed, depending on the desired final properties of the fibre. Embodiments of the present invention fibres can be drawn into fine diameter fibres at generally high drawdown speed, without the individual fibres sticking together below the crystallization point.
- a particular embodiment of the present invention involves the use of the heterophasic copolymers for spunbonded fabrics.
- the spunbonding process is one which is well known in the art of fabric production. Generally, continuous fibres are extruded, laid on an endless belt, and then bonded to each other, and often times to a second layer such as a melt blown layer, often by a heated calander roll, or addition of a binder, or by a mechanical bonding system (entanglement) using needles or hydro jets.
- a typical spunbond process consists of a continuous filament extrusion, followed by drawing, web formation by the use of some type of ejector, and bonding of the web.
- the heterophasic copolymer is visbroken using peroxide into a resin having a narrower molecular weight distribution and about 25 MFR. During this step the polymer granules are converted into pellets.
- the pelletised 25 MFR heterophasic copolymer resin is then fed into an extruder. In the extruder, the pellets simultaneously are melted and forced through the system by a heating melting screw. At the end of the screw, a spinning pump meters the melted polymer through a filter to a spinneret where the melted polymer is extruded under pressure through capillaries, at a rate of 0.3-1.0 grams per hole per minute.
- the spinneret contains up to 6000 capillaries per metre of die width, measuring 0.4-0.6 mm in diameter.
- the polymer is melted at about 30°C -120°C above its melting point to achieve sufficiently low melt viscosity for extrusion.
- the fibres exiting the spinneret are quenched and drawn into fine fibres measuring 10 - 40 microns in diameter by cold air jets, reaching filament speeds of up to 5000 metres per minute.
- the solidified fibre is laid randomly on a moving belt to form a random netlike structure known in the art as web. After web formation the web is bonded to achieve its final strength using a heated textile calander known in the art as thermobond calander.
- the calander consists of two heated steel rolls; one roll is plain ant the other bears a pattern of raised points.
- the web is conveyed to the calander wherein a fabric is formed by pressing the web between the rolls at a bonding temperature of about 130°C -150°C.
- Crystallisation temperatures are determined by DSC measurement according to ISO 3146 at a cooling rate of 10 K/min after a first heating to 200°C.
- the shear thinning index SHI is calculated from the flow curve ⁇ ( ⁇ ) at 200°C - which can be determined with a capillary rheometer according to ISO 11443 or calculated from the complex shear viscosity determined with a plate-plate rheometer according to ISO 6271-10 using the "Cox-Merz rule" relating the shear viscosity to the dynamic viscosity as described in W.P. Cox & E.H. Merz, J.Polym.Sci. 28(1958) 619-623 .
- the SHI (0/50) is defined as the ratio between the zero shear viscosity ( ⁇ 0 ) and the viscosity at a stress ( ⁇ ) value of 50000 Pa.
- the shear thinning index is proportional to the broadness of the molecular weight distribution (MWD) of the polymer. At very high values it can reflect the bimodality of the molecular weight distribution (i.e. the MWD curve shows two maxima or one maximum and a pronounced shoulder). For reasons of processability and homogeneity the higher molecular weight tail will be limited in practice.
- MWD molecular weight distribution
- the melt flow rates were measured with a load of 2.16 kg at 230°C.
- the melt flow rate is that quantity of polymer in grams which the test apparatus standardised to ISO 1133 extrudes within 10 minutes at a temperature of 230 °C under a load of 2.16 kg.
- Ethylene content in propylene polymer was measured by Fourier transmission infrared spectroscopy (FTIR).
- FTIR Fourier transmission infrared spectroscopy
- a thin film of the sample was prepared by hot-pressing.
- the area of -CH2- absorption peak (800 - 650 cm-1) was measured with Perkin Elmer FTIR 1600 - spectrometer.
- the method was calibrated by ethylene content data measured by 13 C NMR.
