CN100363414C - Polyethylene composition for producing L-ring drums - Google Patents
Polyethylene composition for producing L-ring drums Download PDFInfo
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- CN100363414C CN100363414C CNB2003801072971A CN200380107297A CN100363414C CN 100363414 C CN100363414 C CN 100363414C CN B2003801072971 A CNB2003801072971 A CN B2003801072971A CN 200380107297 A CN200380107297 A CN 200380107297A CN 100363414 C CN100363414 C CN 100363414C
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- 239000000203 mixture Substances 0.000 title claims abstract description 39
- -1 Polyethylene Polymers 0.000 title claims abstract description 26
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 23
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 23
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229920001577 copolymer Polymers 0.000 claims abstract description 7
- 238000009826 distribution Methods 0.000 claims abstract description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 6
- 229920001519 homopolymer Polymers 0.000 claims abstract description 3
- 229920001038 ethylene copolymer Polymers 0.000 claims abstract 2
- 229920000642 polymer Polymers 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 7
- 238000005336 cracking Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 238000005259 measurement Methods 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 4
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims description 4
- 230000008961 swelling Effects 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- 238000005829 trimerization reaction Methods 0.000 claims description 3
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims description 2
- 150000002736 metal compounds Chemical class 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- 150000002899 organoaluminium compounds Chemical class 0.000 claims description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical group CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 abstract description 4
- 238000000071 blow moulding Methods 0.000 abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 238000007664 blowing Methods 0.000 description 4
- 239000000206 moulding compound Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000006902 nitrogenation reaction Methods 0.000 description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000002902 bimodal effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 240000004859 Gamochaeta purpurea Species 0.000 description 1
- 239000004705 High-molecular-weight polyethylene Substances 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 240000005373 Panax quinquefolius Species 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminum chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 230000002706 hydrostatic effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000011005 laboratory method Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/001—Multistage polymerisation processes characterised by a change in reactor conditions without deactivating the intermediate polymer
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/08—Butenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/07—High density, i.e. > 0.95 g/cm3
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/12—Melt flow index or melt flow ratio
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
- C08L2666/06—Homopolymers or copolymers of unsaturated hydrocarbons; Derivatives thereof
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to a polyethylene composition with multimodal molecular mass distribution, which is particularly suitable for the blow molding of L-ring drums having a volume in the range of from 50 to 250 dm<SUP>3 </SUP>(I). The composition has a density in the range of from 0.950 to 0.956 g/cm<SUP>3 </SUP>at 23 DEG C. and a MFR<SUB>1gp/21.6 </SUB>in the range from 1.5 to 3.5 dg/min. It comprises from 35 to 45% by weight of a low-molecular-mass ethylene homopolymer A, from 34 to 44% by weight of a high-molecular-mass copolymer B made from ethylene and from another 1-olefin having from 4 to 8 carbon atoms, and from 18 to 26 % by weight of an ultrahigh-molecular-mass ethylene copolymer C.
Description
The present invention relates to have the polyethylene composition of multimodal shape molecular weight distribution, it is particularly suitable for blowing capacity (volume) at 50-250dm
3(l) the L-ring drums of scope, with relate to this method for compositions of preparation, be in the presence of the catalyst system of forming by Z-type catalyst and promotor such as triethyl aluminum, triisobutyl aluminium, alkyl aluminum chloride and alkyl-al hydride, to be undertaken by the multistep method of forming by the successive slurry polymerization.The invention still further relates to the L-annular container of producing by blowing by said composition.
Polyethylene is widely used for the production requirement material and has extra high physical strength, high erosion resistance and various types of moulded works of cocksure permanent stability.Poly another special benefits is that it also has good chemical-resistant and is light material inherently.
EP-A-603 has described before 935 a kind ofly based on polyethylene with have the blow molding composition of bimodal shape molecular weight distribution, and is suitable for producing the moulded work with good mechanical properties.
