CN101657572B - Fibers, tapes or filaments comprising multimodal polyethylene composition - Google Patents
Fibers, tapes or filaments comprising multimodal polyethylene composition Download PDFInfo
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- CN101657572B CN101657572B CN200880009377.6A CN200880009377A CN101657572B CN 101657572 B CN101657572 B CN 101657572B CN 200880009377 A CN200880009377 A CN 200880009377A CN 101657572 B CN101657572 B CN 101657572B
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- 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
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- 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
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Abstract
The present invention is directed to fibres, tapes or filaments comprising a multimodal polyethylene composition, to the preparation process thereof, to the use of a multimodal polyethylene composition, as well as articles comprising said fibres, tapes or filaments.
Description
The present invention relates to the fiber, band and the silk that contain multimodal polyethylene (PE) composition, its preparation method, multimodal polyethylene composition is in the application of preparing in fiber, band or silk, and the goods that contain described fiber, band or silk, a lot of Application Areass comprises technology application, family expenses, indoor (interior) and sports applications.
Background technology
The polythene material that is used to fiber, band and silk product is generally unimodal.Typically, they also have high density, as are greater than 945kg/m
3.
WO2006053709 has described a kind of multimodal polyethylene for the band that stretches, fiber and silk, and it has the 940kg/m of being at least
3density.It is said, compared with the unimodal polyethylene product of equal densities level, it can be for fiber provides similarly or the character improving, as toughness.
In exigent fiber applications occasion, for example technology application or sports applications aspect, fiber need to stand very high mechanical stress and wearing and tearing.In some application scenarios, as moving surface (sport surface) material, fibrous material is soft, but has again good mar proof simultaneously, i.e. ABRASION RESISTANCE, and this is favourable.Fiber also should be preferably flexible and/or toughness, thereby after being subject to mechanical stress effect, reply its original state.And during especially for playing field, now fiber is normally used for artificial grass material, need to there is good UV(ultraviolet) photostability.In order to keep in a long time constant performance and/or outward appearance, above-mentioned character be favourable.
In the prior art, polypropylene-base fiber is used to many exigent application scenarios, for example moving surface.But the fiber of these prior aries, may not have enough flexibilities and UV stability.
The rub resistance abrasiveness of unimodal polyethylene fiber of the prior art is not enough to the performance that keeps constant conventionally, for example, in long-time, guarantee the constant motion/physical culture characteristic of artificial grass.
Therefore, exist thering is heterogeneity combination, to be suitable for or to be exclusively used in the demand of fiber, band and wire material of the final application of variation always.
summary of the invention
An object of the present invention is to provide the other multimodal polyethylene composition for the preparation of fiber, band and silk, described multimodal polyethylene composition can provide for fiber product the combination of unforeseeable character.
Another object of the present invention is to provide other fiber, band and silk, it contains multimodal polyethylene composition, and show the excellent balance of properties that is suitable for various fiber applications occasions, the especially technology application of described application scenario, comprise industry, agricultural and GEOLOGICAL APPLICATION, such as rope, twine, great Bao, net and geotextile, and family expenses, indoor and sports applications, for example for the synthesis of carpet and moving surface, for example, for the stadium of indoor or outdoors and the artificial grass material of sports ground.
In addition, the invention provides a kind of method of preparing fiber of the present invention, band and silk, and the goods that contain described fiber, band and silk.
brief description of drawings
The schematic diagram of the thread path in the braiding simulator shown in Fig. 1, described simulator is used to the abrasion test described in " method of testing ".
Shown in Fig. 2 is znLLDPEl, reference example PE1 and the PE2 of the embodiment of the present invention, is under 1:5 and 1:6 at draw ratio, records the curve map of the balance of toughness and percentage elongation.
Shown in Fig. 3 is the material of znLLDPEl of the present invention, reference example PE1 and PE2, braiding simulator in, under load (every band is 120g), stand 6000 times circulation processing time mar proof, i.e. the curve map of ABRASION RESISTANCE.For every kind of material, prepare 5 band samples, shown in described figure is the number of the band of test process Fracture, and the cycle-index in when fracture.
detailed Description Of The Invention
The present invention relates to a kind of band, fiber and silk, it contains multimodal linear low density polyethylene composition, and described composition has the 940kg/m of being less than
3density.Due to this low-density, compared with being generally used for the fibrous material of higher density of the prior art, can provide softer fibrous material.It is shocking, softer fiber provided by the invention, band and silk have excellent ABRASION RESISTANCE, also referred to as mar proof.Compared with the fiber of being prepared by polyethylene unimodal, higher density in prior art, the ABRASION RESISTANCE of described fiber, band and silk is at least suitable with it, or even can be raising.Therefore, multimodal linear low density polyethylene of the present invention is the fit closely replacement material of fiber, band or silk.
Can be used for polyethylene of the present invention is linear polyethylene.Thereby it is different from tubular type or autoclave, typically be the low density polyethylene (LDPE) (LDPE) that adopts radical initiator, prepared by high-pressure polymerization process.Term used and implication/difference thereof are being known in the art.
Technical staff as polymer arts is known, and density is 940kg/m
3or lower polyethylene composition, in polymer document, be sometimes also defined as having contained, especially medium density polyethylene (MDPE) composition and linear low density polyethylene (LLDPE) composition.In this application, density is less than 940kg/m
3multimodal polyethylene composition, be called " multimodal LLDPE composition " or " multimodal LLDPE " for short, and natch, it has contained the polyethylene within the density range in " MDPE ".
The term " fiber, band or silk " that is used in reference to fiber of the present invention, band and silk in the application, is called " Fibre " for short, and it contains and mean fiber art all known, that can make and used all conventional forms.
In a preferred Fibre embodiment of the present invention, described Fibre can provide, except the balance between above-mentioned unforeseeable flexibility and ABRASION RESISTANCE, preferably can also provide, especially very feasible tensile property, described tensile property, in the time adopting that below " assay method " defined method is measured, is expressed as the balance between toughness and elongation at break.Equally preferably, Fibre of the present invention also can have good UV stability.
Like this, the multimodal LLDPE that can be used for described Fibre also can, according to the desired final application of described Fibre, to one or more other preferred properties in above-mentioned Fibre embodiment, further adjust and optimize.
And the above-mentioned multimodality of described LLDPE contributes to, in Fibre preparation technology, to obtain favourable processing characteristics.
