CN1950445A - Polymer molding compositions - Google Patents

Abstract

The invention relates to formulated compositions which can be easily formed into bottle caps, without the need for a liner, while still maintaining pressure requirements, such as for carbonated beverages. The compositions may include an ethylene polymer having a density in the range of from about 0.947 to 0.962 g/cm<3>, a melt index of from about 1 to about 10 g/10 min., and another ethylene polymer having a density in the range of from about 0.912 to 0.932 g/cm<3>, a melt index of from about 0.25 to about 6 g/10 min., wherein the two ethylene polymers have a density difference of equal to or greater than 0.03 g/cm<3>. In other cases, the composition may include a single component resin with a density in the 0.935 - 0.955 g/cm<3> range with a melt index in the range of 0.3 - 1.2 g/10minutes, and wherein the resin comprises a polyethylene polymer.

Description

Polymer molding compositions

The mutual reference of related application

[0001] the application requires in the U.S. Provisional Patent Application No.60/568 of submission on May 6th, 2004,487 priority according to 35U.S.C. § 119 (e). All introduce this application as a reference at this.

The background technology of invention

The field of invention

[0002] the present invention relates generally to have the polymer composition of the character that requires. More specifically, embodiment of the present invention relate to the closure member that is comprised of polyethylene resin composition.

The background technology of invention

[0003] the present invention relates generally to can be used for the polymer molding compositions that molding is used, and be particularly useful for the application of threaded closure. For threaded closure, such as anker cap, so that good sealing to be provided, this bottle cap closure member has the liner that is comprised of soft Ethylene/vinyl acetate (EVA), PVC, SEBS, TPV or butyl rubber etc. to normal operation polypropylene (PP) polymer as the bottle cap closure member of desirable strength. Yet these two modular constructions are expensive, and the user always seeks the method for dealing with problems with low cost. Use whole closure member and be easier and more easily without liner. Yet such scheme is difficult, is enough to bear the needed intensity of this closure member because this bottle cap closure member must have, and enough soft so that good sealing to be provided, and does not pollute taste or the smell of this bottle content simultaneously. Specifically, except good mobile torque and peel off that torque needs and good color, this bottle cap closure member must keep the pressure of content and have good anti-stress fracture and impact strength.

[0004] along with the appearance of PET (PET) pop bottle, developed polypropylene (PP) bottle cap resin to satisfy the described bottle needs that damage the closure member of (tamper proof) and cheapness easy to use, anti-. This closure member is the form of lid, and this lid is installed to the bottom to have on the bottle that tears label or the anti-infringement of safety collar conduct feature off. Although present PP closure member is cheap, to such an extent as to they itself can not form the gas-tight seal of bottle too firmly. Therefore, in the secondary operation, ethylene vinyl acetate (EVA) copolymer or other liner are attached to the inboard of PP lid as sealant. This provides soft polymeric seal so that airtight closure member to be provided. This closure member or lid structure can work preferably, but because these two modular constructions, its production is expensive. Therefore, need to continue new polymer scheme to satisfy or also to make more cheaply above the industrial needs of closure member. This is applicable to pressurization and non-pressurized container.

[0005] in the process of making great efforts this closure member problem of solution, many examples that can be used for the polymer composition of molding application are arranged, comprise the blend of LLDPE (LLDPE) and high density polyethylene (HDPE) (HDPE). For example, United States Patent (USP) 5,981,664 is incorporated herein its disclosure as a reference, discloses the resin combination that is used for molding, and it comprises that 40-65%'s has a density 0.948/cm³To 0.964g/cm³, melt flow index 6 to 20g/10 minutes and mean mol distribute (Mw/Mn) be 2 to 5 ethene polymers, and 35-60%'s has a density 0.935g/cm³To 0.953g/cm³, melt flow index 0.1 is to the distribute ethene polymers of (Mw/Mn) 6 to 20 of 0.35g/10 minute and mean mol, wherein final composition has 0.948g/cm³To 0.957g/cm³Density, 1.0 mean mols to 2.0g/10 minute melt flow indexes and 3 to 10 distribute (Mw/Mn), and wherein the density contrast of these two components is 0 to 0.029g/cm³ Think that above-mentioned composition can be used for threaded closure.

[0006] yet, still having needs to be molded as the polymer formulators with satisfactory quality closure member, as not needing liner, acceptable taste and smell and satisfied anti-stress fracture and impact strength.

The concise and to the point description of invention

[0007] on the one hand, the present invention relates to ethylene polymer composition, it can be used for replacing polypropylene/ethylene-vinyl acetate (EVA) two modular constructions in the prior art bottle cap is used in certain embodiments, and need not liner. In selected embodiment, said composition has in 100%Igepal＞80 hours environmental stress crack resistance (ESCR) (according to ASTM D-1693 condition B test), when according to ASTM D-4976 preparation and test, have 3000 tensile yields (tensile yield) of arriving 3400psi according to ASTM D-638, but keep enough soft to seal this bottle, therefore do not have the gas effusion and satisfy the needs that this lid machine is opened torque (turn-on turque) or peeled off torque (strip torque).

[0008] on the one hand, the present invention relates to a kind of composition, it comprises the resin of one pack system, and this resin has 0.935-0.955g/cm³Density and 0.3-1.2g/10 minute melt index (MI), and wherein this resin comprises polyethylene polymer.

[0009] on the one hand, the present invention relates to a kind of composition, it comprises about 10 ethene polymers to about 90 % by weight, and this ethene polymers has about 0.947 to 0.962g/cm³Density, about 1 to about 10g/10 minute melt index (MI); With about 90 ethene polymers to about 10 % by weight, this ethene polymers has about 0.912 to 0.932g/cm³Density, about 0.25 to about 6g/10 minute melt index (MI); Wherein component (A) and density contrast (B) (Δ D=D (A)-D (B)) are equal to or greater than 0.03g/cm³。

[0010] on the one hand, the present invention relates to a kind of at least a polyvinyl closure member that comprises, described polyvinyl be characterised in that to have be equal to or greater than about 8% until about 25% short-chain branch distribution content value.

[0011] on the one hand, the present invention relates to a kind of method that forms closure member, the method comprises that the composition of modification claim 1 or 7 is to form closure member.

