EP1469104A1 - Metallocene produced polyethylene for fibres applications - Google Patents

Metallocene produced polyethylene for fibres applications Download PDF

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Publication number
EP1469104A1
EP1469104A1 EP03076128A EP03076128A EP1469104A1 EP 1469104 A1 EP1469104 A1 EP 1469104A1 EP 03076128 A EP03076128 A EP 03076128A EP 03076128 A EP03076128 A EP 03076128A EP 1469104 A1 EP1469104 A1 EP 1469104A1
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EP
European Patent Office
Prior art keywords
tapes
stretched
metallocene
stretching
film
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.)
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Application number
EP03076128A
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German (de)
French (fr)
Inventor
Eric Maziers
Vincent Stephenne
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Total Petrochemicals Research Feluy SA
Original Assignee
Total Petrochemicals Research Feluy SA
Atofina Research SA
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Application filed by Total Petrochemicals Research Feluy SA, Atofina Research SA filed Critical Total Petrochemicals Research Feluy SA
Priority to EP03076128A priority Critical patent/EP1469104A1/en
Priority to US10/553,572 priority patent/US20070178303A1/en
Priority to CNB200480009870XA priority patent/CN100434575C/en
Priority to JP2006505533A priority patent/JP4767839B2/en
Priority to KR1020057019653A priority patent/KR101333394B1/en
Priority to PCT/EP2004/050479 priority patent/WO2004092459A1/en
Priority to EP04726183A priority patent/EP1613797B1/en
Publication of EP1469104A1 publication Critical patent/EP1469104A1/en
Withdrawn legal-status Critical Current

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Classifications

    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00Formation of filaments, threads, or the like
    • D01D5/42Formation of filaments, threads, or the like by cutting films into narrow ribbons or filaments or by fibrillation of films or filaments
    • D01D5/426Formation of filaments, threads, or the like by cutting films into narrow ribbons or filaments or by fibrillation of films or filaments by cutting films
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00Formation of filaments, threads, or the like
    • D01D5/42Formation of filaments, threads, or the like by cutting films into narrow ribbons or filaments or by fibrillation of films or filaments
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/04Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/28Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/30Monocomponent 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
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913Rod, strand, filament or fiber
    • Y10T428/2933Coated or with bond, impregnation or core

