CN100434575C - Metallocene produced polyethylene for fibres applications - Google Patents

Metallocene produced polyethylene for fibres applications Download PDF

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Publication number
CN100434575C
CN100434575C CNB200480009870XA CN200480009870A CN100434575C CN 100434575 C CN100434575 C CN 100434575C CN B200480009870X A CNB200480009870X A CN B200480009870XA CN 200480009870 A CN200480009870 A CN 200480009870A CN 100434575 C CN100434575 C CN 100434575C
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resin
temperature
tension belt
metallocene
film
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CN1774528A (en
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埃里克·梅泽尔斯
文森特·斯蒂芬尼
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Total Petrochemicals Research Feluy SA
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/42—Formation of filaments, threads, or the like by cutting films into narrow ribbons or filaments or by fibrillation of films or filaments
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/42—Formation of filaments, threads, or the like by cutting films into narrow ribbons or filaments or by fibrillation of films or filaments
    • D01D5/426—Formation of filaments, threads, or the like by cutting films into narrow ribbons or filaments or by fibrillation of films or filaments by cutting films
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
    • 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
    • Y—GENERAL 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Artificial Filaments (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

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

Description

The polyethylene that the metallocene of fiber applications generates
The present invention relates to following field: the monofilament and the tension belt (stretched tape) of the polyethene preparation that generates by metallocene.
Monofilament is the thread polymerised unit (strands) of uniaxial orientation, and it has annular cross section.They are made by melt spinning technology, depend on that the final use of product is used, and their size is 0.1 to 2.5mm at diameter.Polyethylene, polypropylene, nylon and polyester are commonly used for the raw material of preparation monofilament.
Tension belt generates from initial film (primary film) by blown film or cast film process.This film can cut into band, be orientated then, otherwise perhaps, orientation cuts into band then earlier.This orientation is following carries out: stretch this film or band are lower than on the air-oven or hot plate of fusing point by temperature simultaneously.This stretching is following to be carried out: make this film or band two groups of rollers through placing air-oven and/or hot plate front and back respectively and moving with friction speed, the speed of second group of roller is greater than the speed of first group of roller.
The polymer that is preferred for these application on the market is the high density polyethylene (HDPE) (HDPE) with Z-N (Ziegler-Natta) Preparation of Catalyst, described HDPE has less than/10 minutes MI2 of 1 gram, for example Solvay Eltex A4009MFN1325 resin or Basell Hostalen GF 7740F1, GF7740F2, GF7740F3, GF7750M2 rank, perhaps disclosed polyvinyl resin among the GB-0023662.The molecular weight distribution MWD of these resins is quite big, and this shows that resin can comprise very long chain and very short chain.
Semi-crystalline polyethylene (PE) and polypropylene (PP) also are used as the raw material of monofilaments stretched tapes and raffia (raffia), for example, and as disclosed among FR-A-2814761, JP-2001342209 or the JP-2001220405.In this manual, raffia is defined as woven (woven) monofilament or woven tension belt.With compare with monofilament by the tension belt of polypropylene preparation, higher percentage elongation when showing fracture by the tension belt of polyethene preparation and monofilament, the trend of bigger flexible and fibrillation is lower.For example, these character are favourable when generating the woven belt fabric.Yet, suffering disadvantageously by the product of polyethene preparation, their toughness is more much lower than the toughness of the product that is prepared by polypropylene.Toughness increases as the function of the degree of orientation of molecular weight, density, chain/crystal, along with molecular weight distribution narrows down and increases.Impact strength is along with density reduces, and molecular weight increases and molecular weight distribution reduces and increases.
Therefore, need below the existence: monofilament or tension belt, non-woven or woven one-tenth raffia, and have better balance of properties.
One of purpose of the present invention is monofilament or the stretched tape products that preparation has high tenacity.
Another object of the present invention is monofilament or the stretched tape products that preparation has high impact.
Another purpose of the present invention is monofilament or the stretched tape products that preparation has high elongation rate when rupturing.
Another object of the present invention is monofilament or the stretched tape products that preparation has flexible touch (soft touch).
Another object of the present invention is monofilament or the stretched tape products that preparation has high flexible.
Therefore, the invention provides monofilament or tension belt, non-woven or woven one-tenth raffia, it is polyethylene (mPE) resins that generated by metallocene, and described polyvinyl resin has long-chain branch (long chain branch).
Preferred metallocene catalyst component is based on the tetrahydro indenyl component or based on constraint physical dimension component (constrained geometry component), more preferably based on the tetrahydro indenyl component.
The present invention also provides by the polyethene preparation raffia of metallocene generation or the method for tension belt, and it comprises the steps:
A) the medium density polyethylene resin that provides metallocene to generate, described polyvinyl resin has long-chain branch;