[0012] other aspect and advantage of the present invention can be found out from following specification and claim significantly.

The detailed description of invention

[0013] just as discussed above, embodiment of the present invention relate to the ethylene polymer composition with selected character. In the application of selecting, composition has in 100%Igepal＞80 hours environmental stress crack resistance (ESCR) and the tensile yield of (according to ASTM D-1693 condition B test) 3000 to 3400psi according to embodiments of the present invention, when according to ASTM D-4976 preparation and test according to ASTM D-638, therefore do not have gas to overflow but it keeps enough soft to seal this bottle, and satisfy this lid machine and open the needs of torque or peel off torque.

[0014] as used herein, peel off torque and be defined as: machine can put on this bottle cap and the torque of not peeling off supporting surface (tread) is measured. Also require to be moved by the consumer easily. This generally is defined as mobile torque. Has in addition CO₂The thermal cycle of confining force is that outstanding (speed bumps) (it can or can use) of this cover design, line strength (modulus) and speed limit is conclusive, and described speed limit is outstanding to prevent that lid from jumping out of suddenly bottle. For can with solvent, moisture, UV-solidifies or other ink printing, the lid of gained should be able to be processed 55 dyne. Under the pressure of about 60psi, this depends on temperature to the content of general fizz at about 30psi.

[0015] carbonated drink manufacturer usually injects and has carbon dioxide pressurized cold liquid, then pours into beverage with bottle under high pressure. This is because the geothermal liquid that adds that cold flowing fluid ratio does not under high pressure pressurize is compared the more gases of dissolving. In above-mentioned beverage bubble not only provide simply fizz, and change the flavour of beverage. Carbon dioxide in carbonated drink forms carbonic acid, and it reduces the sweet taste of beverage. Therefore, flat carbonated drink often taste than sweeter when its filling CO 2. This carbon dioxide not only changes flavour and mouthfeel, and antimicrobial purpose is provided. Show that it also helps prevent some microorganisms to grow in mouth. Every kind of Soda Water comprises the carbon dioxide of different amounts, so it has the pressure of change amount. On an average, 12 ounces of air hydraulic cylinders selling at US have the roughly pressure of 120kPa (17.4psi) when at 4 ℃ of lower seals, and have the pressure of 250kPa (36.3psi) when 20 ℃ of lower storages.

An application of the vinyl composition that [0016] forms according to an embodiment of the present invention is that they can form bottle cap, for example aforesaid pop bottle.

[0017] extrusion process that has a surface (it can damage the outward appearance of bottle cap) of satisfied power tractive force (motor load), inlet pressure, specific output rating and immaculate and melt fracture also is that important character is to form polymer or to obtain by adding various auxiliary agents.

[0018] general, the character of two kinds of polyblend deposits yields is not as the character of independent component or two constitutive property linear interpolations. Yet, surprisingly, in embodiments of the invention, the inventor finds by selecting carefully blend component, can obtain basically improved ESCR character in using required tensile yield scope and has no to lose other important performance characteristics.

[0019] lid that uses according to embodiments of the present invention composition compression moulding to produce has good balance of properties, reduces simultaneously the cost of producer. The flexibility of blend is given the good lid sealability that satisfies standard. Therefore, use the embodiment of the present invention of the blend of component as described below advantageously to show, effectiveness and cost savings are all above the resin that usually uses in bottle cap is used. Can also the injection moulding said composition.

[0020] blend of this resin Composition can be with well known to a person skilled in the art that any mode finishes. For example, blend can be finished by be dry mixed two components at extruder. Perhaps, this polymer composition can be produced with multiple reactor and/or multi-catalyst. This can easily realize and not have incompatibility problem.

[0021] inventor has been found that the polymer composition that is suitable for the molding threaded closure, and it has good taste and adour properties and enough proof stress disruptiveness and impact strengths. Above-mentioned threaded closure when it is made by the present composition, does not need liner. These compositions are take thermoplastic polymer as basis, especially ethene polymers. These polymer compositions of the first comprise:

[0022] (A) about 10 to the ethene polymers of about 90 % by weight, it has about 0.947 to about 0.962g/cm³Density, about 1 to about 10g/10 minute, preferred about 2 to about 8g/10 minute (g/10min), 3 melt index (MI)s that arrive about 7g/10min more preferably from about;

[0023] (B) about 90 to the ethene polymers of about 10 % by weight, it has about 0.912 to about 0.932g/cm³Density, arrived the melt index (MI) of about 3g/10min in about 0.25 to about 6g/10 minute, preferred about 0.5 to about 4g/10min, more preferably from about 0.75; With

[0024] (C) additive of 0 to 6 % by weight, this additive is selected from color improvement agent, lubricant, filler, pigment, antioxidant and processing aid, and preferred scope is that 0.01 to 3 % by weight and most preferred scope are 0.015 to 0.5 % by weight;

[0025] wherein component (A) and density contrast (B) (Δ D=D (A)-D (B)) are equal to or greater than 0.03g/cm³。

[0026] in another embodiment, composition comprises and is characterised in that to have and is equal to or greater than about 8% until the ethene polymers of about 25% short-chain branch distribution content that preferred wherein this ethene polymers comprises the high density fraction less than about 80%.

[0027] in other embodiments, said composition preferably is characterised in that to have about 0.5 % by weight to the 1-hexene content of about 5 % by weight, and the preferred solvable fraction that has greater than about 1.75% (measuring by CRYSTAF) that is characterised in that.

[0028] in addition, owing to make simply, the one pack system resin combination is valuable. In second embodiment, disclose the second polymer composition that comprises the single polymer composition, it is suitable for the threaded closure that molding has good tensile property, good taste and adour properties and enough anti-stress fracture, impact strength and color especially. Above-mentioned threaded closure when being made by the present composition, does not need liner. These compositions are take thermoplastic polymer as basis, especially ethene polymers. The example of above-mentioned composition comprises:

[0029] (A) one pack system resin, it has 0.935-0.955g/cm³The density of scope, preferred 0.938-0.952 and 0.942-0.950g/cm most preferably³Density range, and 0.3-1.2g/10 min, preferred 0.4-1.1g/10min and the melt index (MI) of 0.5-1.0g/10min most preferably;

[0030] (B) additive of 0 to 6 % by weight, this additive is selected from color improvement agent, lubricant, filler, pigment, antioxidant and processing aid, and preferred scope is that 0.01 to 3 % by weight and most preferred scope are 0.015 to 0.5 % by weight.