US-A 5,338, and 589 have described and a kind ofly have even the material of wideer molecular weight distribution, and by using from the known high durability of WO91/18934 (mileage) Preparation of Catalyst, wherein the magnesium alkoxide uses with gelatinous suspensoid form.Unexpectedly, have been found that and in moulded work, use this material to allow to improve simultaneously the character of in the hypocrystalline thermoplastics, oppositely being correlated with usually that these particularly are stiffness on the one hand and are stress cracking resistance and toughness on the other hand.
Yet this known bimodal shape product has low relatively melt strength especially in the course of processing.This means that the parison of extruding will rupture through the molten state of being everlasting, it is responsive to make that extrusion can not receive ground to processing.In addition, especially when producing the heavy-walled container, find wall thickness since curing prepolymer melt from the upper area of mould to the bottom zone flows but uneven.
Therefore, the objective of the invention is to develop a kind of polyethylene composition that is used for blowing, it demonstrates the further improvement above all known materials in by the processing of blowing with production L-ring drums.Especially, the high fondant-strength of composition should allow to operate expressing technique for a long time and not have parison to destroy, and the composition swelling ratio of accurately adjusting should allow the optimization of wall thickness control.In addition, moulding compound must have enough toughness for the V shape lifting of fully loaded L-ring drums and truck haul(ing).
We have been surprised to find that this purpose realizes by starting described composition, the characteristic features of said composition is the low-molecular-weight ethylenic homopolymer A that it comprises 35-45% weight, the high molecular weight copolymer B that is made by ethene and another kind of 1-alkene with 4-8 carbon atom of 34-44% weight and the ultra-high-molecular-weight polyethylene multipolymer C of 18-26% weight, wherein all percent value are based on the gross weight of moulding compound.
The invention still further relates to slurry polymerization with cascade prepares this method for compositions and relates to thus composition and make capacity or volume at 50-250dm
3(l) method of scope and L-ring drums with quite excellent mechanical intensive property.
It is 0.950-0.956g/cm that polyethylene polymer of the present invention has at 23 ℃
3Density in the scope and three wide peak shape molecular weight distribution.High molecular weight copolymer B only contains other olefin monomer unit with 4-8 carbon atom of low ratio, promptly less than 0.1% weight.The example of these comonomers has 1-butylene, 1-amylene, 1-hexene, 1-octene or 4-methyl-1-pentene.The Alathon of ultra-high molecular weight or multipolymer C also contain one or more the above-mentioned comonomers in the 0.1-0.6% weight range.
The melt-flow index ISO1133 that polymer composition of the present invention has is in the scope of 1.5-3.5dg/min, with MFR
190/21.6Expression and viscosity number VN
TotAt 500-600cm
3In the scope of/g, according to ISO/R1191 in naphthalane 135 ℃ of measurements.
Three peak shapes be three independently molecular weight distribution position of centre of gravity measuring and can describing by means of the polymkeric substance that in the successive polymerization stage, forms according to the viscosity number VN of ISO/R1191.Therefore, the relevant band width of the polymkeric substance that forms in each stage of reaction is as follows:
After first polymerization stage to the viscosity number VN of polymer measurement
1Viscosity number VN with low molecular weight polyethylene A
ABe consistent, and be at 160-220cm according to the present invention
3In the scope of/g.
After second polymerization stage to the viscosity number VN of polymer measurement
2The viscosity number VN that is not equal to the High molecular weight polyethylene B that in second polymerization stage, forms
B, but the viscosity number of the mixture of representation polymer A and polymer B, VN
BOnly can determine by calculating.According to the present invention, VN
2Be at 230-320cm
3In the scope of/g.
After the trimerization step of reaction to the viscosity number VN of polymer measurement
3The viscosity number VN that is not equal to the ultrahigh molecular weight copolymer C that forms in the stage at trimerization reaction C
c, but representation polymer A, the viscosity number of the mixture of polymer B and polymkeric substance C, VN
cOnly can determine by calculating.According to the present invention, VN
3Be at 500-600cm
3In the scope of/g.