Like this, Fibre of the present invention is suitable for many fiber applications occasions very much, especially technology application, comprise industry, agricultural and GEOLOGICAL APPLICATION, such as rope and twine, great Bao, net and geotextile, and family expenses, indoor and sports applications, for example for the synthesis of carpet and moving surface, for example, for the stadium of indoor or outdoors and the artificial grass material of sports ground.
Term " carpet " and " artificial grass " are also known wording, it refers in these products, Fibre, by the fixing means of any routine, is connected to and typically is on flat base members, and at least one end of described fiber is freely given prominence to from described base members.Fibre also can, from its core, be fixed on described base members, makes Fibre end have certain drift and energy " freely-movable ".Freely the length of " Fibre end " can change according to desired final application, and this is known in the field.
Equally, the average diameter of Fibre of the present invention/width ratio, can change according to final application.
Like this, be present in the multimodal LLDPE composition in described Fibre, can, about for example listed one or more other preferred properties above, according to the desired final application of described Fibre, further adjust and optimize.
Below defined other features, as other character or scope, conventionally be applicable to be present in the described multimodal LLDPE in Fibre of the present invention, be applicable to the preparation method of described multimodal LLDPE, be applicable to described Fibre of the present invention, be applicable to the preparation method of Fibre and the goods of the present invention that contain described Fibre.Natch, described feature can be with any combination, combined with any order, thereby preferred subgroup, embodiment and variant of the present invention are defined.
Multimodal LLDPE composition
Above or hereinafter described be present in the multimodal LLDPE in described Fibre, can adopt the complex catalyst of any routine to carry out polymerization.Like this, the multimodal LLDPE composition can be used in described Fibre comprises, for example, adopt LLDPE(the present invention of Ziegler Natta polymerization catalyst to be called znLLDPE), adopt LLDPE(the present invention of the single-site catalysts polymerization including metallocene and non-metallocene catalyst that the LLDPE of all single centers base is called to mLLDPE) or adopt the LLDPE of chrome catalysts polymerization.Preferably, multimodal LLDPE composition is multimodal znLLDPE.
Except as otherwise noted, term " multimodal " herein refers to, with regard to molecular weight distribution, to have multimodality, and it also comprises bimodal polymers.Conventionally, the polyethylene that contains at least two kinds of polyethylene components of preparation, (weight average) molecular weight and molecualr weight distribution that obtains having difference under different polymerizing conditions, as LLDPE composition, is called as " multimodal ".Prefix " many " refers to the quantity that is present in the different polymers compositions in polymer.Like this, for example, multimodal polymer comprises so-called " bimodal " polymer being made up of two kinds of components.The form of the molecular weight distribution curve of for example LLDPE of multimodal polymer (, the weight fraction of polymer is as the outward appearance of the curve map of the function of its molecular weight), there is two or more maximum, or compared with the curve of single component, typically obviously broadened.For example, if polymer is in continuous multistage process, adopts the reactor of series connection and adopt different condition preparations, each molecular weight distribution and the weight average molecular weight with oneself of polymers compositions making in differential responses still in each reactor.In the time recording the molecular weight distribution curve of this polymer, from the each single curve of these components together, typically form broadening of total polymeric articles of obtaining molecular weight distribution curve.
Can be used for multimodal LLDPE of the present invention preferably contains compared with lower molecular wt (LMW) component and higher weight average molecular weight (HMW) component.Described LMW component has the molecular weight lower than HMW component.
In a preferred embodiment of Fibre, described multimodal LLDPE comprises that at least (i) is compared with Alathon or the copolymer component of lower molecular wt (LMW), and (ii) Alathon or the copolymer component of higher weight average molecular weight (HMW).Preferably, at least one in described LMW and HMW component is the copolymer of ethene and at least one comonomer.Preferably, at least described HMW component is ethylene copolymer.Selectively, if the one in described component is homopolymers, so preferred described LMW is this homopolymers.
Selectively, described multimodal LLDPE can contain other polymers compositionss, for example three kinds of components, thus become three peak LLDPE.Optionally, multimodal LLDPE also can contain, and for example, up to the known polyethylene prepolymer of 10wt%, described prepolymer is obtained by prepolymerization step known in the field, for example, and described in WO9618662.In the situation that there is this prepolymer, described pre-polymer component can be included in the one in above defined LMW and HMW component, preferably in LMW component.
Preferably, described multimodal LLDPE is bimodal LLDPE, the component that it contains described LMW and HMW component and optional pre-polymerization defined above.
Multimodality as claimed in claim 1 and the density characteristics of multimodal LLDPE, for the present invention has brought unforeseeable effect, especially flexibility and ABRASION RESISTANCE.Other character of described multimodal LLDPE can further contribute to obtain excellent properties of the present invention, and can, according to desired final application, change within the scope of the invention.Therefore, described multimodal LLDPE composition can any combination has mainly by below providing, any preferred character.
Above or hereinafter described can be used for described multimodal LLDPE composition of the present invention, preferably there is 938kg/m
3or lower density.Lower limit is typically greater than 905kg/m
3, be preferably 915kg/m
3or higher, higher is 920kg/m
3or higher.
The melt flow rate MFR of described multimodal LLDPE
2, being preferably 0.01～20g/10 minute, for example 0.05～10g/10 minute, is preferably 0.05～6.0g/10 minute, more preferably 0.1～5g/10 minute.Expect that at some LLDPE has low MFR
2in the Fibre embodiment of value, so, the MFR of described multimodal LLDPE
2even can be and be less than 3g/10 minute, for example 0.1～2.5g/10 minute.
Above or the below MFR of defined multimodal LLDPE
5, can, up to 10g/10 minute, be preferably 0.01～5g/10 minute, for example 0.05～4g/10 minute.The Mw of LLDPE can be 100,000～300, and 000, preferably 150,000～270,000.The molecular weight distribution (MWD) of described multimodal LLDPE, Mw/Mn, is preferably at least 5, is more preferably at least 8, for example, be 10～40, preferably up to 30; And depend on final application scenario, 10～25 Mw/Mn also expects.