[0031] in another embodiment, said composition comprises having and is equal to or greater than about 10% to the ethene polymers of about 24% short-chain branch distribution content that preferred wherein this ethene polymers comprises less than the high density fraction of about 60-85% and the purification of about 5-16%.

[0032] in other embodiments, preferred said composition is characterised in that to have about 0.5 % by weight to the 1-hexene content of about 5 % by weight, and more preferably is characterised in that the solvable fraction (measuring by CRYSTAF) that has greater than about 1.75%.

[0033] in embodiments of the invention, the closure member of being made by any polymer composition demonstrates good mobile torque, peels off torque and the skew of sliding, and can guarantee that sealing reaches 150psi. Mobile torque is concerning unclamp, open or remove the amount of necessary revolving force this closure member from this bottle. According to one embodiment of the invention, this closure member has the mobile torque of about 7 to 17 in-lbs. As mentioned above, peel off that torque is that machine can be applied to this bottle cap and the torque of not peeling off this supporting surface is measured.

[0034] according to one embodiment of the invention, the closure member of being made by any polymer composition demonstrates the torque of peeling off of about 20 to 50 in-lbs. Slipping agent content is introduced in this resin to obtain effectively to slide skew at about slipping agent of 500 to 3000ppm. General slipping agent is erucyl amide (Erucamide). This closure member can guarantee to seal the 150psi that reaches test purpose. Can also introduce the surface without melt fracture of processing aid to be provided for aesthetics or to print easily.

[0035] closure member of being made by any these polymer compositions, especially threaded closure is also within the scope of the invention.

[0036] those skilled in the art generally acknowledge, can use compound this resin of methods known in the art ((add any additive) together with regard to two polymer resins of blend, or blend adding one or more additives). The compound of component and additive can be realized with standard equipment complex well known by persons skilled in the art, include, but are not limited to: forward or reverse, intermeshing or the non-formula of intermeshing, have one, the double-screw mixer of two or more sections, the Melting pump that described double-screw mixer has various screw-rod structures and in-line arrangement promote this resin by template to granulate under water. Alternatively, the Banbury compounding machine (banbury compounder) that has the template that single screw extrusion machine and be used for granulates under water.

[0037] can in the two-stage reactor of series connection, produce the blending resin composition, by the catalyst charge pipe catalyst is put in the first reactor, wherein the mixture of resin and active catalyst is transferred to the second reactor the another kind of polymer of preparation and copolymer blended with from the first reactor on the spot in the second reactor from the first reactor. If requirement can be used plural reactor in this process. These reactors can be independently reactor or the stage in a reactor. This catalyst can have carrier, carrier-free or be the solution form before the reactor of packing into. This catalyst can add in this reaction system to promote smooth operation continuously to, but can be interrupted the of short duration time cycle so that change different batch of catalyst.

[0038] can in this reactor, introduce the gaseous material that uses in the method by recyclegas. This recyclegas is defined as admixture of gas, it comprises ethene itself or ethene and one or more alpha-olefins, preferably one or both alpha-olefins are as comonomer (require alpha-olefin in the first reactor cycles gas and choose wantonly in the second reactor cycles gas), with, randomly, one or more inert gas such as nitrogen (to supply the reactor pressure of requirement), unreactive hydrocarbons and hydrogen. α-alkene can be, for example, and propylene, 1-butylene, 1-hexene, 4-methyl-1-pentene and 1-octene. Alpha-olefin has at the most 12 carbon atoms, preferred 3 to 8 carbon atoms usually. This recyclegas can also be called air inlet or circulating air.

[0039] preferred comonomer combination is as follows:

[0040] first reactor the second reactor

[0041] 1-hexene 1-hexene

[0042] 1-butylene 1-hexene

[0043] 1-butylene 1-butylene

[0044] 1-hexene 1-butylene

[0045] it should be noted that, can in the first or second reactor, produce Alathon, if require preferred the second reactor. Very clear, the blend that usually mixes on the spot can be characterized by dual resin. Yet in some cases, the mean molecule quantity of two components of producing this blend is very approaching, does not namely have noticeable interruption in the molecular weight curve.

[0046] for multistage reactor system, can control by the corresponding productivity ratio of each reactor the ratio of each component. Can control successively the corresponding productivity ratio of each reactor by computer applied algorithm, productivity ratio (measuring by thermal balance) in this computer applied algorithm monitoring reaction device, then in order to satisfy the needs of productivity ratio, productivity ratio shunting and Catalyst Production power, control ethylene partial pressure and catalyst charge amount in each reactor.

[0047] can be in the single reactor system manufacture order component resin composition, by the catalyst charge pipe catalyst is packed in the reactor. This catalyst can have a carrier, carrier-free or before the reactor of packing in solution. This catalyst can add in the reaction system to promote smooth operation continuously to, but can be interrupted the of short duration time cycle so that change different batch of catalyst.

[0048] can the gaseous material that use in the method be incorporated in the reactor by recyclegas. This recyclegas is defined as admixture of gas, it comprise as the ethene of comonomer itself or ethene and one or more alpha-olefins, preferably with one or both alpha-olefins, with, randomly, one or more inert gases such as nitrogen (supplying the reactor pressure of requirement), unreactive hydrocarbons and hydrogen. Alpha-olefin can be, for example, and propylene, 1-butylene, 1-hexene, 4-methyl-1-pentene and 1-octene. Alpha-olefin has at the most 12 carbon atoms, preferred 3 to 8 carbon atoms usually. This recyclegas can also be called air inlet or circulating air.

Catalyst is described

[0049] catalyst system can illustrate with the magnesium of describing in the U.S. Patent No. 4,302,565/titanium catalyst system. All introduce this patent as a reference at this. Another catalyst system is the catalyst system that is formed parent and used with the slurries form by spray-drying. Above-mentioned catalyst Precursors for example, comprises titanium, magnesium and electron donor, and, randomly, aluminum halide. Then this parent is introduced in hydrocarbon medium such as the mineral oil so that the slurries form to be provided. This spray-dired catalyst is described in U.S. Patent No. 5,290, in 745, all introduces it as a reference at this. These catalyst systems can be called ziegler-natta catalyst systems.