Definitions

  • This invention relates to the field of monofilaments and stretched tapes prepared with metallocene-produced polyethylene.
  • Monofilaments are uniaxially oriented wirelike polymer strands having a circular cross section. They are manufactured by melt spinning process and their size ranges from 0.1 to 2.5 mm in diameter, depending upon the end use application. Polyethylene, polypropylene, nylon and polyesters are commonly used as raw materials for making monofilaments.
  • Stretched tapes are prepared from a primary film produced either by a blown or by a cast film process.
  • the film can be cut into tapes and then oriented or reversely, oriented and then cut into tapes.
  • the orientation is carried out by stretching the film or tapes while passing through an air oven or on a hot plate at a temperature below the melting point.
  • the stretching is carried out by passing the film or tapes over two sets of rollers placed respectively before and after the air oven/hot plate and operating at different speeds, the speed of the second set of rellers being larger than that of the first set of rollers.
  • the polymer preferably used in the market for these applications is a high density polyethylene (HDPE) prepared with a Ziegler-Natta catalyst, said HDPE having a MI2 smaller than 1 g/10min such as for example Solvay Eltex A4009MFN1325 resin or Basell Hostalen GF 7740 F1, GF7740 F2, GF7740 F3, GF7750 M2 grades or the polyethylene resins disclosed in GB-0023662.
  • the molecular weight distribution MWD of these resins is quite broad which means that the resins may include very long as well as very short chains.
  • PE polycrystalline polyethylene
  • PP polypropylene
  • raffia is defined as woven monofilaments or woven stretched tapes.
  • the stretched tapes and monofilaments prepared with polyethylene exhibit a higher elongation at rupture, a greater flexibility and a lower tendency to fibrillation than those prepared from polypropylene. These properties are advantageous for example in the production of woven tape fabrics.
  • the products prepared from polyethylene however suffer from the disadvantage their tenacity is much lower than that of the products prepared from polypropylene. Tenacity increases as a function of molecular weight, density, degree of orientation of the chains/crystallites and increases with narrowing of the molecular weight distribution. Impact strength increases with decreasing density, increasing molecular weight and decreasing molecular weight distribution.
  • the present invention provides monofilaments or stretched tapes, unwoven or woven into raffia prepared from metallocene-produced polyethylene (mPE).
  • mPE metallocene-produced polyethylene
  • the invention also provides a process for preparing raffia or stretched tapes with a metallocene-produced polyethylene that comprises the steps of:
  • the primary film can first be cut into strips and then oriented by stretching.
  • the film can be either a blown film or a cast film. Film production is easier with processed material having high melt strength such as polyethylene having long chain branches and/or very long linear chains.
  • Orientation of the primary film or of the cut tapes is carried out by stretching while passing through an air oven or over a hot plate, maintained at a temperature below the melting temperature. Stretching of the primary film or of the cut tapes is done by passing said film or tapes over two sets of rollers (goddet rollers) placed respectively before and after the air oven/hot plate, and operating at different speeds.
  • the stretch ratio S2/S1 is defined by the ratio of the speed of roller 2, S2 to the speed of roller 1, S1 wherein S2 is larger than S1.
  • Stretching at such high temperature results in chain/crystals orientation with a simultaneous increase of crystallinity. These structural changes lead to an increase of tensile strength and concurrently to a reduction of elongation.
  • the tensile strength increases with increasing stretch ratio and with increasing stretching temperature. It is preferred that the stretching temperature is as close as possible to but smaller than the melting temperature.
  • typical values for the stretch ratio are of from 5.0 to 7.0.
  • the typical stretching temperatures depend upon the melting temperature of the polyethylene resins: they must be lower than but as close as possible to the melting temperature. Typically, they are from 5 to 70 °C lower than the melting temperature of the resin, preferably they are from 10 to 50 °C lower than the melting temperature of the resin.
  • the drawn tapes are annealed immediately after the stretching operation in order to minimise shrinkage that could occur as a result of residual stresses in the oriented tapes.
  • Annealing is done by heating the stretched tapes while they are being transferred from the second goddet rollers onto a third roller having a speed S3 that is smaller than the speed of roller 2, S2.
  • speed S3 is about 95 % of speed S2.
  • the annealing ratio AR is defined as (S2-S3)/S2) at a temperature slightly inferior to the stretching temperature.
  • the annealing temperature is from 5 to 10 °C lower than the stretching temperature.
  • Polymers that do not include either very long linear chains or long chain branched molecules have a better stretchability.
  • the low density polyethylene (LDPE) having long chain branches cannot be stretched beyond a certain degree and, to the contrary, the purely linear polyethylene chains usually obtained with a Ziegler-Natta catalyst have a high degree of stretchability.