Term used herein " ethylene copolymer " or " LLDPE copolymer " comprise and contain derived from ethylene and at least one polymer as the repetitive of other C3-20 'alpha '-olefin monomers of comonomer.Preferably, described multimodal LLDPE copolymer can be prepared by ethene and at least one C3-12 alpha-olefin comonomer, and described comonomer is as 1-butylene, 1-hexene or 1-octene.Preferably, described multimodal LLDPE is bipolymer, and described polymer contains ethene and a kind of comonomer; Or terpolymer, described polymer contains ethene and two or three comonomer.Preferably, described multimodal LLDPE comprises ethene hexene copolymer, POE or ethylene-butylene copolymer.With respect to ethene, the amount of the comonomer existing in described multimodal LLDPE is preferably at least 0.25mol%, is more preferably at least 0.5mol%, for example 0.5～12mol%, for example 2～10mol%.In some embodiments, co-monomer content scope is that 4～8mol% is desirable.Selectively, with respect to ethene, the co-monomer content being present in described multimodal LLDPE can be 1.5～10wt%, particularly 2～8wt%.In the HMW component of arbitrarily copolymerization, preferably 0.5mol% at least, for example lmol% at least, as the repetitive up to 10mol% derived from as described in comonomer.
Above or the below LMW component of defined multimodal LLDPE, can have and be at least 50, typically is 50～3000g/10 minute, is preferably at least 100g/10 minute, more preferably the MFR of 110～500g/10 minute
2.The molecular weight of described LMW component is preferably 15,000～50, and 000, for example 20,000～40,000.The density of described LMW component can be 930～980kg/m
3, for example 930～970kg/m
3, for example 935～960kg/m
3; In the situation that being LMW homopolymers, typically be 940～980kg/m
3, be preferably 960～975kg/m
3.
The content of described LMW component is preferably 30～70wt% of described multimodal LLDPE gross weight, for example 40～60wt%.Described HMW component typically accounts for 70～30wt% of described multimodal LLDPE, for example 40～60wt%.In one embodiment, described HMW constituent content accounts for the 50wt% of multimodal LLDPE or hereinafter described or higher above.
Described multimodal LLDPE as defined HMW component above or below, have than the low MFR of described LMW component
2with low density.Preferably, described HMW component has the 1g/10 of being less than minute, is preferably and is less than 0.5g/10 minute, especially for being less than the MFR of 0.2g/10 minute
2.The density of described HMW component can be and is greater than 900kg/m
3, be preferably 910～930, for example, up to 925kg/m
3.The Mw of HMW component can be 100,000～1, and 000,000, be preferably 250,000～500,000.
In a preferred embodiment of Fibre, above or below defined multimodal LLDPE is the multimodal znLLDPE copolymer of ethene and at least one comonomer, as described above.
The preparation of multimodal LLDPE polymer
As above or below defined, be suitable for preparing the multimodal LLDPE of Fibre of the present invention, be preferably znLLDPE, can be any routine, the polymer composition that is for example purchased.As an example of the useful multimodal LLDPE polymer being purchased, can be by, especially Borealis is with trade mark Borecene
fBXXXX, as Borecene
the acquisitions such as FB4370 (being not limited to these).
Selectively, suitable multimodal LLDPE polymer composition can adopt known mode, according to or similarly according to the conventional polymerization technique preparation of describing in polymer chemistry document, comprise polymerisation in solution, slurry polymerization and gas-phase polymerization process.
Can be used for multimodal of the present invention (for example bimodal) LLDPE, can be by by two or more, the separately polymers compositions mechanical blending of preparation and obtaining, or preferably, in the preparation process of polymers compositions, in multistage polymerization technique, carry out in-situ blending and obtain.Mechanical blending and in-situ blending are all known in the field.
Therefore, preferred multimodal LLDPE polymer, is by the multistage, i.e. prepared by the polymerization technique situ blend in two or more stages; Described polymerization technique comprises polymerisation in solution, slurry polymerization and the gas-phase polymerization of carrying out with random order.Selectively, described multimodal LLDPE can, by a polymerization stage, adopt two or more different polymerization catalysts, comprises multicenter or two centers catalyse agent, and prepares.
Preferably, multimodal LLDPE is adopting identical catalyst Ru Dan center or Ziegler-Natta catalyst, is at least in the polymerization in two stages and prepares.Like this, for example, can adopt two slurry reaction stills or two gas phase reaction kettles or their any combination of random order.But preferably, multimodal LLDPE carries out slurry polymerization in loop reactor (loop reactor), in gas phase reaction kettle, carry out gas-phase polymerization subsequently and prepare.
Loop reactor-gas phase reaction kettle system is known as Borealis technology, i.e. BORSTAR
reactor system.Like this, be present in any multimodal LLDPE in Fibre of the present invention, preferably in two-stage process, prepare, described technique comprises a first slurry loop polymerization stage, follows by the gas-phase polymerization stage.This multistage process is disclosed in, for example, in EP517868.
The condition adopting in this technique is known.For slurry reaction still, reaction temperature is generally 60～110 ℃, and for example 85～110 ℃, reactor pressure is generally 5～80 bar, for example 50～65 bar, and the time of staying is generally 0.3～5 hour, for example 0.5～2 hour.It is the aliphatic hydrocarbon of-70～+ 100 ℃ that the diluent adopting is generally boiling point.In these reactors, if desired, can be in polymerization under supercriticality.Slurry polymerization also can large quantities of (in bulk) carry out, and wherein, reaction medium is formed by the monomer in polymerization just.
For gas phase reaction kettle, the reaction temperature of employing is generally 60～115 ℃, for example, and 70～110 ℃; Reactor pressure is generally 10～25 bar, and the time of staying is generally 1～8 hour.Gas used is generally non-reacted gas, as nitrogen or low boiling hydrocarbon, as with monomer as the propane together with ethene.
As an example of chain-transferring agent, be preferably hydrogen, be added into as requested in reactor, and when prepare LMW component in the reactor of loop time, in this loop reactor, add at least 100 to preferably at least 200, and up to 1500, preferably up to being 800 moles of H
2/ kilomol ethene; When prepare HMW component in gas phase reaction kettle time, in this gas phase reaction kettle, add 0～60 or 0～50 mole of H
2/ kilomol ethene, and depend on again desired final application scenario, in specific embodiment, adds even up to 100, or up to 500 moles of H
2/ kilomol ethene.
Preferably, low-molecular weight polymer component is prepared in the loop reactor of continuously operation, and in this reactor, in the case of existing polymerization catalyst mentioned above and chain-transferring agent as hydrogen, ethene is aggregated.Diluent typically is inertia aliphatic hydrocarbon, is preferably iso-butane or propane.Then, product is transferred to, and is preferably in the gas phase reaction kettle of continuous operation.Then,, in gas phase reaction kettle, preferably adopt identical catalyst to prepare HMW component.