Polyethylene by in slurry in 60-90 ℃ temperature range, obtain at polymerization single polymerization monomer under the pressure of 0.15-1MPa and in the presence of the high-mileage ziegler catalyst that constitutes as organo-aluminium compound by transistion metal compound and triethyl aluminum.Polyreaction is carried out in three stages, i.e. in the stage of three serial arrangement, each molecular weight is regulated by means of the hydrogen charging.
Polyethylene composition of the present invention can comprise other additive and polyethylene side by side.The example of these additives has thermo-stabilizer, antioxidant, UV absorption agent, photostabilizer, metal passivator destroys the compound of superoxide and consumption in 0-10% weight, preferably at the alkaline auxiliary stablizer of 0-5% weight, and filler, toughener, softening agent, lubricant, emulsifying agent, pigment, optical brightener, fire retardant, static inhibitor, whipping agent, or their combination, total amount is a 0-50% weight, based on the gross weight of mixture.
Composition of the present invention is particularly suitable for blow molding process producing the L-ring drums, by at first plastifying polyethylene composition and then be expressed in the mould by die head in forcing machine in 200-250 ℃ temperature range, blows at this and to be cooled then and to solidify.
Composition of the present invention is in the special good processing properties of blow molding process generation that is used for producing the L-ring drums, because it has the swelling ratio in the 180-220% scope, the L-ring drums of Sheng Chaning has extra high physical strength thus, because moulding compound of the present invention has at 60-90KJ/m
2Notched Izod impact strength (ISO) in the scope.Its stress cracking resistance (FNCT) is in the scope of 15-25h.
Notched Izod impact strength (ISO) according to ISO 179-1/leA/DIN 53453 23 ℃ of mensuration.Specimen size is that 10 * 4 * 80mm and V breach use 45 ℃ of angles to insert, and the degree of depth is that 2mm and breach base radius are 0.25mm.
The stress cracking resistance of moulding compound of the present invention is determined by internal test method and is provided with hour (h).This laboratory method by M.Fleissner at Kunststoffe 77 (1987), the 45th and subsequently page or leaf describe and corresponding to ISO/CD 16770, the latter enters into force.The disclosure text display in creep test, measure determining of crack growth slowly to the sample that has circumferential notch and carry out according to ISO1167 long-term in and the fragility cross section of hydrostatic pressure test between exist and concern.As the medium that promotes stress cracking and when using the tensile stress of 3.5MPa down for 80 ℃, rupture time shortens because the stress time of causing is shortened by breach (1.6mm/ blade) at ethylene glycol.Sample is by producing from following three samples that are of a size of 10 * 10mm * 110mm of the thick compacting bladed saw of 10mm.These samples are being made a center breach (seeing Fig. 5 in the open text) for this purpose and on the special blanking units with blade.Notch depth is 1.6mm.
Work embodiment
Be arranged in series three reactors in ethene continuous processing polymerization.As WO 91/18934, the Z-type catalyst of the 5.5mmol/h of embodiment 2 described preparations amount, but operand is 2.2 in WO, is added in first reactor with thinner (hexane), ethene and the hydrogen of 150mmol/h triethyl aluminum and capacity.Adjust ethene amount (=49.4kg/h) and the amount (18g/h) of hydrogen so that the percentage of ethene of measuring in the gas phase of first reactor and hydrogen is respectively 49% volume and 43% volume, remaining is the mixture of the thinner of nitrogen and evaporation.
Polyreaction in first reactor is carried out at 73 ℃.
Then the slurry in first reactor is transferred in second reactor, wherein the per-cent of hydrogen has been reduced to 20% volume in the gas phase, and the 1-butylene of 15g/h joins in this reactor with the ethene of 46.9kg/h.The amount of hydrogen is by intermediary H
2Depressurization and reducing.In the gas phase of second reactor, be measured to 72% volume of ethylene, 20% volume of hydrogen and＜0.1% volume 1-butylene, remaining is the mixture of the thinner of nitrogen and evaporation.
Polyreaction in second reactor is carried out at 85 ℃.