  • the metallocene used to prepare the high density polyethylene can be a bis-indenyl represented by the general formula: R" (Ind) 2 MQ 2 or a bis-cyclopentadienyll represented by the formula (Cp) 2 MQ 2 wherein (Ind) is an indenyl or an hydrogenated indenyl, substituted or unsubstituted, Cp is a cyclopentadienyl ring substituted or unsubstituted, R" is a structural bridge between the two indenyls to impart stereorigidity that comprises a C 1 -C 4 alkylene radical, a dialkyl germanium or silicon or siloxane, or a alkyl phosphine or amine radical, which bridge is substituted or unsubstituted; Q is a hydrocarbyl radical having from 1 to 20 carbon atoms or a halogen, and M is a group IVb transition metal or Vanadium.
  • each indenyl or hydrogenated indenyl compound may be substituted in the same way or differently from one another at one or more positions in the cyclopentadienyl ring, the cyclohexenyl ring and the bridge.
  • each substituent on the indenyl may be independently chosen from those of formula XR v in which X is chosen from group IVA, oxygen and nitrogen and each R is the same or different and chosen from hydrogen or hydrocarbyl of from 1 to 20 carbon atoms and v+1 is the valence of X.
  • X is preferably C.
  • the cyclopentadienyl ring is substituted, its substituent groups must be so bulky as to affect coordination of the olefin monomer to the metal M.
  • Substituents on the cyclopentadienyl ring preferably have R as hydrogen or CH 3 . More preferably, at least one and most preferably both cyclopentadienyl rings are unsubstituted.
  • both indenyls are unsubstituted.
  • each cyclopentadienyl ring may be substituted in the same way or differently from one another at one or more positions in the cyclopentadienyl ring.
  • each substituent on the cyclopentadienyl may be independently chosen from those of formula XR* v in which X is chosen from group IVA, oxygen and nitrogen and each R* is the same or different and chosen from hydrogen or hydrocarbyl of from 1 to 20 carbon atoms and v+1 is the valence of X.
  • X is preferably C and the most preferred substituent is n-butyl.
  • R" is preferably a C1-C4 alkylene radical (as used herein to describe a difunctional radical, also called alkylidene), most preferably an ethylene bridge (as used herein to describe a difunctional radical, also called ethylidene), which is substituted or unsubstituted.
  • the metal M is preferably zirconium, hafnium, or titanium, most preferably zirconium.
  • Each Q is the same or different and may be a hydrocarbyl or hydrocarboxy radical having 1 to 20 carbon atoms or a halogen.
  • Suitable hydrocarbyls include aryl, alkyl,alkenyl,alkylaryl or arylalkyl.
  • Each Q is preferably halogen.
  • metallocenes used in the present invention one can cite bis tetrahydro-indenyl compounds and bis indenyl compounds as disclosed for example in WO 96/35729 or bis(cyclopentadienyl) compounds.
  • the most preferred metallocene catalysts are ethylene bis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride and bis(n-butyl-cyclopentadienyl) zirconium dichloride.
  • the metallocene may be supported according to any method known in the art.
  • the support used in the present invention can be any organic or inorganic solids, particularly porous supports such as talc, inorganic oxides, and resinous support material such as polyolefin.
  • the support material is an inorganic oxide in its finely divided form.
  • alumoxane is used to ionise the catalyst during the polymerization procedure, and any alumoxane known in the art is suitable.
  • the preferred alumoxanes comprise oligomeric linear and/or cyclic alkyl alumoxanes represented by the formula : for oligomeric, linear alumoxanes And for oligomeric, cyclic alumoxanes, wherein n is 1-40, preferably 10-20, m is 3-40, preferably 3-20 and R is a C 1 -C 8 alkyl group and preferably methyl.
  • Methylalumoxane is preferably used.
  • aluminiumalkyl(s) can be used as cocatalyst in the reactor.
  • the aluminiumalkyl is represented by the formula AIR x can be used wherein each R is the same or different and is selected from halides or from alkoxy or alkyl groups having from 1 to 12 carbon atoms and x is from 1 to 3.
  • Especially suitable aluminiumalkyl are trialkylaluminium, the most preferred being triisobutylaluminium (TIBAL).
  • the catalyst may be prepolymerised prior to introducing it in the reaction zone and/or prior to the stabilization of the reaction conditions in the reactor.
  • the polyethylene resin of the present invention has a density ranging from 0.925 to 0.950 g/cm 3 , preferably, from 0.930 to 0.940 g/cm 3 and most preferably about 0.935 g/cm 3 .
  • the melt index MI2 is within the range 0.1 to 5 g/10 min, preferably in the range 0.2 to 1.5 g/10 min.
  • the density is measured following the method of standard test ASTM D 1505 at 23 °C and the melt index Ml2 is measured following the method of standard test ASTM D 1238 at 190 °C and under a load of 2.16 kg.
  • the metallocene-prepared polyethylenes produce very strong stretched tapes and raffia products, mainly because of their narrow molecular weight distribution and because they have long chain branches.
  • the final products have improved tensile and elongation properties properties.
  • Resin R1 is a medium density polyethylene resin prepared with isopropylidene (tetrahydroindenyl) zirconium dichloride. It had a density of 0.934 g/cm 3 and a melt index MI2 of 0.9 g/10 min. It was additivated as follows:
  • Resin R2 was a commercial resin prepared with a Ziegler-Natta catalyst system: (GF7740 F1 from Hostalen). It had a density of 0.946 g/cm 3 and a melt index MI2 of 0.5 g/10min.
  • the final products, whether unwoven or woven (nets) obtained from the metallocene-produced resin R1 had a high tenacity, an excellent elongation at rupture and a very high break strength. It also had a soft touch and a high flexibility.
  • the titre is measured in tex or g/km: this is a measure of the linear mass of a filament or fibre.
  • the raffia products prepared according to the present invention has thus improved properties with respect to those of the prior art.

