CN100363413C - Polyethylene blow moulding composition for producing jerry cans - Google Patents
Polyethylene blow moulding composition for producing jerry cans Download PDFInfo
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- CN100363413C CN100363413C CNB2003801072863A CN200380107286A CN100363413C CN 100363413 C CN100363413 C CN 100363413C CN B2003801072863 A CNB2003801072863 A CN B2003801072863A CN 200380107286 A CN200380107286 A CN 200380107286A CN 100363413 C CN100363413 C CN 100363413C
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- 239000000203 mixture Substances 0.000 title claims abstract description 37
- -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
- 238000000071 blow moulding Methods 0.000 title abstract description 6
- 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 14
- 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
- 238000000465 moulding Methods 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 7
- 238000005336 cracking Methods 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
- 239000000206 moulding compound Substances 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- 239000000126 substance Substances 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
- 150000001336 alkenes Chemical class 0.000 abstract description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000007664 blowing Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 238000006243 chemical reaction 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
- 238000002360 preparation method Methods 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000002902 bimodal effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 240000004859 Gamochaeta purpurea Species 0.000 description 1
- 239000004705 High-molecular-weight polyethylene Substances 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
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000000996 additive effect Effects 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
- 230000006378 damage 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
- 239000003112 inhibitor Substances 0.000 description 1
- 238000011005 laboratory method Methods 0.000 description 1
- 230000007774 longterm Effects 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
- 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
- 150000003609 titanium compounds Chemical class 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
Classifications
-
- 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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/06—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type
- C08F297/08—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-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
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/06—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type
- C08F297/08—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins
- C08F297/083—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins the monomers being ethylene or propylene
- C08F297/086—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins the monomers being ethylene or propylene the block polymer contains at least three blocks
-
- 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
- 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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2314/00—Polymer mixtures characterised by way of preparation
- C08L2314/02—Ziegler natta catalyst
Abstract
The invention relates to a polyethylene composition with multimodal molecular mass distribution, which is particularly suitable for the blow moulding of canisters having a volume in the range of from 2 to 20 dm<SUP>3 </SUP>(I). The composition has a density in the range from 0.950 to 0.958 g/cm<SUP>3 </SUP>at 23 DEG C. and an MFR<SUB>190/5 </SUB>in the range of from 0.30 to 0.50 dg/min. It comprises from 40 to 50% by weight of a low-molecular-mass ethylene homopolymer A, from 25 to 35% by weight of a high-molecular-mass copolymer B made from ethylene and from another olefin having from 4 to 8 carbon atoms, and from 24 to 28% 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 the blowing capacity at 2-20dm
3(1) bucket (jerry can of scope, jerry can), with relate to the method for preparing this polyethylene composition, be in the presence of the catalyst system of forming by Z-type catalyst and promotor, to be undertaken by the polystep reaction method of forming by the successive slurry polymerization.The invention still further relates to the bucket of producing by blowing by moulding compound.
Polyethylene is widely used for the production requirement material and has extra high physical strength, high erosion resistance and various types of blowing product 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 the poly blow molding composition with bimodal shape molecular weight distribution, and is suitable for producing the moulded work with good mechanical properties.
US-A5,338,589 have described and have a kind ofly had 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 in moulded work, particularly use this material to allow to improve simultaneously the character of oppositely being correlated with usually in pipe in the hypocrystalline thermoplastics, these particularly are stiffness and creep 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 owing to melt from upper area 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 the production bucket.Especially, the high fondant-strength of moulding compound should allow to operate expressing technique for a long time and not have parison destruction and the accurate composition swelling ratio of adjusting should allow the optimization of wall thickness control.
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 40-50% weight, the high molecular weight copolymer B that is made by ethene and another kind of 1-alkene with 4-8 carbon atom of 25-35% weight and the ultra-high-molecular-weight polyethylene-1-olefin copolymer C of 24-28% weight, wherein all percent value are based on the gross weight of composition.
The invention still further relates to slurry polymerization with cascade prepares this method for compositions and relates to thus composition and make capacity at 2-20dm
3(1) method of scope and bucket with quite excellent mechanical intensive property.