- xylene solubles fraction For the determination of the xylene solubles fraction, 2.0 g of polymer are dissolved in 250 ml p-xylene at 135°C under agitation. After 30 ⁇ 2 min the solution is allowed to cool for 15 min at ambient temperature and then to settle for 30 min at 25 ⁇ 0.5°C. The solution is filtered with filter paper into two 100 ml flasks. The solution from the first 100 ml flask is evaporated in nitrogen flow and the residue is dried under vacuum at 90 °C until constant weight is achieved.
- XS largely correlates to the rubber content of the heterophasic polymer.
- the tests are carried out in accordance with ISO 6721-2 on specimens of 60x10x1 mm cut from compression moulded plaques.
- a temperature range of at least -100 to +150°C. is covered, using a heating rate of 1°C/min.
- the storage modulus G' and the tangent of the loss angle tan( ⁇ ) are the primary results of the tests; from tan( ⁇ ) the temperatures - peak position and peak broadness - of the various mobility transitions, such as the glass transition temperature T g , in the systems, which can be attributed to the phases present, can be determined.
- the mechanical properties of the fibres were determined on a Textechno Statimat M. according to ISO 5079.
- the gauge length used has been 100 mm for fibres and 200 mm for nonwoven, the speed was 100 m/min.
- the tensile test method which was used for nonwoven was Edana 20.2-89.
- Example 1 (invention, propylene/ethylene random heterophasic copolymer)
- a continuous multistage process was used.
- the process comprised a prepolymerisation step, a loop reactor and a fluidized bed gas phase reactor.
- the catalyst used was highly active, stereospecific transesterified MgCl 2 -supported Ziegler-Natta catalyst prepared according to US 5,234,879 at a titanisation temperature of 135°C.
- the catalyst was contacted with a co-catalyst (triethylaluminium, TEAL), and an external donor (di-cyclopentyl dimethoxysilane) with the Al/Ti ratio of 200 and an Al/Donor ratio of 10, to yield a catalyst system.
- TEAL triethylaluminium
- an external donor di-cyclopentyl dimethoxysilane
- the catalyst system and propylene were fed into the prepolymerisation reactor which was operated at ca. 30°C and ca. 30 bar.
- the prepolymerised catalyst was used in the subsequent polymerisation reactors.
- Propylene, ethylene and hydrogen and the prepolymerised catalyst were fed into the loop reactor which was operated as bulk reactor at a temperature of ca. 70°C and a pressure of ca. 30 bar. Then, the polymer slurry stream was fed from the loop reactor into the gas phase reactor which was operated at a temperature of ca. 70°C and a pressure of ca. 20 bar. More propylene, ethylene and hydrogen were fed into the gas phase reactor to control the desired properties of the final polymer.
- the process comprised a prepolymerisation step and a loop reactor.
- the catalyst used was highly active, stereospecific transesterified MgCl 2 -supported Ziegler-Natta catalyst prepared according to US 5,234,879 at a titanisation temperature of 135°C.
- the catalyst was contacted with a co-catalyst (triethylaluminium, TEAL), and an external donor (di-cyclopentyl dimethoxysilane) with the Al/Ti ratio of 200 and an Al/Donor ratio of 10, to yield a catalyst system.
- TEAL triethylaluminium
- an external donor di-cyclopentyl dimethoxysilane
- the catalyst system and propylene were fed into the prepolymerisation reactor which was operated at ca. 30 C and ca. 30 bar.
- the prepolymerised catalyst was used in the subsequent polymerisation reactors.
- Propylene, ethylene and hydrogen and the prepolymerised catalyst were fed into the loop reactor which was operated as bulk reactor at a temperature of ca. 70°C and a pressure of ca. 30 bar.
- the product was degassed before being fed to an extruder for pelletisation.
- Spinning trials have been performed on a Fourné long spin pilot line.
- the spinneret used has 52 holes, each having a diameter of 0.5 mm.
- the throughput per hole has been kept constant at 0.3 g/hole ⁇ min.
- the take-up speed has been increased stepwise until fibre break.
- the data of the maximum take-up speeds are shown in table 1. Fibre samples have been taken and mechanical properties have been tested. The results can be seen in Fig. 1 and 2 .