Abstract

The present invention provides monofilaments or stretched tapes, unwoven or woven into raffia, prepared with metallocene-produced polyethylene.

Description

  • This invention relates to the field of monofilaments and stretched tapes prepared with metallocene-produced polyethylene.
  • Monofilaments are uniaxially oriented wirelike polymer strands having a circular cross section. They are manufactured by melt spinning process and their size ranges from 0.1 to 2.5 mm in diameter, depending upon the end use application. Polyethylene, polypropylene, nylon and polyesters are commonly used as raw materials for making monofilaments.
  • Stretched tapes are prepared from a primary film produced either by a blown or by a cast film process. The film can be cut into tapes and then oriented or reversely, oriented and then cut into tapes. The orientation is carried out by stretching the film or tapes while passing through an air oven or on a hot plate at a temperature below the melting point. The stretching is carried out by passing the film or tapes over two sets of rollers placed respectively before and after the air oven/hot plate and operating at different speeds, the speed of the second set of rellers being larger than that of the first set of rollers.
  • The polymer preferably used in the market for these applications is a high density polyethylene (HDPE) prepared with a Ziegler-Natta catalyst, said HDPE having a MI2 smaller than 1 g/10min such as for example Solvay Eltex A4009MFN1325 resin or Basell Hostalen GF 7740 F1, GF7740 F2, GF7740 F3, GF7750 M2 grades or the polyethylene resins disclosed in GB-0023662. The molecular weight distribution MWD of these resins is quite broad which means that the resins may include very long as well as very short chains.
  • Semi-crystalline polyethylene (PE) and polypropylene (PP) have also been used as materials for monofilaments stretched tapes and raffia, such as disclosed for example in FR-A-2814761, JP-2001342209 or JP-2001220405. Throughout this description, raffia is defined as woven monofilaments or woven stretched tapes. The stretched tapes and monofilaments prepared with polyethylene exhibit a higher elongation at rupture, a greater flexibility and a lower tendency to fibrillation than those prepared from polypropylene. These properties are advantageous for example in the production of woven tape fabrics. The products prepared from polyethylene however suffer from the disadvantage their tenacity is much lower than that of the products prepared from polypropylene. Tenacity increases as a function of molecular weight, density, degree of orientation of the chains/crystallites and increases with narrowing of the molecular weight distribution. Impact strength increases with decreasing density, increasing molecular weight and decreasing molecular weight distribution.
  • There is thus a need for monofilaments or stretched tapes, unwoven or woven into raffia having a better balance of properties.
  • It is an object of the present invention to prepare monofilament or stretched tape products having high tenacity.
  • It is another object of the present invention to prepare monofilament or stretched tape products having high impact strength.
  • It is also an object of the present invention to prepare monofilament or stretched tape products having high elongation at rupture.
  • It is a further object of the present invention to prepare monofilament or stretched tape products having a soft touch.
  • It is yet another object of the present invention to prepare monofilament or stretched tape products having great flexibility.
  • Accordingly the present invention provides monofilaments or stretched tapes, unwoven or woven into raffia prepared from metallocene-produced polyethylene (mPE).
  • The invention also provides a process for preparing raffia or stretched tapes with a metallocene-produced polyethylene that comprises the steps of:
  • a) providing a metallocene-produced medium density polyethylene resin;
  • b) producing a film from the polyethylene resin of step a)
  • c) orienting the film obtained from step b) by stretching;
  • d) cutting the stretched film of step c) into strips.
  • Alternatively, the primary film can first be cut into strips and then oriented by stretching.
  • The film can be either a blown film or a cast film. Film production is easier with processed material having high melt strength such as polyethylene having long chain branches and/or very long linear chains.
  • Orientation of the primary film or of the cut tapes is carried out by stretching while passing through an air oven or over a hot plate, maintained at a temperature below the melting temperature. Stretching of the primary film or of the cut tapes is done by passing said film or tapes over two sets of rollers (goddet rollers) placed respectively before and after the air oven/hot plate, and operating at different speeds. The stretch ratio S2/S1 is defined by the ratio of the speed of roller 2, S2 to the speed of roller 1, S1 wherein S2 is larger than S1.