It is 0.950-0.958g/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, i.e. 0.2-0.5% 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 1-2% weight range.
The melt-flow index ISO1133 that composition of the present invention has is in the scope of 0.3-0.5dg/min, with MFR
190/5Expression and viscosity number VN
TotAt 330-380cm
3In the scope of/g, particularly at 340-370cm
3In/g the scope, according to ISO/R 1191 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/R 1191.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 60-80cm 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 160-200cm
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 in the trimerization step of reaction, forms
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 330-380cm
3In the scope of/g, particularly at 350-370cm
3In the scope of/g.
Polyethylene by in slurry in 70-90 ℃ scope, in the preferred 80-90 ℃ of scope, at polymerization single polymerization monomer under the pressure of 0.15-1MPa and in the presence of the high-mileage ziegler catalyst that constitutes by transistion metal compound and organo-aluminium compound such as triethyl aluminum, triisobutyl aluminium, alkyl aluminum chloride and alkyl-al hydride and obtain.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 bucket, by at first plastifying polyethylene composition and then be expressed in the mould by die head in forcing machine in 200-250 ℃ of scope, is cooled and solidifies at this.
Composition of the present invention is in the special good processing properties of blow molding process generation that is used for producing bucket, because it has the swelling ratio in the 130-145% scope, the bucket of producing thus has extra high physical strength, because moulding compound of the present invention has at 14-17KJ/m
2Notched Izod impact strength (ISO) in the scope.Its stress cracking resistance (FNCT) is in the scope of 150-220h.
Notched Izod impact strength (ISO) according to ISO 179-1/1eA/DIN 53453 23 ℃ of mensuration.Specimen size is that 10 * 4 * 80mm and V breach use 45 to insert, and the degree of depth is 2mm and breach base radius for O.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/FDIS 16770, the latter enters into force.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 * 90mm 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.
Embodiment 1
Be arranged in series three reactors in ethene continuous processing polymerization.As WO 91/18934, embodiment 2 described preparations be the Z-type catalyst of 1.3mol/h amount with respect to titanium compound, but operand is 2.2 in WO, is added in first reactor with thinner (hexane), ethene and the hydrogen of 2.7mol/h triethyl aluminum and capacity.Adjust ethene amount (=6.75t/h) and the amount (7.3kg/h) of hydrogen so that the percentage of ethene of measuring in the gas phase of first reactor and hydrogen is respectively 18% volume and 70% volume, remaining is the mixture of the thinner of nitrogen and evaporation.
Polyreaction in first reactor is carried out at 84 ℃.
Then the slurry in first reactor is transferred in second reactor, wherein the per-cent of hydrogen has been reduced to the 10-12% volume in the gas phase, and the 1-butylene of 16.6kg/h joins in this reactor with the ethene of 4.35t/h.The amount of hydrogen is by intermediary H
2Depressurization and reducing.Be measured to 70% volume of ethylene, 10.5% volume of hydrogen and 1.1% volume 1-butylene in the gas phase of second reactor, remaining is the mixture of the thinner of nitrogen and evaporation.
Polyreaction in second reactor is carried out at 82 ℃.
Slurry in second reactor is transferred in the 3rd reactor, with further middle H
2Depressurization is adjusted the amount of hydrogen in the gas phase of the 3rd reactor to 0.5% volume.
The 1-butylene of 67kg/h and the ethene of 3.90t/h are added in the 3rd reactor together.Be measured to the per-cent of 85% volume of ethylene, 0.5% volume of hydrogen and 2.2% volume 1-butylene in the gas phase of the 3rd reactor, residue is the mixture of the thinner of nitrogen and evaporation.
Polyreaction in the 3rd reactor is carried out at 80 ℃.
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 material drying.