- Polymer 3 has been evaluated on a Reicofil 3.1 pilot line. It was run on a single beam at a melt temperature of 257°C at the die and a throughput of 180 kg/m/h. Spinning stability was good and at a cabin pressure of 6916 Pa the filament titer was 1.6 denier.
- the mechanical properties obtained on a 17 g/m 2 web are listed in Table 2 below. Table 2 MD tensile strength (N/5cm) 32.75 CD tensile strength (N/5cm) 22.08 MD elongation (%) 67.57 CD elongation (%) 72.88
- the samples used for determining softness were yarns produced at 1000 m/min and 235°C from the spinnability test. 600 m of yarn are wound on a reel, doubled (i.e. folded) and the ends secured between 3 cardboard sheets. Evaluation of softness was by black box panel. Seven persons tested each fibre material and marked their tactile impressions on a scale from 1-5. "1" means that the fibre has about the same softness as a fibre from a propylene homopolymer produced under the same conditions. "5" means that the fibre is very much softer than a fibre from a propylene homopolymer produced under the same conditions. The results are shown in Table 3. Table 3 Polymer-no. 1 2 3 4 softness relative to homopolymer persons tester no. 1 1 5 5 1 tester no. 2 1 5 5 1 tester no. 3 1 5 5 1 tester no. 4 1 5 5 1 tester no. 5 1 5 5 1 tester no. 6 1 5 5 1 tester no. 7 1 5 5 1
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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)
- Nonwoven Fabrics (AREA)
- Multicomponent Fibers (AREA)
- Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Dental Preparations (AREA)
- Materials For Medical Uses (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Claims (9)
- Fibre comprenant un copolymère hétérophasique de propylène contenanta) 80-99 % en poids d'une phase formant matrice comprenant un copolymère statistique de propylène avec 0,2-15 % en poids d'éthylène et/ou d'au moins une α-oléfine en C4 - C8 etb) 1-20 % en poids d'une phase dispersée comprenant un copolymère caoutchouc d'éthylène avec 20-80 % en poids d'éthylène et 80-20 % en poids d'au moins une α-oléfine en C3 - C8,dans laquelle le copolymère hétérophasique possède au moins deux pics Tg.
- Fibre selon la revendication 1, caractérisée en ce que le copolymère caoutchouc d'éthylène est un caoutchouc d'éthylène-propylène.
- Fibre selon l'une quelconque des revendications 1 et 2, caractérisée en ce que le copolymère hétérophasique statistique de propylène contient 2-15 % en poids , de préférence 5-12 % en poids, du copolymère caoutchouc d'éthylène.
- Fibre selon l'une quelconque des revendications 1 à 3, caractérisée en ce que le copolymère hétérophasique de propylène possède un MFR de 0,1 - 50 g/10 min, de préférence de 2,5 - 30 g/10 min.
- Fibre selon l'une quelconque des revendications 1 à 3, caractérisée en ce que le copolymère hétérophasique de propylène possède un MFR de 200 - 2000 g/10 min.
- Fibre selon l'une quelconque des revendications 1 à 5, caractérisée en ce que le copolymère hétérophasique de propylène possède une teneur totale en éthylène de 1,0 - 15,0 % en poids.
- Fibre selon l'une quelconque des revendications 1 à 6, caractérisée en ce que le copolymère hétérophasique de propylène possède une première Tg dans la plage de -15 à +5°C, de préférence aux environs de 0°C, et une seconde Tg dans la plage de -35 à -65°C, de préférence de -40 à -60°C, et plus particulièrement aux environs de -50°C.
- Fibre selon l'une quelconque des revendications 1 à 7, caractérisée en ce que le copolymère hétérophasique de propylène contient 80-95 % en poids d'une phase formant matrice comprenant un copolymère statistique de propylène avec 1,0-15,0 % en poids d'éthylène et 5-20 % en poids d'une phase dispersée comprenant un caoutchouc d'éthylène-propylène avec 20-40 % en poids d'éthylène et 80-60 % en poids de propylène, le copolymère hétérophasique de propylène ayant une teneur totale en éthylène de 4,0-12,0 % en poids et deux pics Tg distincts.