[0050] catalyst system of general magnesium/titanium base can be described below: parent can have chemical formula Mg_dTi(OR) _eX _f(ED) _g, wherein R is aliphatic or aromatic hydrocarbon radical or the COR ' with 1 to 14 carbon atom, wherein R ' is aliphatic or the aromatic hydrocarbyl with 1 to 14 carbon atom; Each OR group can be identical or different; X is chlorine, bromine or iodine independently; ED is electron donor; D is 0.5 to 56; E is 0,1 or 2; F is 2 to 116; With g be 1.5d+2. It can be by titanium compound, magnesium compound and electron donor preparation. Spendable titanium compound has chemical formula Ti (OR) in these parents of preparation_eX _h, wherein R, X and e are as defined above; H is 1 to 4 integer; And e+h is 3 or 4. Some instantiations of titanium compound are TiCl₃、TiCl ₄、Ti(OC ₂H ₅) ₂Br ₂、Ti(OC ₆H ₅)Cl ₃、Ti(OCOCH ₃)Cl ₃, and Ti (OCOC₆H ₅)Cl ₃。TiCl ₃And TiCl₄It is preferred compound. This magnesium compound comprises magnesium halide such as MgCl₂、MgBr ₂And MgI₂ Anhydrous MgCl₂It is preferred compound. Every mole of titanium compound uses about 0.5 to 56, preferred about 1 to 10 mole magnesium compound.

[0051] this electron donor is organic lewis base, and preferably at about 0 ℃ of liquid that arrives under about 200 ℃ of temperature, wherein magnesium and titanium compound dissolve. This electron donor can be Arrcostab, aliphatic ketone, aliphatic amine, aliphatic alcohol, alkyl or cycloalkyl ether or its mixture of aliphatic or aromatic carboxylic acid, and each electron donor has 2 to 20 carbon atoms. Among these electron donors, preferably have alkyl and the cycloalkyl ethers of 2 to 20 carbon atoms; Dialkyl group, diaryl and alkylaryl ketone with 3 to 20 carbon atoms; Alkyl, alkoxyl and alkyl alkoxy ester with the alkyl with 2 to 20 carbon atoms and aryl carboxylic acid class. Most preferred electron donor is oxolane. The example of the electron donor that other is suitable is methyl formate, ethyl acetate, butyl acetate, ether, dioxane, two-n-propyl ether, butyl oxide, ethanol, 1-butanols, Ethyl formate, methyl acetate, ethyl anisate, ethylene carbonate, oxinane and ethyl propionate.

[0052] if the product of titanium compound and electron donor is provided to body with excess electrons at first, every mole of titanium compound of final reacting product comprises about 1 to about 20 moles electron donor, and preferred every mole of titanium compound about 1 is to about 10 moles electron donor.

[0053] this catalyst Precursors can in advance activation before changing into catalyst. The parent activator compound that uses in the pre-activation step of part can be the mixture of a kind of compound or two kinds of different compounds. Every kind of compound can have chemical formula M (Rn) X (3-n), and wherein M is Al or B; Each X is chlorine, bromine or iodine independently; Each R is the radical of saturated aliphatic alkyl with 1 to 14 carbon atom independently, and condition is that n is 1 to 3 when M is Al, and n is 0 to 1.5 when M is B. The example of R base is methyl, ethyl, normal-butyl, isobutyl group, n-hexyl and n-octyl. The example of n is 1,1.5,2 and 3 when M is aluminium. The example of n is 0,1 or 1.5 when M is boron. Preferred activator compound comprises diethylaluminum chloride, triethyl aluminum, tri-n-hexyl aluminum, chlorodimethylalumiu and tri-n-octylaluminium. Especially preferred activator compound is the order mixture of diethylaluminum chloride and tri-n-hexyl aluminum; The order mixture of diethylaluminum chloride and triethyl aluminum; With diethylaluminum chloride or tri-n-hexyl aluminum.

[0054] carried out the part activation of this parent before in this parent introducing reactor. The catalyst of this part activation can play polymerization catalyst, but greatly to reduce and commercial unsatisfied Catalyst Production power. For obtaining completely activation, require in polymer reactor, to finish activation by attaching co-catalyst.

[0055] in preferred mode (often being called online restoring system), this parent is introduced in the hydrocarbon solvent slurries supply tank; Then these slurries are passed through immediately the static mixer in activator injection port downstream, there, these slurries and activator mix; Then this mixture is passed immediately second static mixer in the second activator injection port downstream, there it and the second activator mix. Can vertically settle static mixer. Can provide satisfied mixing with the Kenics  static mixer of 2 feet (Unit 32). This low-energy blender by constantly in circular pattern along with pipe that this blender links to each other in flow to separated flow and reverse flow is always moved. The activator compound that depends on use reacts for the activator with catalyst Precursors chemical combination, may need some reaction time. This carries out with time of staying zone expediently, this zone can by the interpolation length of slurry feed pipe or basically plug flow holding vessel (plug flow holding vessel) form. Time of staying zone can be used for activator compound both, or be used for only a kind of, or all need not, this depends on the reaction rate between activator compound and catalyst Precursors fully.

[0056] then entire mixture is introduced in the reactor, in this case, the first reactor is finished activation with co-catalyst there. Usually under about 60 ℃ temperature, carry out the part activation, preferred about 30 to about 45 ℃ about 10. The mol ratio of every kind of parent activator compound and electron donor can be at about 0.1: 1 within about 0.6: 1 scope. Molecule and the denominator of this ratio represent respectively, the parent activator compound total amount of using in the method and electron donor total amount.

[0057] mol ratio of activator and titanium can arrive within about 8: 1 scope at about 0.1: 1, preferably arrives in about 5: 1 scope at about 1: 1. The hydrocarbon that is used for forming slurries can be any without gas and anhydrous aliphatic or aromatic hydrocarbon basically, it and catalyst Precursors composition and catalyst activator compound, catalyst Precursors, parent activator compound and co-catalyst Fails To Respond.