Prepolymerization step can be carried out before actual polymerization technique.
HMW component be in the second step at multistage polymerization, prepare, can not be directly its character of measurement.But, for example, in above-mentioned polymerization technique of the present invention, the density of HMW component, MFR
2deng, can adopt Kim McAuley equation to calculate.Like this, adopt K.K.McAuley and J.F.McGregor:On-line Inference of Polymer Properties in an Industrial Polyethylene Reactor, AIChE Journal, in June, 1991, the 37th the 6th phase of volume, 825-835 page, can obtain density and MFR
2.Density is calculated by McAuley equation 37, and in this equation, the density after final density and the first reactor is known.MFR
2calculated by McAuley equation 25, in this equation, calculate final MFR
2with the MFR after the first reactor
2.
As above or below defined, be suitable for multimodal LLDPE of the present invention, can adopt the catalyst of any routine, for example chromium, single-site catalysts, comprise metallocene well known in the art or Nonmetallocene, or be that Ziegler-Natta catalyst well known in the art is prepared equally.Preferred catalyst is the Ziegler Natta catalyst of any routine, and is inessential for the preparation of the selection of the single catalyst of znLLDPE.
The in the situation that of multimodal znLLDPE, polyethylene polymer composition adopts Ziegler-Natta catalysis to prepare.Preferred Ziegler-Natta catalyst comprises transition metal component and activator.Described transition metal component comprises that the metal of periodic system (IUPAC) the 4th or 5 families is as active metal.In addition, it also can comprise other metals or element, for example the 2nd, the element of 13 and 17 families.Preferably, described transition metal component is solid.More preferably, it is loaded on carrier material, as inorganic oxide carrier or magnesium halide.The example of this catalyst, especially providing in WO95/35323, WO01/55230, WO2004/000933, EP810235 and WO 99/51646 etc.
In highly preferred embodiment of the present invention, polyethylene composition adopts disclosed Ziegler Natta catalyst in WO2004/000933 or EP688794 to prepare.
Also can adopt conventional co-catalyst commonly known in the art, supporter/carrier, electron donor etc.
The product that described multimodal LLDPE polymerization technique obtains, typically granulation in known manner, then, multimodal LLDPE pellet is used to Fibre preparation.
Fibre of the present invention also can contain other polymer that are different from multimodal LLDPE.Preferably, described Fibre is made up of multimodal LLDPE.Described term " composition ", when in the Fibre that is used to the application when existing polymer composition, only refer in this Fibre embodiment, there are not other polymers compositionss, but natch, described Fibre in this embodiment can contain conventional fiber additive, as antioxidant, UV stabilizing agent, Masterbatch, plumper, nucleator, anti-blocking agent, slip agent etc., and polymer processing aids (PPA).As everyone knows, it can in the preparation process of fiber, for example, in the process of preparing polymer, join in polymer composition.
Fibre preparation
Above or below defined, the multimodal LLDPE polymer product that typically is pellet form, in the mode of recording in known and prior art, is converted into Fibre of the present invention.
Fiber can preferably be prepared by film expressing technique, for example casting films or blown film process, and by cutting film with preparation, especially, band; Or by direct expressing technique preparation silk, preferably monofilament.
In the time of mixture that Fibre of the present invention contains multimodal LLDPE and other polymers compositionss, typically, before extruding, different polymers compositionss is fully mixed, this is known in the field.
According to a selectable method conventionally adopting, adopt known silk expressing technique, described multimodal LLDPE polymer product can be extruded and form fiber, band or silk, be preferably monofilament.The useful technique of one for the preparation of Fibre of the present invention is described in Hans
lenz, in Herman F.Mark " Fiber Technology ", ISBN:0-8247-7097-8.
Also be in the selectable method conventionally adopting at second, described multimodal LLDPE composition is extruded to formation film in known manner, subsequently described film cutting is slit into fiber and band.These two kinds of methods are all conventional, well-known methods in the preparation of fiber, band and silk.
For first forming film, be then cut to the Fibre preparation technology of fiber or band: described film can, by the film-forming process preparation of any routine, comprise expressing technique, as casting films or blown film expressing technique, lamination process or their any combination.Described film can be single thin film or plural layers, for example, and the plural layers of coextrusion.The in the situation that of plural layers, preferably, thin layer can have identical or different polymer composition, and at least one deck has described multimodal LLDPE of the present invention thus.Preferably, all layers of plural layers all contain, and more preferably, are made up of described multimodal LLDPE composition.
Particularly preferably, described film is to extrude preparation by blown film, and the in the situation that of multi-layer film structure, prepares by blown film coextrusion processes.Typically, described LLDPE composition can be extruded at 160 ℃～240 ℃ in blowing (being total to), and cooling by being blown into the gas (normally air) of 10～50 ℃, thereby be provided as the frost line height of 1 or 2～8 times (frost line height) of port mould diameter.Blow-up ratio should be less than 6 conventionally, for example, be less than 4, is more preferably 1.0～1.5, and even more preferably 1.0～1.2.
For example, film can (be total to) and extrude first to form bubble, then subsides also cooling, if necessary, the tubular-film obtaining is cut into fiber.Selectively, (being total to) extruded bubble and can be subsided, and is divided into two rete zoariums.Then the film forming is cut into Fibre.
Selectively, Fibre can be formed by casting films cutting, and described casting films is prepared by method well known in the art.
In an embodiment very preferably of the present invention, Fibre is stretching, the i.e. form of orientation.Preferably, Fibre is uniaxial tension, more preferably, and in longitudinally (machine direction (MD)) upper stretching.Therefore, first straight forming can selection scheme in, after extruding and forming silk, described Fibre is stretched to desirable draw ratio.Prepare at second Fibre can selection scheme in, wherein first form film and be cut into Fibre, described film is being cut into the Fibre of stretching, for example, before band, can be stretched, or described film is first cut into, for example band, the band then forming is stretched to form final Fibre.Preferably, first film is cut into, for example band, and then described band is stretched to desirable draw ratio to form final Fibre.About first forming film, be cut to the preparation technology of the fiber of fiber and band, can be referring to known Lenzing technique (before cutting into band, first oriented film) and Iso technique (film cutting being slit into band, the band that then stretches and form).
Like this, as preferred embodiment, can provide and be preferably in stretching, be orientated form, be preferably the Fibre of the stretching of uniaxial orientation form.