- Objets comprenant des fibres selon l'une quelconque des revendications 1 à 8, en particulier des tissus non-tissés, par exemple des couches, des blouses et masques médicaux ; des tissus tissés, par exemple des tapisseries d'ameublement, des vêtements, des cordes, des ficelles et des tapis.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP04709618A EP1597418B1 (fr) | 2003-02-26 | 2004-02-10 | Fibres de polypropylene |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP03004115 | 2003-02-26 | ||
EP03004115A EP1452630A1 (fr) | 2003-02-26 | 2003-02-26 | Fibres de polypropylène |
PCT/EP2004/001210 WO2004076726A1 (fr) | 2003-02-26 | 2004-02-10 | Fibres de polypropylene |
EP04709618A EP1597418B1 (fr) | 2003-02-26 | 2004-02-10 | Fibres de polypropylene |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1597418A1 EP1597418A1 (fr) | 2005-11-23 |
EP1597418B1 true EP1597418B1 (fr) | 2008-12-17 |
Family
ID=32748793
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP03004115A Withdrawn EP1452630A1 (fr) | 2003-02-26 | 2003-02-26 | Fibres de polypropylène |
EP04709618A Expired - Lifetime EP1597418B1 (fr) | 2003-02-26 | 2004-02-10 | Fibres de polypropylene |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP03004115A Withdrawn EP1452630A1 (fr) | 2003-02-26 | 2003-02-26 | Fibres de polypropylène |
Country Status (6)
Country | Link |
---|---|
EP (2) | EP1452630A1 (fr) |
AT (1) | ATE417948T1 (fr) |
DE (1) | DE602004018464D1 (fr) |
DK (1) | DK1597418T3 (fr) |
PL (1) | PL378558A1 (fr) |
WO (1) | WO2004076726A1 (fr) |
Families Citing this family (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1935938A1 (fr) * | 2006-12-18 | 2008-06-25 | Borealis Technology Oy | Appareil électronique |
EP2025712A1 (fr) * | 2007-08-09 | 2009-02-18 | Borealis Technology Oy | nouvelles compositions de polyoléfine et bandes, fibres et filaments étirés fabriqués à partir de celles-ci |
DE602007003738D1 (de) * | 2007-10-11 | 2010-01-21 | Borealis Tech Oy | Weiche Polypropylenzusammensetzung mit Soft-Touch-Gefühl |
WO2009058477A1 (fr) * | 2007-10-31 | 2009-05-07 | Exxonmobil Chemical Patents Inc. | Fibres en polypropylène pour non-tissé |
EP2151512A1 (fr) * | 2008-08-01 | 2010-02-10 | Total Petrochemicals Research Feluy | Fibres et non-tissés dotés d'une rugosité de surface améliorée |
PL2174980T5 (pl) * | 2008-10-07 | 2019-04-30 | Borealis Ag | Polipropylen heterofazowy o dużej płynności |
EP2223943B1 (fr) * | 2009-02-25 | 2011-10-19 | Borealis AG | Polymère de propylène multimodal, composition le contenant et son procédé de fabrication |
WO2015022127A1 (fr) | 2013-08-14 | 2015-02-19 | Borealis Ag | Composition de propylène ayant une résistance au choc améliorée à basse température |
JP2016528368A (ja) | 2013-08-21 | 2016-09-15 | ボレアリス・アクチェンゲゼルシャフトBorealis Ag | 高い剛性および靭性を有する高流動ポリオレフィン組成物 |
CN105452365B (zh) | 2013-08-21 | 2018-04-17 | 博里利斯股份公司 | 具有高刚度和韧性的高流动聚烯烃组合物 |
PT2853563T (pt) | 2013-09-27 | 2016-07-14 | Borealis Ag | Filmes adequados para processamento de bopp a partir de polímeros com xs elevada e tm elevado |