Slurry in second reactor is transferred in the 3rd reactor, used further middle H2 depressurization to adjust the amount of hydrogen in the gas phase of the 3rd reactor less than 0.1% volume.
The 1-butylene of 90g/h and the ethene of 27.2kg/h are added in the 3rd reactor together.In the gas phase of the 3rd reactor, be measured to 91% volume of ethylene, less than the per-cent of 0.1% volume of hydrogen and 0.22% volume 1-butylene, remaining is the mixture of the thinner of nitrogen and evaporation.
Polyreaction in the 3rd reactor is carried out at 76 ℃.
The desired long-term polymerisation catalysts activity of above-mentioned Cascading Methods provides by the Z-type catalyst of the described specific development of beginning among the WO.Measuring of this catalyzer availability is its extra high hydrogen-sensitivity and 1-8 hour for a long time even high reactivity.
From the polymer slurries that leaves the 3rd reactor, remove thinner, with the granulation then of polymkeric substance drying.
Below shown in table 1 provided viscosity number and the quantitative ratio w of polymer A, B and C in the polyethylene composition of embodiment 1 preparation
A, w
B, and w
c
Table 1
| Embodiment | |
| Density [g/cm 3] | 0.953 |
| ?MFR 190/21，6[dg/min] | 2.6 |
| ?W A[% weight] | 40 |
| ?W B[% weight] | 38 |
| Wc[% weight] | 22 |
| ?VN 1[cm 3/g] | 210 |
| ?VN 2[cm 3/g] | 260 |
| ?VN tot[cm 3/g] | 540 |
| ?SR[％] | 200 |
| ?FNCT[h] | 17.5 |
| ?NIS ISO[kJ/m 2] | 80 |
The physical properties abbreviation has following meaning in the table 1:
-SR (=swelling ratio) is with [%] expression, at 190 ℃ and shearing rate 1440S
-1Measure in the high pressure capillary rheometer in the 2/2 rounded section die head that has conical entrance (angle=15 ℃) down.
-FNCT=represents with [h] with the stress cracking resistance (full notch creep test) of the close beta method test of M.Fleissner.
-NIS
ISO=notched Izod impact strength, according to described in the ISO 179-1/leA/DIN 53453 23 ℃ of mensuration, with [kJ/m
2] expression.
Claims (10)
1. polyethylene composition with multimodal shape molecular weight distribution has at 23 ℃ and is 0.950-0.956g/cm
3Density and the MFR in the 1.5-3.5dg/min scope in the scope
190/21.6The low-molecular-weight ethylenic homopolymer A that comprises 35-45% weight, the high molecular weight copolymer B that makes by ethene and another kind of 1-alkene of 34-44% weight and 18-26% weight with 4-8 carbon atom have the ultrahigh molecular weight copolymer C that the 1-alkene of 4-8 carbon atom is made by ethene and another kind, wherein all percent value are based on the gross weight of composition.
2. polyethylene composition as claimed in claim 1, wherein high molecular weight copolymer B contain based on the weight meter of multipolymer B less than the comonomer with 4-8 carbon atom of the low ratio of 0.1% weight and wherein the ethylene copolymer C of ultra-high molecular weight contain based on the comonomer in the weight meter 0.1-0.6% weight range of multipolymer C.
3. as the polyethylene composition of claim 1 or 2, it contains 1-butylene as comonomer, 1-amylene, 1-hexene, 1-octene, 4-methyl-1-pentene, or the mixture of these comonomers.
4. as the polyethylene composition of claim 1 or 2, the viscosity number VN that has
TotBe 500-600cm
3/ g, according to ISO/R 1191 in naphthalane 135 ℃ of measurements.
5. as the polyethylene composition of claim 1 or 2, it has the swelling ratio in the 180-220% scope, at 60-90KJ/m
2Notched Izod impact strength and the stress cracking resistance in the 15-25h scope in the scope.