[0058] in practice, be used for the final use of packaging for foodstuff because find many final polymer products, so aromatic hydrocarbon not preferred slurries solvent. Although under suitable engineering design condition, can use low viscosity solvent such as isopentane, hexane and heptane as the slurries solvent, but the precipitation that hydrocarbon slurries solvent generally is selected from hydrogenation " mineral oil " or plants at feed pipe etc. with the minimum catalyst solid with respect to full-bodied cycloalkanes oils. Owing to use the slurries of low viscosity and easier precipitation to introduce the complexity of adding as catalyst, so these are not particularly preferred. The viscosity of hydrocarbon slurries solvent enough low so that these slurries can be expediently via pre-activating apparatus pumping and enter in the polymer reactor at last. Preferred solvent is viscosity greater than about 50 centipoises (cps), especially greater than about 100cps and less than about 5, the aliphatic hydrocarbon of 000cps. Especially preferred solvent is naphthenic mineral oil, and typical material is with trade name Kaydol by Witco^, the Kaydol series that provides of Hydrobrite 380 and Hydrobrite 550 food-grade mineral oil.

[0059] this co-catalyst, normally hydrocarbyl aluminium promoter can be used chemical formula R₃Al or R₂AlX represents that wherein each R is alkyl, cycloalkyl, aryl or hydrogen independently; At least one R is alkyl; And two or three R bases formation heterocycle structure that can link to each other. Each R is alkyl, can have 1 to 20 carbon atom and preferably have 1 to 10 carbon atom. X is halogen, preferred chlorine, bromine or iodine. The example of hydrocarbyl aluminium compound is as follows: triisobutyl aluminium, tri-n-hexyl aluminum, diisobutyl-alanate, dihexyl alanate, diisobutyl-hexyl aluminium, isobutyl group dihexyl aluminium, trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, triisopropylaluminiuand, three n-butylaluminum, trioctylaluminum, three decyl aluminium, three (12) alkyl aluminum, tribenzyl aluminium, triphenyl aluminum, three naphthyl aluminium, trimethylphenyl aluminium, chlorination dibutyl aluminium, diethylaluminum chloride, di-isobutyl aluminum chloride and ethylaluminium sesquichloride. Introduce co-catalyst so that the Al that arrived about 100: 1 interpolation in about 10: 1 to be provided with enough amounts: the Ti atomic ratio, and be preferably greater than about 20: 1 to about 50: 1 Al: Ti. This amount can be finished the activation of parent.

[0060] preferably do not use carrier. Yet in wishing those situations of this parent of load, silica is preferred carrier. Other suitable carrier is inorganic oxide such as aluminum phosphate, alumina, silica/bauxite mixtures, with the silica of organo-aluminum compound such as triethyl aluminum modification with the silica of diethyl zinc modification. General carrier is basically to solid, particle, the porous material of polymerization inertia. It uses with the form of xeraphium, and this xeraphium has about 10 to about 250 microns and preferred about 30 to about 100 microns particle mean size; At least 200 meters squared per gram and preferred surface area at least about 250 meters squared per gram; With at least about 100 dusts with preferably at least about the pore size of 200 dusts. Usually, the carrier amount of use is that every gram carrier provides about 0.1 to about 1.0 mMs of titaniums, and preferred every gram carrier provides about 0.4 to about 0.9 mM of titanium.

[0061] can be by in electron donating solvent or other solvent, mixing this parent and silica gel, going down to desolventize at the pressure that reduces above-mentioned catalyst Precursors is impregnated in the silica supports subsequently. Then it the solid catalyst of gained is become free-pouring slurries with aforesaid aliphatic hydrocarbon so that can be pumped in this process with the form of liquid. Be described in United States Patent (USP) 5,290,745 and the catalyst Precursors of european patent application 771 820 especially can be used for method of the present invention, when it is put into the hydrocarbon slurries with unactivated state.

[0062] as mentioned above, part activates this parent before polymerization. In reactor, finish activation with co-catalyst. Preferably when ethylene flow begins, in polymer reactor, add respectively pure co-catalyst or add respectively co-catalyst with the solution form in atent solvent such as isopentane.

[0063] in independent embodiment, in the single reactor structure, use the second chromium-based catalysts, although it is not limited to single reactor, and it can use in two or more tandem reactors.

[0064] by the polyvinyl resin of these chromium-based catalysts polymerizations and to prepare their method normally known in the art. This comprises gas-phase, liquid phase and slurries-phase polymerisation process. The concrete importance of the present invention is with the resin of gas-phase process preparation, uses chrome catalysts, particularly is the metatitanic acid chrome catalysts.

[0065] general, the effective catalyst that is comprised of chromium (VI) compound (general form with oxide) loads on the high surface area refractory carrier. Usually this carrier is amorphous microspheric silica, silica alumina, silicon dioxide and titanium dioxide or aluminate or phosphate. This catalyst is by preparing at the carrier that activation contains chromium in dry, oxygen containing atmosphere under the 400-1000 ℃ of temperature. Material modified such as titanium and usually interpolation before activation of fluoride.

[0066] common, catalyst is commercially available by using, added the silica preparation in chromium source. Can after the Cr Compound deposition or before this deposition, process this silica base material with titanium ester (titanium ester) (normal operation tetraisopropyl titanate or titanium tetraethoxide). This carrier is usually predrying to remove physical absorption water under about 150-200 ℃. Can add titanate in the isopentane solvent silica slurry or directly add in the fluid bed of carrier with the form of solution. If add with the slurries form, dry these slurries. Usually, will be convertible into Cr already⁺⁶The Cr compound add in this carrier. Then change this carrier into active catalyst by under the highest 1000 ℃ temperature, in air, calcining.

[0067] between pot-life, changes titanium into certain oxide on surface. Chromium compound (usually chromium (III) acetate) is transformed into certain Cr⁺⁶Oxide. Also can add fluorization agent during the activation process with the hole of in carrier, collapsing selectively, thus the molecular weight response of modified catalyst. Can process this activating catalyst with reducing agent before this external use, such as the carbon monoxide in fluid bed or other reducing agent such as alkyl aluminum, boron alkyl, lithium alkylide etc.