  • Stretching at such high temperature results in chain/crystals orientation with a simultaneous increase of crystallinity. These structural changes lead to an increase of tensile strength and concurrently to a reduction of elongation. The tensile strength increases with increasing stretch ratio and with increasing stretching temperature. It is preferred that the stretching temperature is as close as possible to but smaller than the melting temperature. For high density polyethylene, typical values for the stretch ratio are of from 5.0 to 7.0. The typical stretching temperatures depend upon the melting temperature of the polyethylene resins: they must be lower than but as close as possible to the melting temperature. Typically, they are from 5 to 70 °C lower than the melting temperature of the resin, preferably they are from 10 to 50 °C lower than the melting temperature of the resin.
  • Preferably, the drawn tapes are annealed immediately after the stretching operation in order to minimise shrinkage that could occur as a result of residual stresses in the oriented tapes. Annealing is done by heating the stretched tapes while they are being transferred from the second goddet rollers onto a third roller having a speed S3 that is smaller than the speed of roller 2, S2. Preferably, speed S3 is about 95 % of speed S2. The annealing ratio AR is defined as (S2-S3)/S2) at a temperature slightly inferior to the stretching temperature. Typically, the annealing temperature is from 5 to 10 °C lower than the stretching temperature.
  • Polymers that do not include either very long linear chains or long chain branched molecules have a better stretchability. For example, the low density polyethylene (LDPE) having long chain branches cannot be stretched beyond a certain degree and, to the contrary, the purely linear polyethylene chains usually obtained with a Ziegler-Natta catalyst have a high degree of stretchability.
  • The metallocene used to prepare the high density polyethylene can be a bis-indenyl represented by the general formula: R" (Ind)2 MQ2 or a bis-cyclopentadienyll represented by the formula (Cp)2 MQ2 wherein (Ind) is an indenyl or an hydrogenated indenyl, substituted or unsubstituted, Cp is a cyclopentadienyl ring substituted or unsubstituted, R" is a structural bridge between the two indenyls to impart stereorigidity that comprises a C1-C4 alkylene radical, a dialkyl germanium or silicon or siloxane, or a alkyl phosphine or amine radical, which bridge is substituted or unsubstituted; Q is a hydrocarbyl radical having from 1 to 20 carbon atoms or a halogen, and M is a group IVb transition metal or Vanadium.
  • In formula (I), each indenyl or hydrogenated indenyl compound may be substituted in the same way or differently from one another at one or more positions in the cyclopentadienyl ring, the cyclohexenyl ring and the bridge.
  • In formula (I), each substituent on the indenyl may be independently chosen from those of formula XRv in which X is chosen from group IVA, oxygen and nitrogen and each R is the same or different and chosen from hydrogen or hydrocarbyl of from 1 to 20 carbon atoms and v+1 is the valence of X. X is preferably C. If the cyclopentadienyl ring is substituted, its substituent groups must be so bulky as to affect coordination of the olefin monomer to the metal M. Substituents on the cyclopentadienyl ring preferably have R as hydrogen or CH3. More preferably, at least one and most preferably both cyclopentadienyl rings are unsubstituted.
  • In a particularly preferred embodiment, both indenyls are unsubstituted.
  • In formula (II), each cyclopentadienyl ring may be substituted in the same way or differently from one another at one or more positions in the cyclopentadienyl ring.
  • In formula (II), each substituent on the cyclopentadienyl may be independently chosen from those of formula XR*v in which X is chosen from group IVA, oxygen and nitrogen and each R* is the same or different and chosen from hydrogen or hydrocarbyl of from 1 to 20 carbon atoms and v+1 is the valence of X. X is preferably C and the most preferred substituent is n-butyl.
  • R" is preferably a C1-C4 alkylene radical (as used herein to describe a difunctional radical, also called alkylidene), most preferably an ethylene bridge (as used herein to describe a difunctional radical, also called ethylidene), which is substituted or unsubstituted.
  • The metal M is preferably zirconium, hafnium, or titanium, most preferably zirconium.
  • Each Q is the same or different and may be a hydrocarbyl or hydrocarboxy radical having 1 to 20 carbon atoms or a halogen. Suitable hydrocarbyls include aryl, alkyl,alkenyl,alkylaryl or arylalkyl. Each Q is preferably halogen.