In drawing process, for example, in the process of line drawing (in line stretching), typically, can apply heat.Draw ratio can mode well known in the art, for example, determined by the speed ratio of the godet roller before and after heater.Be well known that equally, depend on the needs of final application, can be optimized and adaptive change stretching and heat setting ratio.Can adopt for example baking oven or heating plate as heater.
Therefore, Fibre preparation technology preferably includes following steps: the silk of extruding that stretches, the fiber/band that stretches and formed by film cutting, or oriented film before cutting into fiber/band, stretches preferably upper at longitudinal (MD) thus, carries out with the draw ratio that is at least 1:3.
Like this, preferably Fibre preparation technology comprises the steps: described multimodal LLDPE to be extruded into:
-Fibre, its be optionally stretched, preferably on MD, stretch to its initial length with at least 3 times, or
-film, its be optionally stretched, preferably on MD, stretch to its initial length with at least 3 times, cut into subsequently Fibre, or described film is first cut into Fibre, described Fibre is optionally stretched, preferably on MD, stretch to its initial length with at least 3 times.
More preferably, the fiber of extruding, the fiber/band being formed by film cutting or the film before being cut into fiber/band,, stretch on MD to its initial length with 3～10 times.Wording " be stretched to its initial length 3 times " and " tractive is to 3 times of its initial length ", implication is identical, and can be expressed as " draw ratio that is at least 1:3 " and " being at least the tractive ratio of 1:3 ", " 1 " wherein represents the initial length of film, and " 3 " represent 3 times to initial length of stretching/tractive.The preferred film of the present invention is with 1:4 at least, more preferably 1:5～1:8, and the draw ratio of for example 1:5～1:7 stretches.The effect of stretching (being tractive) is that similarly, the thickness of film has also reduced.Like this, the tractive that is at least 1:3 means than preferably, and the thickness of film is at least little 3 times than original depth.
Then, Fibre is further processed into goods, as rope, twine, net, bag or the fabric for technology and agricultural, or, in particular for, the artificial grass of such as sports ground etc.
Fibre of the present invention
Fibre can be the form of fiber, band or silk, and it contains multimodal LLDPE, is preferably znLLDPE, as copolymer defined above.Described Fibre has formed a part of the present invention.
Preferably, described Fibre, by forming as the defined multimodal LLDPE copolymer of claim or below, is preferably multimodal znLLDPE copolymer above.
In a preferred embodiment, Fibre of the present invention does not contain hollow core, on the contrary, on its cross section, is solid.Therefore, if when Fibre of the present invention is not hollow, be, preferred.
Like this, term Fibre has been contained fiber, band and the silk of arbitrary shape and size naturally.Their size depends on final Application Areas, and this is known in the field.Silk is preferably monofilament.
In a preferred embodiment, Fibre is defined stretching form above.
For example, when Fibre is made into the form of being with, so, this band of the present invention can typically have at least width of 0.5mm, is preferably at least 1mm.The upper limit of the width of band is unimportant, for example can be up to 10mm, preferably up to 6mm.The thickness of band of the present invention can be, and for example at least 5 μ m, are preferably at least 10 μ m.Equally, the upper limit of the thickness of band does not limit, and can be for example up to 80 μ m, preferably up to 50 μ m, in some final application, preferably up to 20 μ m.In fiber and silk in the situation that, their size typically with the magnitude range of band given above, size is corresponding.Width range given above and other sizes, be applicable to the Fibre of the Fibre of the form of stretching and the form that do not stretch.Preferably, Fibre is stretching form, and can have width defined above and other sizes.
As described above, Fibre has the balance between excellent flexibility and ABRASION RESISTANCE, and preferably, and one or more with following performance are also advantageously: UV stability, toughness and/or elastic performance.The Application Areas of Fibre does not limit, and against expectation finds: " soft " of the present invention Fibre is suitable for the application strict to mechanical property requirements especially feasiblely, and the mechanical property that described application requirements is good, as good ABRASION RESISTANCE.
Further preferably, Fibre shows good tensile property, described tensile property is expressed as works as according to ISO 2062 (1993), when the tension test described in employing as below " assay method " is measured, and the balance between toughness and elongation at break.Stretch and measure sample used, according to the method preparation " sample preparation " Suo Shu.
In one embodiment, Fibre of the present invention contains above or defined multimodal LLDPE in claim, described multimodal LLDPE works as according to ISO 2062 (1993), adopt formed by described multimodal LLDPE with sample and be stretched to 6 times of initial length when measuring, there is the toughness that is at least 0.40N/tex, be at least 13%, be preferably at least 15% remaining elongation at break.Described method is described in " assay method " below.Prepare according to the method for " preparation of Fibre sample " hereinafter described with sample.
Preferably, Fibre of the present invention, in the time being stretched to 6 times of its initial length, in the time that the ISO 2062 according to hereinafter described (1993) measures, have and be at least the toughness of 0.40N/tex and be at least 13%, be preferably at least 15% remaining elongation at break.
The example of final Application Areas has, and for technology application, comprises industry, agricultural and GEOLOGICAL APPLICATION, family expenses, indoor application and sports applications etc.
Described Fibre can be used to prepare goods.Therefore, the present invention also provides a kind of goods, and it contains fiber defined above, band or silk.The example of goods is, especially rope and twine, great Bao, net and geotextile, and synthetic carpet and moving surface are if the carpet of the artificial grass for indoor or outdoors stadium and sports ground or individual or public building is as for corridor, office and showroom.
For example, on moving surface, as artificial grass, Fibre of the present invention can be enough soft, and have good ABRASION RESISTANCE, and they can be wear-resistant.Preferably, the UV stability that they also have good elasticity and/or need especially in outdoor utility.
Assay method
Except as otherwise noted, for measuring the fiber sample of above-mentioned and following character of described Fiber, be to be " preparation of Fibre sample " according to title prepared by method.Naturally, be to be understood that, the character of given Fibre of the present invention in description above and claims below, is not limited to the Fibre sample that adopts in described mensuration, but is generally applicable to the Fibre of the present invention in claims and/or preferred embodiment.Defined Fibre sample is only used to meet the fully requirement of open/reproducibility of the present invention herein.
The density of material is according to ISO 1183:1987 (E), and method D, measures as gradient liquid using isopropanol-water.In the time of crystallization sample, the cooldown rate of dull and stereotyped (plaque) is 15 ℃/min.The adjusting time is 16 hours.
MFR
2, MFR
5and MFR
21mensuration be according to ISO 1133, at 190 ℃, load be respectively 2.16,5.0 and 21.6kg under carry out.