B) produced film from the polyvinyl resin of step a);
C) the film orientation that obtains in the step b) by stretching, making;
D) stretched film with step c) cuts into strip.
Alternatively, initial film can at first cut into strip, stretch orientation then.
This film can be blown film or casting films.Carry out film preparation easily with the processed materials with high fondant-strength, described material for example has the long-chain branch and/or the unusual polyethylene of long linear.The polyvinyl resin particularly suitable that preparation is had long-chain branch based on the metallocene catalyst system of tetrahydro indenyl component or constraint physical dimension component.
In the preparation blown film, provide very stable bubble (bubble) with the resin of tetrahydro indenyl catalytic component preparation, do not have or the film of very few folding line (crease) with presenting thereby cause having uniform thickness.When film being cut into band and stretching, uneven thickness and folding line are weakness.
In the preparation casting films, the resin for preparing with the tetrahydro indenyl catalytic component has stable elongation viscosity (elongational viscosity), thereby causes stable and regular thickness.
Also further observe: when density was lower than the linear resins with same mechanical performance, the resin with long-chain branch kept favorable mechanical performance, for example anti-traction property (traction resistance) and toughness.Operation has the following advantages under the low-density: provide to have the material that improves flexible, low melting glass and good workability.
Orientation initial film or cutting belt is following carries out: stretch simultaneously through keeping air-oven and the hot plate that is lower than fusion temperature.Stretching initial film or cutting belt are following carries out: make described film or band two groups of rollers through placing air-oven/hot plate front and back respectively and moving with friction speed.Draw ratio S2/S1 is defined as the speed S2 of roller 2 and the ratio of the speed S1 of roller 1, and wherein S2 is greater than S1.
Stretching under this high temperature causes chain/crystal orientation, increases degree of crystallinity simultaneously.The variation of these structures causes tensile strength to increase, and percentage elongation reduces simultaneously.Tensile strength increases along with draw ratio and draft temperature (stretching temperature) increases and the increase draft temperature preferably approaches as far as possible but less than fusion temperature.For medium density polyethylene, the value of draw ratio is generally 5.0-7.0.Typical draft temperature depends on the fusion temperature of polyvinyl resin: they must be lower than, but as far as possible near fusion temperature.Usually, they hang down 5-70 ℃ than the fusion temperature of resin; Preferably, they hang down 10-70 ℃ than the fusion temperature of resin; More preferably, skill than low 15-50 ℃ of the fusion temperature of resin.
Preferably, after stretched operation, immediately to the annealing of drawn tapes row, so that the contraction that takes place owing to the residual stress in the orientation band minimizes.Following the finishing of annealing: the heating tension belt is that S3 is less than the speed S2 of roller 2 on the 3rd roller of S3 with them from second godet roller (goddet roller) speed of being transferred to simultaneously.Preferably, speed S3 is about 95% of speed S2.Under the temperature a little less than draft temperature, annealing rate AR is defined as (S2-S3)/S2).Usually, annealing temperature is lower 5-10 ℃ than draft temperature.
The polymer that does not contain unusual long linear or long-chain branch molecule has better tensility.For example, the low density polyethylene (LDPE) (LDPE) with long-chain branch can not stretch and surpass to a certain degree, yet the Polyethylene Chain of the pure straight chain that obtains with Ziegler-Natta catalyst usually has the tensility of height.
The metallocene that is used to prepare high density polyethylene (HDPE) can be two indenyls (bis-indenyl) of being represented by following general formula:
R″(Ind) 2MQ 2 (I)
The bicyclic pentadiene that perhaps following general formula is represented
R″(Cp) 2MQ 2 (II)
The perhaps constraint physical dimension component of following general formula
R″(Cp)(NR′)MQ 2 (III)
Wherein (Ind) be replace or unsubstituted indenyl or hydrogenation indenyl, Cp is that replace or unsubstituted cyclopentadienyl rings, R ' is hydrogen or the alkyl with 1-20 carbon atom, R, and " be the structure bridge of giving upright structure rigidity (stereorigidity) between two indenyls, it comprises C 1-C 4Alkylidene, dialkyl group gallium or silicon or siloxanes, perhaps alkylphosphines or amido, this bridge are that replace or unsubstituted; Q is alkyl or the halogen with 1-20 carbon atom, and M is IVb group 4 transition metal or vanadium.
In general formula (I), each indenyl or hydrogenation indenyl compound can be in an identical manner or mutually different modes on the one or more positions on cyclopentadienyl rings, cyclohexene ring and the described bridge, be substituted.
In general formula (I), each substituting group on the indenyl can independently be selected from general formula X R vThose, wherein X is selected from IVA family, oxygen and nitrogen, each R is identical or different, be selected from hydrogen or have the alkyl of 1-20 carbon atom, and v+1 is the chemical valence of X.X is preferably C.If cyclopentadienyl rings replaces, then substituting group must be big, so that influence the coordination of olefinic monomer to metal M.Substituting group on the cyclopentadienyl rings preferably has and is hydrogen or CH 3R.More preferably, at least one cyclopentadienyl rings is unsubstituted; Most preferably, two cyclopentadienyl rings are unsubstituted.
In preferred embodiments, two indenyls are unsubstituted, and most preferred catalytic component is a tetrahydro indenyl.