  • Among the preferred metallocenes used in the present invention, one can cite bis tetrahydro-indenyl compounds and bis indenyl compounds as disclosed for example in WO 96/35729 or bis(cyclopentadienyl) compounds. The most preferred metallocene catalysts are ethylene bis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride and bis(n-butyl-cyclopentadienyl) zirconium dichloride.
  • The metallocene may be supported according to any method known in the art. In the event it is supported, the support used in the present invention can be any organic or inorganic solids, particularly porous supports such as talc, inorganic oxides, and resinous support material such as polyolefin. Preferably, the support material is an inorganic oxide in its finely divided form.
    The addition on the support, of an agent that reacts with the support and has an ionising action, creates an active site.
  • Preferably, alumoxane is used to ionise the catalyst during the polymerization procedure, and any alumoxane known in the art is suitable.
  • The preferred alumoxanes comprise oligomeric linear and/or cyclic alkyl alumoxanes represented by the formula :
    Figure 00060001
    for oligomeric, linear alumoxanes
    And
    Figure 00060002
    for oligomeric, cyclic alumoxanes,
    wherein n is 1-40, preferably 10-20, m is 3-40, preferably 3-20 and R is a C1-C8 alkyl group and preferably methyl.
  • Methylalumoxane is preferably used.
  • One or more aluminiumalkyl(s) can be used as cocatalyst in the reactor. The aluminiumalkyl is represented by the formula AIRx can be used wherein each R is the same or different and is selected from halides or from alkoxy or alkyl groups having from 1 to 12 carbon atoms and x is from 1 to 3. Especially suitable aluminiumalkyl are trialkylaluminium, the most preferred being triisobutylaluminium (TIBAL).
  • Further, the catalyst may be prepolymerised prior to introducing it in the reaction zone and/or prior to the stabilization of the reaction conditions in the reactor.
  • The polyethylene resin of the present invention has a density ranging from 0.925 to 0.950 g/cm3, preferably, from 0.930 to 0.940 g/cm3 and most preferably about 0.935 g/cm3. The melt index MI2 is within the range 0.1 to 5 g/10 min, preferably in the range 0.2 to 1.5 g/10 min.
  • The density is measured following the method of standard test ASTM D 1505 at 23 °C and the melt index Ml2 is measured following the method of standard test ASTM D 1238 at 190 °C and under a load of 2.16 kg.
  • The metallocene-prepared polyethylenes produce very strong stretched tapes and raffia products, mainly because of their narrow molecular weight distribution and because they have long chain branches. The final products have improved tensile and elongation properties properties.
  • Example.
  • Several resins have been tested for preparing raffia products.
  • Resin R1 is a medium density polyethylene resin prepared with isopropylidene (tetrahydroindenyl) zirconium dichloride. It had a density of 0.934 g/cm3 and a melt index MI2 of 0.9 g/10 min. It was additivated as follows:
    • 94.5 wt% of resin R1;
    • 4 % red masterbatch PE 44930 from Clariant;
    • 1 % polymer processing aid AMF 702 from Schuman;
    • 0.5 % antibloc masterbatch B1981 from Clariant.
  • Resin R2 was a commercial resin prepared with a Ziegler-Natta catalyst system: (GF7740 F1 from Hostalen). It had a density of 0.946 g/cm3 and a melt index MI2 of 0.5 g/10min.
  • These two resins were treated under the same conditions for blown film production, and for stretching.
    • Melt die temperature: 220 °C.
    • Thickness of primary film: 60 microns;
    • Orientation temperature: varied progressively from 80 to 120 °C.
    • Stretch ratio: 7:1
  • The final products, whether unwoven or woven (nets) obtained from the metallocene-produced resin R1 had a high tenacity, an excellent elongation at rupture and a very high break strength. It also had a soft touch and a high flexibility.
  • The properties of the stretched tapes obtained from resins R1 and R2 are summarised in Table I.
    R1 R2
    Tenacity at rupture cN/Tex 24.9 22.1
    Elongation at rupture % 33.2 29.3
    Strength at rupture cN 593 525
    Titre Tex 23.8 20.8
  • The elongation, the strength and the tenacity at rupture of the stretched tapes have been measured following the method of standard test ISO-2062 (1993).
  • The titre is measured in tex or g/km: this is a measure of the linear mass of a filament or fibre.
  • The properties of the woven stretched tapes or raffia are displayed in Table II.
    R1 R2
    Elongation at rupture % 30.6 29.4
    Strength at rupture cN 997 811
  • The raffia products prepared according to the present invention has thus improved properties with respect to those of the prior art.
  • The elongation and strength at rupture of the raffia have been measured following the method of standard test ISO-5081 (1977).