The mensuration of molecular weight and molecualr weight distribution Mn, Mw and MWD is to adopt gel permeation chromatography (GPC), carry out by the following method: weight average molecular weight Mw and molecular weight distribution (MWD=Mw/Mn, wherein Mn is number-average molecular weight, and Mw is weight average molecular weight) be to adopt the method based on ISO16014-4:2003 to measure.The Waters150CV plus instrument of refractive index detector and in-line viscometer is equipped with in employing, together with the 3 × HT6E styragel post (styrene-divinylbenzene) available from Waters with as 1 of solvent, 2,4-trichloro-benzenes (TCB, with 2 of 250mg/L, 6-di-tert-butyl-4-methy phenol is stable), be to measure under 1mL/ minute at 140 ℃, constant flow rate.The sample solution of 500 μ L is all injected in each analysis.Described column device adopts common calibration steps (according to ISO 16014-2:2003), adopts polystyrene (PS) standard specimen of 15 narrow MWD within the scope of 1.0kg/mol～12000kg/mol to calibrate.For polystyrene and polyethylene, and employing Mark Houwink constant (for PS, K:9.54 × 10
-5dL/g, a:0.725; For PE, K:3.92 × 10
-4dL/g, a:0.725).All samples are all prepared by the following method: 0.5～3.5mg polymer is dissolved in to the TCB (identical with mobile phase) that 4mL (at 140 ℃) is stable, before entering GPC instrument, at 140 ℃, keep 3 hours, at 160 ℃, keep again also rocking once in a while for 1 hour sample simultaneously.。
Melt temperature and crystallization temperature, Tm and Tcr, the two is measured on Perkin Elmer DSC-7 differential scanning calorimeter all according to ISO 11357-1.Heating curves is chosen for-10 ℃～200 ℃, and heating rate is 10 ℃/min.At 200 ℃, keep 10 minutes.Cooling curve is chosen for 200 ℃～-10 ℃, and rate of temperature fall is 10 ℃/min.Choose endothermic peak and exothermic peak as melting and crystallization temperature.Degree of crystallinity is by comparing and calculate with the poly melting heat (being 290J/g) of perfect crystallization.
Co-monomer content (mol%) is based on measuring through the Fourier transform infrared spectroscopy (FTIR) of C13-NMR calibration.
Toughness and elongation at break pass through stretching test measurement.Tension test is according to ISO 2062 (1993) standard, carry out on Instron instrument, and adopts following measure setup:
Toughness (N/Tex) is calculated by following formula:
(fracture tensile strength)/Tex
Wherein, the weight of Tex=1000m fiber (g)
Mar proof, i.e. ABRASION RESISTANCE, adopts braiding simulator to measure
By adopting the braiding simulator of being developed by Centexbel, on yarn level, measure mar proof, i.e. ABRASION RESISTANCE.The schematic diagram of thread path as shown in Figure 1.
In the process of braiding simulation, yarn is conducted through three metal bars.In test process, there is excellent bar and move up and down, make to produce and rub between yarn and described metal bar.Wearing and tearing occur in the region of 2 × 10cm of per share yarn.By adopt distance bar between left side and right side yarn, avoid the friction of yarn/yarn.Wearing and tearing process before and afterwards, according to ISO mentioned above 2062 (1993) method, on Instron equipment, carry out extension test.
Adopt following measure setup:
braiding simulator:
Motion frequency: 100/min
Weight: 120g
Cycle-index: 60000
Number of yarns: 5 kinds
tension test:
The preparation of Fibre sample
Definition and the embodiment of the common character of measuring for above-mentioned employing Fibre sample, described Fibre sample is band sample, it adopts up-to-date pilot scale type casting films tension belt production line (cast film stretch tape line) preparation.Extruder is equipped with measuring pump, to guarantee constant discharging.Water quench tank, godet roller and baking oven used are all
parts.The extruder temperature adopting is distributed as 225 ℃, 230 ℃ and 235 ℃.Mouth mould remains on 235 ℃.Film mouth mould has the gap width of 0.1mm.Extrude the primary film of 75 microns, enter into the water-bath of water quench tank (30 ℃).The speed of first godet roller is left in selection, makes it remain 10m/ minute.To be with incision, and stretch in hot-air drawing oven, draw ratio (being tractive ratio) sees below.Anneal at the 3rd seal wire platform.The temperature of three godet rollers of this seal wire platform remains on 90,100 and 100 ℃.
Except as otherwise noted, for the PE material of every kind of test, preparation has 2 test sample series of different stretch ratio: 1.Fibre sample series: the band sample and the 2.Fibre sample series that are stretched to 5 times (draw ratio is 1:5) of its initial length: the band sample that is stretched to 6 times (draw ratio is 1:6) of its initial length.
Embodiment
ZnLLDPE1 of the present invention: multimodal znLLDPE, MFR
2for 0.4g/10 minute, MFR
5for 2.2g/10 minute, density is 937kg/m
3.
With reference to PEl: the unimodal znPE copolymer being purchased of fiber rank (grade for fiber), MFR
2for 0.60g/10 minute, MFR
21for 19g/10 minute, density is 947kg/m
3.
With reference to PE2: other unimodal polyethylene and ethylene copolymers that be purchased, that adopt Cr catalyst to prepare of fibre-grade, MFR
2for 0.4g/10 minute, MFR
21for 28g/10 minute, density is 945kg/m
3.
Embodiment
The preparation of polymer
Embodiment: znLLDPE1 of the present invention
Multimodal znLLDPE1 polymer is to prepare in the multistage reactor system of pilot-scale with loop reactor and gas phase reaction kettle.Before actual polymerization step, carry out prepolymerization step.Prepolymerisation stage is in slurry, carries out under the following conditions: at 50dm
3loop reactor in, temperature is approximately 80 ℃, and pressure is approximately 65 bar, adopts the polymerization catalyst of preparing with the similar method of embodiment 3 of EP 688794, it is the silica supports of 25 μ m that described catalyst adopts average grain diameter, and triethyl aluminum is as co-catalyst.The mol ratio of the titanium in aluminium and catalyst in co-catalyst is approximately 20.Ethene is with the ratio feeding of (200g C2)/(1g/ catalyst).Adopt propane as diluent, and feeding hydrogen, its amount can be by the MFR of prepolymer
2be adjusted to about 10g/10 minute.