[0068] catalyst of this type has been described in a lot of patents, such as WO2004094489, EP0640625, US4100105 and the list of references wherein quoted. This all introduce them each as a reference. For example, effectively catalyst is chromium that carrier is arranged-titanium catalyst (or metatitanic acid chromium oxide catalyst), it in shape basically right and wrong spherical or irregular, and have widely size distribution, and at least in the hole of its pore volume of 70% in about 200 to the 500 dust scopes in aperture. The complex of above-mentioned load can be by in the presence of oxygen, from about 850 ℃ of heat-activated under the sintering temperature of the complex of load. As those be described among the US6022933, comprise Cr equally⁺⁶The catalyst of component also can be used for the present invention. Introduce equally its full content herein as a reference.

Be used for the description of the concrete catalyst of blend composition

[0069] in order to prepare this blend component, prepares the titanium trichloride catalyst parent by at first producing magnesium chloride and the titanium trichloride solution in oxolane. Remain under the blanket of nitrogen (less than 5ppm H always₂O)。

[0070] will comprise the H less than 200ppm₂The oxolane of O (THF) adds in the container. Analysis moisture content, the triethyl aluminum and the water that then add q.s react. THF is heated to 50 ℃ temperature, adds granular magnesium metal and titanium tetrachloride. Add enough titanium tetrachlorides to produce Ti content as the solution of 0.09-0.10 mM/gram solution. To add magnesium metal with the mol ratio of titanium tetrachloride as 0.5/1 amount. Adding this titanium tetrachloride in half an hour approximately.

[0071] constantly stirs this mixture. By heating temperature was kept approximately other four hours at about 70 ℃. When this time finished, adding basically anhydrous magnesium dichloride was the solution with from 0.45 to 0.60 mM of content of magnesium/gram solution in order to make this solution. Continuing under the stirring other eight hours of 70 ℃ of heating. Then the filter by 100 microns filters this mixture (solution) to remove undissolved magnesium dichloride and unreacted magnesium.

[0072] within about period more than two hours, be that 0.1 to 1 micron the hydrophobic pyrogenic silica of nominal adds in the mixture of preparation with having granularity. During this time stir this mixture by turbine stirrer and after this stir several hours in case in this solution dispersed silicon dioxide fully. Before adding pyrogenic silica, this solution can be cooled to about 35 ℃. Cab-O-Sil TS610 is as pyrogenic silica. Add enough pyrogenic silicas in order to the Cab-O-Sil total content of about 6wt% is provided.

[0073] use is equipped with the slurries of the enclosed circulation spray dryer spray-drying gained of rotary atomizer. The speed of regulating this rotary atomizer has the catalyst particle of the D50 of requirement with production. Regulate the inlet temperature of dry gas in order to obtain the final content of tetrahydrofuran that requires of catalyst Precursors. General inlet temperature scope is 120-165 ℃. The washer of spray dryer is partly maintained 0 to-10 ℃ temperature in order to reclaim the solvent of evaporation.

[0074] spray-dired catalyst Precursors comprises the Ti of 2 to 2.5 % by weight, the Mg of 5.5 to 7 % by weight and the THF of 22 to 30 % by weight. The slurries that comprise about 28 % by weight solid catalyst parents in the container of turbine stirrer with mineral oil with formation under blanket of nitrogen, discrete catalyst Precursors particle are being equipped with.

[0075] for part activates this catalyst slurry, when delivering to this slush pump in the reactor, adds the 50 % by weight solution of tri-n-hexyl aluminum (TnHAl) in mineral oil. This mixture is remained in the time of staying container rough 1-4 hour, and this depends on the absolute inlet amount of catalyst. Use the TnHAl solution of q.s in order to every mole of desired TnHAl mol ratio of THF is provided in catalyst.

[0076] subsequently, add the 30 % by weight solution of diethylaluminum chloride (DEAC) in mineral oil, this mixture was kept rough 1-4 hour in other time of staying container, this also depends on the absolute inlet amount of catalyst. Use the DEAC of q.s in order to every mole of desired DEAC mol ratio of THF is provided in catalyst. Then the part activating catalyst is sent out the second time of staying container, directly enter in the polymer reactor, the co-catalyst with final quantity activates it fully there.

[0077] as noted above, activate this parent in polymerization with forward part. In reactor, finish activation by co-catalyst. Preferably when ethylene flow begins, in polymer reactor, add respectively pure co-catalyst or add co-catalyst with the solution form in atent solvent such as isopentane.

[0078] the whole catalyst system that comprises part activation parent and co-catalyst is added in the first reactor. With this catalyst system, that is, part activates parent and co-catalyst, mixes with the copolymer that produces in the first reactor or homopolymers, then changes this mixture over to second reactor. In the scope that catalyst system relates to, if requirement is only added co-catalyst to second reactor from external source.

[0079] gas phase is carried out polymerization in each reactor in using the method for continuous fluidized bed, but can also carry out in slurries or solution. For example, in U.S. Patent No. 5,844,045, U.S. Patent No. 5,869, and 575 and U.S. Patent No. 6,448,341 have especially described at least one reactor with homogeneous catalyst with at least one and have come solution copolymerization ethene and C with heterogeneous catalysis in other the reactor₃-C ₂₀Alpha-olefin. U.S. Patent No. 6,566,446 people such as () Parikh and 6,538,070 people such as () Cardwell disclose and used the homogeneous catalyst copolymerization of ethylene in two different reactors, wherein change polymerizing condition in order to affect the reactivity of catalyst. In these all situations, this reactor can be sequentially or parallel running. All introduce all these patents as a reference at this.

[0080] said composition can also be produced in the following manner: heterogeneous ethylene/alpha-olefin polymer is fractionated into each fraction has narrow composition (namely, branching) the particular polymers fraction that distributes, selection has the fraction of specified properties, and with selected fraction with an amount of and other ethene polymers blend. This method does not obviously have U.S. Patent No. 5,844, and 045, the in-situ copolymerization method economy of U.S. Patent No. 5,869,575 and U.S. Patent No. 6,448,341, but can be used for obtaining composition of the present invention. All introduce all these patents as a reference at this.

[0081] in addition various other patent disclosure the polymerization technology, comprise USP 4,076,698 (people such as Andersen), USP 5,977,251 (people such as Kao) and WO 97/36942 (people such as Kao) all introduce each disclosure as a reference herein.