Claims (8)

  1. Monofilaments or stretched tapes, unwoven or woven into raffia prepared from metallocene-produced polyethylene.
  2. The monofilaments or stretched tapes of claim 1 wherein the metallocene is a tetrahydroindenyl.
  3. A process for preparing stretched tapes that comprises the steps of:
    a) providing a metallocene-produced medium density polyethylene resin;
    b) producing a film from the polyethylene resin of step a)
    c) orienting the film obtained from step b) by stretching;
    d) cutting the stretched film of step c) into strips
    e) optionally, annealing the stretched tapes.
  4. The process of claim 4 wherein step d) is performed before step c)
  5. The process of claim 4 or claim 5 wherein the stretching temperature is of from 10 to 70 °C lower than the melting temperature of the resin.
  6. The process of claim 6 wherein the stretching temperature is of from 15 to 50 °C lower than the melting temperature of the resin
  7. The process of any one of claims 4 to 7 wherein the ratio of the rollers' velocities is in the range of 5 to 7.
  8. The process of any one of claims 4 to 8 wherein the annealing temperature, if annealing is performed, is of from 5 to 10 °C lower than the stretching temperature
EP03076128A 2003-04-16 2003-04-16 Metallocene produced polyethylene for fibres applications Withdrawn EP1469104A1 (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
EP03076128A EP1469104A1 (en) 2003-04-16 2003-04-16 Metallocene produced polyethylene for fibres applications
US10/553,572 US20070178303A1 (en) 2003-04-16 2004-04-07 Metallocene produced polyethylene for fibres applications
CNB200480009870XA CN100434575C (en) 2003-04-16 2004-04-07 Metallocene produced polyethylene for fibres applications
JP2006505533A JP4767839B2 (en) 2003-04-16 2004-04-07 Polyethylene made using metallocene with fiber applications
KR1020057019653A KR101333394B1 (en) 2003-04-16 2004-04-07 Metallocene produced polyethylene for fibres applications
PCT/EP2004/050479 WO2004092459A1 (en) 2003-04-16 2004-04-07 Metallocene produced polyethylene for fibres applications
EP04726183A EP1613797B1 (en) 2003-04-16 2004-04-07 Monofilaments or stretched tapes from metallocene-produced polyethylene