The slurry obtaining, together with triethyl aluminum catalyst, is introduced into 500dm with prepolymerization catalyst
3loop reactor in, in this reactor, also introduce continuously propane, ethene and hydrogen.The feeding of H2/C2 is than being 395mol/kmol.Described loop reactor moves under the pressure of the temperature of 95 ℃ and 60 bar.Regulate processing conditions, to obtain MFR
2for 400g/10 minute, density are about 970kg/m
3polymer.
Then, the slurry obtaining is transferred in fluid bed gas phase reaction kettle, in this reactor, also adds other ethene, 1-butylene comonomer and hydrogen and the nitrogen as inert gas, thereby in the situation that there is LMW component, preparation HMW component.Described gas phase reaction kettle moves under the pressure of the temperature of 80 ℃ and 20 bar; And well known to a person skilled in the art mode, regulate H2/C2 feeding ratio and C4/C2 feeding ratio, thereby the final bimodal polymers of preparation polymerization, after collecting described polymer, by itself and additive blend, and extrude in counterrotating double screw extruder JSW CIM90P, forming pellet, the polymer obtaining has the MFR of 0.4g/10 minute
2, 937kg/m
3density.The ratio of the polymer of preparing in the reactor of loop and the polymer prepared in gas phase reaction kettle is 43/57.
Mechanics Performance Testing
The Fibre sample that contains multimodal LLDPE polymeric material of the present invention, test fiber sample with contrast, prepare according to defined method in " preparation of Fibre sample ", it is carried out to following table 1 and the listed Mechanics Performance Testing of table 2, and be further shown in accompanying drawing 2 and 3.
Extension test: with two serial band samples, carry out balance between toughness and percentage elongation and measure, be stretched to the sample series of 5 times of its initial lengths and be stretched to the sample series of 6 times of its initial lengths.
Toughness test shows, the fiber of the very feasible and same prior art that be purchased, that have higher density of the toughness of Fibre of the present invention and the balance of elongation at break is for example suitable with reference to PE2.Fig. 2 represents that toughness can improve by improving draw ratio, still can keep feasible percentage elongation thus.
Therefore, usually, " softer " of the present invention Fibre can, for being generally used for the commercial fibre of physical culture and technology application scenario, provide a replacement scheme that feasibility is very high.
Table 1: toughness and test of elongation rate result
Mar proof: ABRASION RESISTANCE, i.e. mar proof, described in " assay method ", adopts the band Specimen Determination of 6 times (draw ratio is 1:6) being stretched to its initial length according to above.For every kind of material, make 5 to stand the circular treatment of 60000 times with sample, each weight load with sample is 120g.After 6000 circulations, stop test.For some material, before described processing finishes, band has just ruptured.After applied processing, mechanical property is assessed again.For the band of each fracture, select remaining power and 0% percentage elongation.Shown in Fig. 3,5 of each group of the test material test result with sample, and cycle-index when the fracture of the band of any fracture.Shown in table 2, after " braiding " test, the stretch test result being recorded by test sample.This test shows, Fibre of the present invention has extraordinary ABRASION RESISTANCE, and it improves compared with the commercial fibre of the prior art that contains higher density PE.
Table 2: after processing on braiding simulator, residual tensile strength and elongation at break
Claims (14)
1. comprise an artificial sport surface for fiber, band or silk, described fiber, band or silk contain linear low density polyethylene composition, and wherein, described composition has 938kg/m
3or less density, and when according to ISO1133, at 190 ℃, while measurement under the load of 2.16kg, there is 5g/10 minute or lower MFR
2; And wherein said composition is multimodal with regard to molecular weight distribution, and at least comprises:
(i) there is 50g/10 minute or higher MFR
2compared with Alathon or the copolymer component of lower molecular wt (LMW), and
(ii) Alathon or the copolymer component of higher weight average molecular weight (HMW);
Condition is: described compared with at least one copolymer for ethene and at least one comonomer in lower molecular wt (LMW) and higher weight average molecular weight (HMW) component;
Wherein, MFR
2be according to ISO1133, at 190 ℃, load is the melt flow rate (MFR) of measuring under 2.16kg.
2. artificial sport as claimed in claim 1 surface, wherein, when according to ISO1133, at 190 ℃, while measurement under the load of 2.16kg, described fiber, band or silk have the MFR of 0.1～5g/10 minute
2.
3. artificial sport as claimed in claim 1 or 2 surface, wherein, the linear low density polyethylene composition of described multimodal has the molecular weight distribution MWD that is at least 5, wherein MWD=Mw/Mn, Mw is weight average molecular weight, Mn is number-average molecular weight.
4. artificial sport as claimed in claim 1 or 2 surface, wherein, the linear low density polyethylene composition of described multimodal has the molecular weight distribution MWD that is less than 40, wherein MWD=Mw/Mn, Mw is weight average molecular weight, Mn is number-average molecular weight.
5. artificial sport as claimed in claim 1 or 2 surface, wherein, the linear low density polyethylene composition of described multimodal has 10～30 molecular weight distribution MWD, wherein MWD=Mw/Mn, Mw is weight average molecular weight, Mn is number-average molecular weight.
6. artificial sport as claimed in claim 1 or 2 surface, wherein, the linear low density polyethylene composition of described multimodal can, by adopting Ziegler Natta catalyst, be obtained with at least one comonomer polymerization by ethene.
7. artificial sport as claimed in claim 1 or 2 surface, wherein, described fiber, band or silk are made up of the linear low density polyethylene composition of described multimodal.
8. artificial sport as claimed in claim 1 or 2 surface, wherein, described fiber, band or silk are stretching forms.
9. artificial sport as claimed in claim 1 or 2 surface, wherein, described fiber, band or silk are stretching forms, have at least 3 times to the draw ratio of its initial length.
10. artificial sport as claimed in claim 1 or 2 surface, wherein said fiber, band or silk are stretching forms, have the draw ratio of 1:5～1:8.
Manufacture the method on the artificial sport surface described in claim 1 or 2 for 11. 1 kinds, described method comprises:
-under the existence of comonomer and catalyst system, in multistage process, by vinyl monomer polymerization to prepare the linear low density polyethylene composition of multimodal as claimed in claim 1 or 2, and
-linear low density polyethylene composition of described multimodal is processed into the form of fiber, band or silk;
-described fiber, band or silk are configured as to artificial sport surface.
12. methods as claimed in claim 11, wherein, described caltalyst is Ziegler Natta catalyst system.