6. produce method as each polyethylene composition among the claim 1-5, wherein monomer in slurry in 60-90 ℃ temperature range, under the pressure of 0.15-1.0MPa scope, with polymerization in the presence of the high-mileage ziegler catalyst that constitutes by transistion metal compound and organo-aluminium compound, this method comprises carries out polyreaction in three stages, and wherein the poly molecular weight for preparing in each stage is regulated by means of hydrogen.
7. method as claimed in claim 6, the concentration of wherein regulating hydrogen in first polymerization stage is so that the viscosity number VN of low molecular weight polyethylene A
1At 160-220cm
3In/g the scope.
8. as the method for claim 6 or 7, the concentration of wherein regulating hydrogen in second polymerization stage is so that the viscosity number VN of the mixture of polymer A and polymer B
2At 230-320cm
3In/g the scope.
9. as the method for claim 6 or 7, the concentration of wherein regulating trimerization hydrogen in the stage is so that the viscosity number VN of the mixture of polymer A, polymer B and polymkeric substance C
3At 500-600cm
3In/g the scope.
10. be used for the production capacity at 50-250dm as each polyethylene composition among the claim 1-5
3The purposes of the L-ring drums in the scope wherein at first plastifies polyethylene composition and then is expressed in the mould by die head in 200-250 ℃ temperature range in forcing machine, blow at this to be cooled then and to solidify.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10261064A DE10261064A1 (en) | 2002-12-24 | 2002-12-24 | Polyethylene molding composition with multimodal molecular weight distribution, used for making large blow-molded L-ring containers, contains low-molecular homopolyethylene and high- and ultrahigh-molecular copolyethylenes |
| DE10261064.9 | 2002-12-24 | ||
| US60/445,165 | 2003-02-05 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1729249A CN1729249A (en) | 2006-02-01 |
| CN100363414C true CN100363414C (en) | 2008-01-23 |
Family
ID=32478007
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2003801072971A Expired - Lifetime CN100363414C (en) | 2002-12-24 | 2003-12-10 | Polyethylene composition for producing L-ring drums |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN100363414C (en) |
| AR (1) | AR042813A1 (en) |
| DE (1) | DE10261064A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ATE497992T1 (en) * | 2006-12-22 | 2011-02-15 | Basell Polyolefine Gmbh | MULTIMODAL POLYETHYLENE COMPOSITION, MIXED CATALYSAOTR AND METHOD FOR PREPARING THE COMPOSITION |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4336352A (en) * | 1979-08-24 | 1982-06-22 | Asahi Kasei Kogyo Kabushiki Kaisha | Blend of three ethylene polymers |
| US4536550A (en) * | 1983-04-21 | 1985-08-20 | Asahi Kasei Kogyo Kabushiki Kaisha | Polyethylene composition |
| CN1376170A (en) * | 1999-09-24 | 2002-10-23 | 巴塞尔聚烯烃有限公司 | Polyethylene moulding compound with an improved ESCR/stiffness relation and an improved swelling rate, a method for the production and the use thereof |
-
2002
- 2002-12-24 DE DE10261064A patent/DE10261064A1/en not_active Withdrawn
-
2003
- 2003-12-10 CN CNB2003801072971A patent/CN100363414C/en not_active Expired - Lifetime
- 2003-12-23 AR ARP030104828A patent/AR042813A1/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4336352A (en) * | 1979-08-24 | 1982-06-22 | Asahi Kasei Kogyo Kabushiki Kaisha | Blend of three ethylene polymers |
| US4536550A (en) * | 1983-04-21 | 1985-08-20 | Asahi Kasei Kogyo Kabushiki Kaisha | Polyethylene composition |
| CN1376170A (en) * | 1999-09-24 | 2002-10-23 | 巴塞尔聚烯烃有限公司 | Polyethylene moulding compound with an improved ESCR/stiffness relation and an improved swelling rate, a method for the production and the use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| DE10261064A1 (en) | 2004-07-08 |
| CN1729249A (en) | 2006-02-01 |
| AR042813A1 (en) | 2005-07-06 |
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