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EP03076128A EP1469104A1 (en) 2003-04-16 2003-04-16 Metallocene produced polyethylene for fibres applications

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EP1469104A1 true EP1469104A1 (en) 2004-10-20

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EP03076128A Withdrawn EP1469104A1 (en) 2003-04-16 2003-04-16 Metallocene produced polyethylene for fibres applications
EP04726183A Not-in-force EP1613797B1 (en) 2003-04-16 2004-04-07 Monofilaments or stretched tapes from metallocene-produced polyethylene

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US (1) US20070178303A1 (en)
EP (2) EP1469104A1 (en)
JP (1) JP4767839B2 (en)
KR (1) KR101333394B1 (en)
CN (1) CN100434575C (en)
WO (1) WO2004092459A1 (en)

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EP2184302A1 (en) * 2004-12-22 2010-05-12 Total Petrochemicals Research Feluy Patent Dept. Blow moulded milk bottles
WO2010089415A1 (en) * 2009-02-09 2010-08-12 Total Petrochemicals Research Feluy High impact resistance polyethylene
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CN101370657B (en) * 2006-01-19 2012-09-05 巴塞尔聚烯烃股份有限公司 Polyethylene composition for stretched tape products
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WO2005021846A1 (en) * 2003-09-03 2005-03-10 Innovene Manufacturing Belgium Nv Polyethylene composition for nets
EP1659136A1 (en) * 2004-11-19 2006-05-24 Total Petrochemicals Research Feluy Solid state properties of polyethylene prepared with tetrahydroindenyl-based catalyst system
EP2184302A1 (en) * 2004-12-22 2010-05-12 Total Petrochemicals Research Feluy Patent Dept. Blow moulded milk bottles
CN101370657B (en) * 2006-01-19 2012-09-05 巴塞尔聚烯烃股份有限公司 Polyethylene composition for stretched tape products
WO2007082817A1 (en) * 2006-01-19 2007-07-26 Basell Polyolefine Gmbh Polyethylene composition for stretched tape products
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WO2012038471A1 (en) 2010-09-23 2012-03-29 Total Petrochemicals Research Feluy Artificial grass
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WO2012056053A1 (en) * 2010-10-29 2012-05-03 Dow Global Technologies Llc Polyethylene-based oriented monofilaments and strips and method for the preparation thereof
WO2018060224A1 (en) * 2016-09-27 2018-04-05 Dsm Ip Assets B.V. Transparent drawn article
US11400639B2 (en) 2016-09-27 2022-08-02 Dsm Ip Assets B.V. Transparent drawn article
WO2020023215A1 (en) * 2018-07-26 2020-01-30 Dow Global Technologies Llc Heat-shrinkable woven raffia fabric and methods of using such a fabric

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CN1774528A (en) 2006-05-17
EP1613797B1 (en) 2013-03-06
KR101333394B1 (en) 2013-11-28
JP2006523784A (en) 2006-10-19
CN100434575C (en) 2008-11-19
EP1613797A1 (en) 2006-01-11
KR20060010750A (en) 2006-02-02
US20070178303A1 (en) 2007-08-02
WO2004092459A1 (en) 2004-10-28
JP4767839B2 (en) 2011-09-07

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