In general formula (II), each cyclopentadienyl rings can be in an identical manner or mutually different modes on the one or more positions on the cyclopentadienyl rings, be substituted.
In general formula (II), each substituting group on the cyclopentadienyl group can be independently selected from general formula X R * vThose, wherein X is selected from IVA family, oxygen and nitrogen, each R *Identical or different, be selected from hydrogen or have the alkyl of 1-20 carbon atom, and v+1 is the chemical valence of X.X is preferably C, and most preferred substituting group is a normal-butyl.
R " is preferably C 1-C 4Alkylidene (is used to describe two functional groups herein, be also referred to as alkylidene radical (alkylidene)), most preferably be ethylene bridge (ethylene bridge) (be used to describe two functional groups, be also referred to as ethidine (ethylidene)) herein, they are that replace or unsubstituted.
Metal M is preferably zirconium, hafnium or titanium, most preferably is zirconium.
Each Q is identical or different, and can be alkyl or carboxyl or the halogen with 1-20 carbon atom.Suitable alkyl comprises aryl, alkyl, alkenyl, alkaryl or aralkyl.Each Q is preferably halogen.
In the present invention in the preferred metallocene of Shi Yonging, for example can enumerate among the WO 96/35729 disclosed pair of tetrahydro indenyl compound and two indenyl compounds or two (cyclopentadienyl group) compound.Most preferred metallocene catalyst is isopropylidene-two (4,5,6,7-tetrahydrochysene-1-indenyl) zirconium chloride.
Can be according to any method well known in the art, load metallocene.Under by the situation of load, the carrier that the present invention uses can be any organic or inorganic solid, particularly porous carrier, for example talcum, inorganic oxide, and resinous support material, for example polyolefin.Preferably, carrier material is the inorganic oxide of meticulous pulverised form.The reagent that will react and have ionization with carrier is added into and has produced activity site on the carrier.
Preferably, in polymerization process, use the aikyiaiurnirsoxan beta ionized catalyst, any aikyiaiurnirsoxan beta well known in the art is suitable.
Preferred aikyiaiurnirsoxan beta comprises oligomeric straight chain and/or the cyclic alkyl aikyiaiurnirsoxan beta that following general formula is represented:
Oligomeric straight chain aikyiaiurnirsoxan beta:
Figure C20048000987000071
With
The oligomeric cyclic aikyiaiurnirsoxan beta:
Wherein n is 1-40, is preferably 10-20, and m is 3-40, is preferably 3-20, and R is C 1-C 8Alkyl is preferably methyl.The preferred methylaluminoxane of using.
In reactor, one or more alkyl aluminums can be used as co-catalyst.Can use by general formula AlR xThe alkyl aluminum of expression, wherein each R is identical or different, and is selected from halide or has the alkoxyl or the alkyl of 1-12 carbon atom, and x is 1-3.Specially suitable alkyl aluminum is a trialkylaluminium, most preferably triisobutyl aluminium (TIBAL).
In addition, can be before catalyst be introduced conversion zone and/or before reactor internal reaction conditional stability, pre-polymerized catalyst.
The density of polyvinyl resin of the present invention is 0.925-0.950g/cm 3, be preferably 0.930-0.940g/cm 3, most preferably be about 0.935g/cm 3Melt index (MI) MI2 is 0.1-5g/10min, is preferably 0.2-1.5g/10min.
At 23 ℃ of following density measurements, under 190 ℃ and 2.16kg load, measure melt index (MI) according to standard testing ASTM D 1505 methods according to standard testing ASTM D1238 method.
The polyethylene of metallocene-prepared produces very strong tension belt and raffia products, and this mainly is because of their narrow molecular weight distribution and because they have long-chain branch.Final products have improved tension force and elongation performance, and they have improved flexible and processing characteristics simultaneously.
Embodiment
Tested several resins, with the preparation raffia products.
Resin R1 is the medium density polyethylene resin with the preparation of isopropylidene (tetrahydro indenyl) zirconium dichloride.Its density is 0.934g/cm 3, melt index (MI) MI2 is 0.9g/10min.Its adding ingredient is as follows:
-94.5wt% resin R1;
-4% red masterbatch PE 44930 (available from Cariant);
-1% polymer processing aids AMF 702 (available from Schuman);
-0.5% agglomeration resistance masterbatch B1981 (available from Cariant).
Resin R2 is the resin of industry with the ziegler-natta catalyst systems preparation: (available from the GF7740F1 of Hostalen).Its density is 0.946g/cm 3, melt index (MI) MI2 is 0.5g/10min.
Under identical condition, handle this resin, to carry out the blown film preparation and to stretch.
-melt die temperature: 220 ℃.
The thickness of-initial film: 60 microns;
-orientation temperature: from 80 to 120 ℃ change gradually.
-draw ratio: 7: 1
The final products that the resin R1 that generates from metallocene obtains, non-woven or woven (net) has high tenacity, the percentage elongation of excellence and very high fracture strength during fracture.It also has flexible touch and high flexible.
The character of the tension belt that obtains from resin R1 and R2 is summarized in the Table I.
Table I
R1 R2
Toughness during fracture, cN/Tex 24.9 22.1
Percentage elongation during fracture, % 33.2 29.3
Intensity during fracture, cN 593 525
Fiber number (Titre), Tex 23.8 20.8
According to standard testing ISO-2062 (1993), measured percentage elongation, intensity and the toughness of tension belt when fracture.
Fiber number is measured as tex or g/km: this is measuring of the silk or the linear mass of fiber.
The character of woven tension belt or raffia as shown in Table II.
Table II
R1 R2
Percentage elongation during fracture, % 30.6 29.4
Intensity during fracture, cN 997 811
With respect to those products of prior art, the raffia products of the present invention preparation thereby have improved character.
Percentage elongation and the intensity of raffia when fracture is measured according to standard testing ISO-5081 (1977).