ES2568615T3 (es) | 2013-10-11 | 2016-05-03 | Borealis Ag | Película para etiquetas orientada en la dirección de la máquina |
WO2015059229A1 (fr) | 2013-10-24 | 2015-04-30 | Borealis Ag | Homopolymère pp à bas point de fusion ayant une haute teneur en regioerreurs et un poids moléculaire élevé |
ES2644829T3 (es) | 2013-11-22 | 2017-11-30 | Borealis Ag | Homopolímero de propileno de baja emisión con alto flujo de masa fundida |
CN105793298B (zh) | 2013-12-04 | 2019-06-28 | 博里利斯股份公司 | 用于熔喷纤维的不含邻苯二甲酸酯的pp均聚物 |
CN105980457B (zh) | 2013-12-18 | 2019-03-22 | 博里利斯股份公司 | 具有改善的刚性/韧性平衡的bopp膜 |
CN105829364B (zh) | 2014-01-17 | 2017-11-10 | 博里利斯股份公司 | 用于制备丙烯/1‑丁烯共聚物的方法 |
CN112225997B (zh) | 2014-02-06 | 2023-09-22 | 北欧化工公司 | 高冲击强度的柔性共聚物 |
PL3102634T3 (pl) * | 2014-02-06 | 2020-11-16 | Borealis Ag | Miękkie i przezroczyste kopolimery odporne na uderzenia |
EP2907841A1 (fr) | 2014-02-14 | 2015-08-19 | Borealis AG | Composition de polypropylène |
ES2659731T3 (es) * | 2014-05-20 | 2018-03-19 | Borealis Ag | Composición de polipropileno para aplicaciones en interiores de automóviles |
CN111424360A (zh) * | 2020-04-23 | 2020-07-17 | 吴宁西 | 一种具备长效可反复使用的n90级别口罩及其制备方法 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CZ5693A3 (en) * | 1992-01-23 | 1993-10-13 | Himont Inc | Elastic yarn of polypropylene polymer and articles made therefrom |
IT1264840B1 (it) * | 1993-06-17 | 1996-10-17 | Himont Inc | Fibre adatte per la produzione di tessuti non tessuti con migliorate caratteristiche di tenacita' e sofficita' |
US6235664B1 (en) * | 1997-03-04 | 2001-05-22 | Exxon Chemical Patents, Inc. | Polypropylene copolymer alloys for soft nonwoven fabrics |
EP1041111A1 (fr) * | 1997-12-11 | 2000-10-04 | Sumitomo Chemical Company, Limited | Composition d'elastomere thermoplastique, poudre, pastilles et articles moules |
DE69927221T2 (de) * | 1998-01-29 | 2006-07-13 | Sumitomo Chemical Co., Ltd. | Thermoplastische elastomerzusammensetzung in pulverform, pulverformverfahren unter verwendung derselben und formteile |
-
2003
- 2003-02-26 EP EP03004115A patent/EP1452630A1/fr not_active Withdrawn
-
2004
- 2004-02-10 EP EP04709618A patent/EP1597418B1/fr not_active Expired - Lifetime
- 2004-02-10 WO PCT/EP2004/001210 patent/WO2004076726A1/fr active Application Filing
- 2004-02-10 AT AT04709618T patent/ATE417948T1/de not_active IP Right Cessation
- 2004-02-10 DE DE602004018464T patent/DE602004018464D1/de not_active Expired - Lifetime
- 2004-02-10 DK DK04709618T patent/DK1597418T3/da active
- 2004-02-10 PL PL378558A patent/PL378558A1/pl unknown
Also Published As
Publication number | Publication date |
---|---|
EP1597418A1 (fr) | 2005-11-23 |
WO2004076726A1 (fr) | 2004-09-10 |
ATE417948T1 (de) | 2009-01-15 |
EP1452630A1 (fr) | 2004-09-01 |
DK1597418T3 (da) | 2009-03-30 |
DE602004018464D1 (de) | 2009-01-29 |
PL378558A1 (pl) | 2006-05-02 |
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