[0082] composition disclosed herein can also be formed by any easily method, comprise being dry mixed and close independent component, melting mixing or mix by pre-fusion in the independent extruder (for example, banbury mixer (Banbury mixer), Haake mixing roll, Brabender banbury or counter-rotating or co-rotating twin screw extruder) subsequently.

[0083] usually in the first reactor, prepares relatively low-density copolymer. Preferably the mixture of polymer and active catalyst is transferred to second reactor as the interconnecting device of transfer medium from the first reactor by use nitrogen or the second reactor cycles gas. The higher copolymer of preparation density in the second reactor. Alternatively, can in the first reactor, prepare high density copolymer, and in the second reactor, can prepare low density copolymer.

[0084] said composition has widely molecular weight distribution, and is aforesaid, and it can be characterized by bimodal. The extensive molecular weight distribution that shows is about 3 to Mw/Mn ratios about 10, preferred about 3 to about 8. Mw is weight average molecular weight; Mn is number-average molecular weight; Can be called polydispersity index with Mw/Mn ratio, it is the yardstick of measuring the molecular weight distribution width.

The polymerisation of blend composition is described

[0085] copolymer for preparing in the low-density reactor can arrive within about 90: 10 scope at about 10: 90 with the weight ratio of the copolymer for preparing in high density reactors, and preferably arrives in about 80: 20 scope, most preferably in the scope of about 20-30: 80-70 at about 20: 80. This also is commonly referred to as shunting (split). To comprise co-catalyst, ethene, alpha-olefin and, the catalyst system of the transition metal base of optional hydrogen constantly closely expects in the first reactor; Polymer/active catalytic agent composition is constantly transferred to the second reactor from the first reactor; With ethene and, randomly, alpha-olefin and hydrogen, and co-catalyst constantly is supplied in the second reactor. These final products are removed from the second reactor continuously. Preferred mode is to obtain in batches product from the first reactor, then uses the dividing potential drop that produces by the recyclegas compression system that they are transferred in the second reactor. With U.S. Patent No. 4,621, similar system described in 952 is especially effective.

[0086] pressure in the first and second reactors is approximately identical. Depend on the mixture of polymer and contained catalyst is delivered to the concrete grammar of the second reactor from the first reactor, the second reactor pressure can be higher than or slightly be lower than the pressure of the first reactor. If the second reactor pressure is low, can use this pressure reduction with help the polyalcohol catalyst mixture to be delivered to the reactor 2 from reactor 1. If the pressure of the second reactor is higher, the pressure reduction that passes recycle gas compressor can be as the power that transmits polymer.

[0087] pressure, i.e. stagnation pressure in reactor, can be about 200 to about 500psig (pounds/square inch) within the scope, and preferably arrive in the scope of about 450psig about 280. Ethylene partial pressure in the first reactor can arrive within the scope of about 150psig and preferably about 10 and arrive in the scope of about 80psig about 20. According to the amount of copolymer, the ethylene partial pressure in the second reactor is set, wish that the product in this reactor obtains above-mentioned shunting. Notice, increase the increase that ethylene partial pressure in the first reactor can cause ethylene partial pressure in the second reactor. The balance of stagnation pressure is provided by the alpha-olefin except ethene and inert gas such as nitrogen. In addition, the vapour pressure under the temperature and pressure that in reactor, experiences according to them, other unreactive hydrocarbons, as the condensing agent that brings out for example isopentane, hexane also help gross pressure in the reactor.

[0088] general fluidized-bed reactor can be as described below: this is comprised of the identical granular resin that produces in this reactor usually. Therefore, between polymerization period, this comprises the polymer beads of formation, polymer beads and the catalyst particle of growth, they by polymerization and modification to be enough to causing that particle separation and the gaseous component of introducing as flow rate or the speed of fluid come fluidisation. This fluidizing gas is by initial charging, supply charging and circulation (recycling) gas, that is, comonomer and, if requirement, modifier and/or inert carrier gas composition.

[0089] basic element of character of reaction system is that container, bed, gas distribution plate, entrance and exit pipe, compressor, recycle gas cooler and product are discharged system. In this container, on this bed, there is a speed to reduce district and the district that in this bed, responds. They are all on gas distribution plate.

[0090] general fluidized-bed reactor is further described in U.S. Patent No. 4,482, in 687. Preferably the gaseous feed flow of ethene, other gaseous state alpha-olefin and hydrogen (if use) are fed in reactor cycles line and liquid alpha-olefin and the co-catalyst solution. Randomly, the liquid co-catalyst can directly be fed in the fluid bed. The catalyst Precursors that preferably will partly activate is injected in the fluid bed with the form of solid or mineral oil slurry. In reactor, use co-catalyst to finish activation. Can recently change this product composition by the mole that changes the comonomer of introducing fluid bed. When under polymerizing condition, increasing bed content, constantly from reactor with the form emission product of granular or particle. Come the production control rate by regulating catalyst charge amount and/or the ethylene partial pressure in two reactors, which is hereby incorporated by reference for this patent.

[0091] can regulate hydrogen: the mole of ethene is recently controlled mean molecule quantity. Alpha-olefin (except ethene) can exist with the total amount of maximum 15 % by weight of copolymer, if use, the total amount that preferably comprises in copolymer is about 1 to about 10 % by weight, with the weighing scale of copolymer.

[0092] reactant, catalyst and the time of staying of resin blend thing in each fluid bed that comprise gaseous state and liquid reactants can arrive within about 12 hours scope about 1, and preferably arrive in about 5 hours scope about 2.

[0093] if requirement, this reactor can move with condensing mode. This condensing mode is described in United States Patent(USP) Nos. 4,543, and 399,4,588,790 and 5,352,749. All introduce all these patents as a reference at this.

[0094] this blend can be from during having two separate reactors of afterreaction blend (each uses identical or different catalyst) or have the material of producing in the reactor of two compatible catalysts and prepare, and described compatible catalysts produces the component that requires under single sets of conditions. For the second situation, this catalyst is charging or together charging respectively.