Below shown in table 1 provided viscosity number and the quantitative ratio w of polymer A, B and C in the polyethylene molding composition of embodiment 1 preparation
A, w
B, and w
c
Table 1
| Embodiment number | 1 |
| Density [g/cm 3] | 0.954 |
| MFR 190/5[dg/min] | 0.40 |
| W A[% weight] | 45 |
| W B[% weight] | 29 |
| W C[% weight] | 26 |
| VN 1[cm 3/g] | 70 |
| VN 2[cm 3/g] | 180 |
| VN tot[cm 3/g] | 360 |
| SR[％] | 135 |
| FNCT[h] | 170 |
| NIS ISO[kJ/m 2] | 16 |
The physical properties abbreviation has following meaning in the table 1:
-SR (=swelling ratio) is with [%] expression, at 190 ℃ and shearing rate 1440S
-1In the high pressure capillary rheometer of the 2/2 rounded section die head that has conical entrance (angle=15 °), measure 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 179-1/1eA/DIN 53453 23 ℃ of mensuration, with [kJ/m
2] expression.
Claims (10)
1. polyethylene molding composition with multimodal shape molecular weight distribution has at 23 ℃ and is 0.950-0.958g/cm
3Density and the MFR in the 0.30-0.50dg/min scope in the scope
190/5It comprises the low-molecular-weight ethylenic homopolymer A of 40-50% weight, the high molecular weight copolymer B that makes by ethene and another kind of 1-alkene of 25-35% weight and 24-28% 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 moulding compound.
2. polyethylene molding composition as claimed in claim 1, wherein high molecular weight copolymer B contain based on the comonomer with 4-8 carbon atom of the low ratio of the weight meter 0.2-0.5% weight of multipolymer B and wherein the ethylene copolymer C of ultra-high molecular weight contain based on the comonomer in the weight meter 1-2% weight range of multipolymer C.
3. as the polyethylene molding 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 molding composition of claim 1 or 2, the viscosity number VN that has
TotBe 330-380cm
3/ g, according to ISO/R 1191 in naphthalane 135 ℃ of measurements.
5. as the polyethylene molding composition of claim 1 or 2, it has the swelling ratio in the 130-145% scope, at 14-17KJ/m
2Notched Izod impact strength and the stress cracking resistance in the 150-220h scope in the scope.
6. produce method as each polyethylene molding composition among the claim 1-5, wherein monomer in slurry in 20-120 ℃ temperature range, under the pressure of 0.15-1MPa 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 60-80cm
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 160-200cm
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 330-380cm
3In/g the scope.
10. be used for the production capacity at 2-20dm as each polyethylene molding composition among the claim 1-5
3The purposes of the bucket in the scope wherein at first plastifies polyethylene composition and then is expressed in the mould by die head in 200-250 ℃ of scope in forcing machine, at first blow at this to be cooled then and to solidify.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10261066.5 | 2002-12-24 | ||
| DE10261066A DE10261066A1 (en) | 2002-12-24 | 2002-12-24 | Polyethylene molding composition with multimodal molecular weight distribution, used for making blow-molded cans, contains low-molecular homo polyethylene and high- and ultrahigh-molecular co polyethylenes |
| US60/445,163 | 2003-02-05 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1729248A CN1729248A (en) | 2006-02-01 |
| CN100363413C true CN100363413C (en) | 2008-01-23 |
Family
ID=32478009
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2003801072863A Expired - Lifetime CN100363413C (en) | 2002-12-24 | 2003-12-06 | Polyethylene blow moulding composition for producing jerry cans |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN100363413C (en) |
| AR (1) | AR042814A1 (en) |
| DE (2) | DE10261066A1 (en) |
Families Citing this family (2)
| 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 |
| US9493590B2 (en) * | 2009-11-20 | 2016-11-15 | Basell Polyolefine Gmbh | Trimodal polyethylene for use in blow moulding |
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 DE10261066A patent/DE10261066A1/en not_active Withdrawn
-
2003
- 2003-12-06 CN CNB2003801072863A patent/CN100363413C/en not_active Expired - Lifetime
- 2003-12-06 DE DE60306814T patent/DE60306814T2/en not_active Expired - Lifetime
- 2003-12-23 AR ARP030104829A patent/AR042814A1/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 |
|---|---|
| AR042814A1 (en) | 2005-07-06 |
| DE10261066A1 (en) | 2004-07-08 |
| CN1729248A (en) | 2006-02-01 |
| DE60306814D1 (en) | 2006-08-24 |
| DE60306814T2 (en) | 2007-02-22 |
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| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
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Granted publication date: 20080123 |