Claims (11)

1. monofilament or tension belt, it is non-woven or woven one-tenth raffia, and it is the polyvinyl resin preparation that generated by metallocene, and described polyvinyl resin has long-chain branch.
2. the monofilament of claim 1 or tension belt, wherein said metallocenes is a tetrahydro indenyl.
3. prepare the method for tension belt, it comprises the steps:
A) the medium density polyethylene resin that provides metallocene to generate, described polyvinyl resin has long-chain branch;
B) from the polyvinyl resin produced film of step a);
C) the film orientation that obtains in the step b) by stretching, making;
D) stretched film with step c) cuts into strip;
E) randomly, tension belt is annealed.
4. the method for claim 3, wherein step d) was carried out before step c).
5. the method for claim 3, wherein draft temperature is than low 10-70 ℃ of the fusion temperature of resin.
6. the method for claim 4, wherein draft temperature is than low 10-70 ℃ of the fusion temperature of resin.
7. the method for claim 5, wherein draft temperature is than low 15-50 ℃ of the fusion temperature of resin.
8. the method for claim 6, wherein draft temperature is than low 15-50 ℃ of the fusion temperature of resin.
9. each method among the claim 3-8, the ratio of the speed of its central roll is in the scope of 5-7.
10. each method among the claim 3-8, if wherein anneal, then annealing temperature is lower 5-10 ℃ than draft temperature.
11. the method for claim 9, if wherein anneal, then annealing temperature is lower 5-10 ℃ than draft temperature.
CNB200480009870XA 2003-04-16 2004-04-07 Metallocene produced polyethylene for fibres applications Expired - Fee Related CN100434575C (en)

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EP03076128.2 2003-04-16
EP03076128A EP1469104A1 (en) 2003-04-16 2003-04-16 Metallocene produced polyethylene for fibres applications

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KR (1) KR101333394B1 (en)
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WO (1) WO2004092459A1 (en)

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