13. methods as described in claim 11 or 12, wherein, the step that the linear low density polyethylene composition of multimodal is processed into fiber, band or silk comprises extrusion step, thereby the linear low density polyethylene composition of described multimodal is configured as:
-fiber, band or silk, it is optionally stretched at least 3 times of its initial length, or
-film, it is optionally stretched at least 3 times of its initial length, and is cut into subsequently fiber, silk or band; Or described film is cut into fiber, silk or band, described fiber, silk or band are optionally stretched at least 3 times of its initial length.
14. 1 kinds comprise the goods on artificial sport as claimed in claim 1 surface, and wherein said artificial sport surface is artificial grass.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP07005908.4 | 2007-03-22 | ||
| EP07005908A EP1972703A1 (en) | 2007-03-22 | 2007-03-22 | Fibers, tapes or filaments comprising a multimodal polyethylene composition |
| PCT/EP2008/002190 WO2008113567A1 (en) | 2007-03-22 | 2008-03-19 | Fibres, tapes or filaments comprising a multimodal polyethylene composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101657572A CN101657572A (en) | 2010-02-24 |
| CN101657572B true CN101657572B (en) | 2014-05-14 |
Family
ID=38319555
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200880009377.6A Expired - Fee Related CN101657572B (en) | 2007-03-22 | 2008-03-19 | Fibers, tapes or filaments comprising multimodal polyethylene composition |
Country Status (4)
| Country | Link |
|---|---|
| EP (2) | EP1972703A1 (en) |
| CN (1) | CN101657572B (en) |
| AT (1) | ATE517201T1 (en) |
| WO (1) | WO2008113567A1 (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1972704A1 (en) * | 2007-03-22 | 2008-09-24 | Borealis Technology Oy | Fibre, tapes or filaments comprising a polyethylene composition |
| WO2010075098A1 (en) | 2008-12-15 | 2010-07-01 | Textile Management Associates, Inc. | Method of recycling synthetic turf and infill product |
| US9605360B2 (en) * | 2010-04-30 | 2017-03-28 | Basell Polyolefine Gmbh | Polyethylene fiber or filament |
| WO2012004422A1 (en) | 2010-07-06 | 2012-01-12 | Dow Global Technologies Llc | Ethylene polymer blends and oriented articles with improved shrink resistance |
| KR101401370B1 (en) | 2010-09-23 | 2014-05-29 | 토탈 리서치 앤드 테크놀로지 펠루이 | Artificial grass |
| US9120914B2 (en) | 2013-09-23 | 2015-09-01 | Milliken & Company | Thermoplastic polymer composition |
| US9200142B2 (en) | 2013-09-23 | 2015-12-01 | Milliken & Company | Thermoplastic polymer composition |
| US9580575B2 (en) | 2013-09-23 | 2017-02-28 | Milliken & Company | Polyethylene articles |
| US9193845B2 (en) | 2013-09-23 | 2015-11-24 | Milliken & Company | Thermoplastic polymer composition |
| US9200144B2 (en) | 2013-09-23 | 2015-12-01 | Milliken & Company | Thermoplastic polymer composition |
| CN105017625B (en) * | 2014-04-15 | 2017-07-14 | 中国石化扬子石油化工有限公司 | A kind of ethylene-alpha-olefin copolymer, its manufacture method and its application |
| US11124902B2 (en) * | 2015-12-10 | 2021-09-21 | Dow Global Technologies Llc | Polyethylene compositions for the preparation of tapes, fibers, or monofilaments |
| CN111745927B (en) * | 2020-06-30 | 2022-01-28 | 中国石油化工科技开发有限公司 | High-wear-resistance high-lubrication polyethylene product and preparation method thereof |
| CN114990719B (en) * | 2022-06-10 | 2023-06-20 | 湖北工业大学 | Fiber yarn for artificial lawn and preparation method thereof |
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| CN1668689A (en) * | 2002-06-20 | 2005-09-14 | 博里利斯技术公司 | Breathable films |
| CN1914365A (en) * | 2003-12-20 | 2007-02-14 | 卡罗文有限公司 | Polyethylene-based, soft nonwoven fabric |
| CN1926185A (en) * | 2004-03-26 | 2007-03-07 | 北方科技有限公司 | Polymer composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6316549B1 (en) † | 1991-10-15 | 2001-11-13 | The Dow Chemical Company | Ethylene polymer fiber made from ethylene polymer blends |
| FI96216C (en) | 1994-12-16 | 1996-05-27 | Borealis Polymers Oy | Process for the production of polyethylene |
| JP3342661B2 (en) † | 1998-03-23 | 2002-11-11 | ダイヤテックス株式会社 | Artificial grass |
| US7230054B2 (en) * | 2004-06-29 | 2007-06-12 | Equistar Chemicals, Lp | Polymer resins with improved environmental stress crack resistance |
| GB0425444D0 (en) * | 2004-11-18 | 2004-12-22 | Solvay | Multimodal composition for tapes, fibres and filaments |
| US20060247373A1 (en) † | 2005-04-28 | 2006-11-02 | Nova Chemicals (International) S.A. | Dual reactor polyethylene resins for electronic packaging-films, tapes, bags and pouches |
-
2007
- 2007-03-22 EP EP07005908A patent/EP1972703A1/en not_active Withdrawn
-
2008
- 2008-03-19 AT AT08716622T patent/ATE517201T1/en active
- 2008-03-19 CN CN200880009377.6A patent/CN101657572B/en not_active Expired - Fee Related
- 2008-03-19 WO PCT/EP2008/002190 patent/WO2008113567A1/en active Application Filing
- 2008-03-19 EP EP08716622.9A patent/EP2137344B2/en not_active Not-in-force
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1668689A (en) * | 2002-06-20 | 2005-09-14 | 博里利斯技术公司 | Breathable films |
| CN1914365A (en) * | 2003-12-20 | 2007-02-14 | 卡罗文有限公司 | Polyethylene-based, soft nonwoven fabric |
| CN1926185A (en) * | 2004-03-26 | 2007-03-07 | 北方科技有限公司 | Polymer composition |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2137344B1 (en) | 2011-07-20 |
| EP2137344A1 (en) | 2009-12-30 |
| WO2008113567A1 (en) | 2008-09-25 |
| EP2137344B2 (en) | 2015-03-04 |
| EP1972703A1 (en) | 2008-09-24 |
| ATE517201T1 (en) | 2011-08-15 |
| CN101657572A (en) | 2010-02-24 |
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