[0095] as mentioned above, the gaseous material that uses in the method can be incorporated in the reactor by recyclegas. This recyclegas is defined as admixture of gas, it comprises ethene itself or ethene and one or more alpha-olefin, preferred one or two kind of alpha-olefin, as comonomer, and randomly, one or more inert gas such as nitrogen (supplying desired reactor pressure), unreactive hydrocarbons and hydrogen. Alpha-olefin can be, for example, and propylene, 1-butylene, 1-hexene, 4-methyl-1-pentene and 1-octene. This alpha-olefin has at the most 12 carbon atoms usually, and preferred 3 to 8 carbon atoms. This recyclegas can also be called air inlet or recycling gas.

[0096] as mentioned above, before polymerization, with this parent fraction activation. In reactor, finish activation by co-catalyst. Preferably, when ethene begins to flow, in polymer reactor, add respectively pure co-catalyst or add co-catalyst with the solution form in atent solvent such as isopentane.

[0097] use the continuous fluid bed process in gas phase, to carry out this polymerization. According to the improved ASTM D-1238 of Dow, under 190 ℃ and 2.16 kilograms, measure melt index (MI) (I₂), and to restrain per 10 minutes or minute grams per minute record. According to the ASTM D-1238 of Dow modification, under 190 ℃ and 21.6kg weight, measure flow index (I_21.6), and to restrain per 10 minutes or minute grams per minute record. Melt flows is than the ratio (I that is flow index and melt index (MI)_21.6/I _2.16). The product that shifts out from this reactor can have about 0.02 to the per 10 minutes melt index (MI) of about 300 grams, and preferably has approximately＞0.04 to the per 10 minutes melt index (MI) of about 50 grams. The melt flows ratio arrives within about 50 the scope about 20, and preferably arrives in about 35 the scope about 20. The density of this polymer normally at least 0.900 restrains every cubic centimetre, with preferably in the scope of every cubic centimetre of 0.915 to 0.960 gram, and be more preferably in the scope of every cubic centimetre of 0.935-0.955 gram and most preferably in the density range of every cubic centimetre of 0.940-0.950 gram.

The mensuration of molecular weight distribution

[0098] polyvinyl molecular weight distribution uses gel permeation chromatography (GPC) being equipped with differential refractometer and three 150 ℃ of high temperature chromatograms of Waters unit that mix the post of porosity to measure. This post is provided by Polymer Laboratories, and usually fills granularity 10³、10 ⁴、 10 ⁵With 10⁶. Solvent is 1,2,4-trichloro-benzenes, by its sample solution for the preparation of about 0.3 % by weight of injection. Flow rate approximately is 1.0 ml/min, and the cell operation temperature is about 140 ℃, and injection volume is about 100 microlitres.

[0099] molecular weight determination for main polymer chain uses polystyrene standard (from Polymer Laboratories) and their elution volume of Narrow Molecular Weight Distribution to derive together. (Williams and Ward are described in Journal of Polymer Science to the molecular weight of polyethylene of equivalence by using suitable polyethylene and the Mark-Houwink coefficient of polystyrene, Polymer Letters, the 6th volume, the 621st page, 1968) the following formula that derives is measured:

M _Polyethylene＝a*(M _Polystyrene) ^b

[00100] in this formula, a=0.4316 and b=1.0. Calculate weight average molecular weight Mw:M according to following general formula in normal way_j＝(∑w _i(M _i ^j)) ^j W wherein_iTo have molecular weight M_iThe weight fraction of molecule, described molecule is from the GPC post elution among fraction i, j=1 when calculating Mw, and j=-1 when calculating Mn. New composition has and is less than or equal to 3.3, preferably is less than or equal to 3 and from about 2.4 to about 3 Mw/Mn particularly.

[00101] in the reactor of blend composition: alpha-olefin (if use) can arrive within about 0.8: 1 scope at about 0.01: 1 with the mol ratio of ethene, and preferably arrives in about 0.25: 1 scope at about 0.005: 1. Hydrogen (if use) can arrive within about 2: 1 scope at about 0.001: 1 with the mol ratio of ethene, and preferably arrives in about 0.3: 1 scope about 0.05. Operating temperature can be within about 60 to 120 ℃ scope and preferably in about 80 to 110 ℃ scope. Notice that these ratios only comprise the hexene product and do not cover dual catalyst system that it requires the modification of catalyst type and is used for the mensuration of the condition of catalyst type.

[00102] this pressure, that is, the stagnation pressure in reactor, can be about 200 to about 500psig (pounds/square inch) scope within, and preferably arrive in the scope of about 450psig about 280. This ethylene partial pressure can arrive within the scope of about 200psig about 10, and preferably arrives in the scope of about 170psig about 60. Use alpha-olefin (if use) and inert gas such as nitrogen that the balance of stagnation pressure is provided. In addition, according to the vapour pressure under the temperature and pressure that in reactor, experiences, other unreactive hydrocarbons, as the condensing agent that brings out (induced condensing agent) for example isopentane, hexane help the gross pressure in the reactor. General fluidized-bed reactor can be as described below:

[00103] this is comprised of the above-mentioned granular resin that will produce in this reactor usually. Therefore, between polymerization period, this comprises the polymer beads of formation, polymer beads and the catalyst particle of growth, they by polymerization and modification to be enough to causing that particle separation and the gaseous component of introducing as flow rate or the speed of fluid come fluidisation. This fluidizing gas is by initial charging, supply charging and circulation (recycling) gas, that is, comonomer and, if requirement, modifier and/or inert carrier gas composition.

[00104] basic element of character of reaction system is that container, bed, gas distribution plate, entrance and exit pipe, compressor, recycle gas cooler and product are discharged system. In this container, on this bed, there is a speed to reduce district and the district that in this bed, responds. They are all on gas distribution plate.

[00105] general fluidized-bed reactor is further described in U.S. Patent No. 4,482, in 687, is incorporated herein its full content as a reference.

[00106] preferably the gaseous feed flow of ethene, other gaseous state alpha-olefin (if use) and hydrogen (if use) are fed in reactor cycles line and the liquid alpha-olefin (if use). Preferably the form of activating catalyst parent with solid or mineral oil slurry is injected in the fluid bed. Can change this product composition by change introducing comonomer in the fluid bed and the mol ratio of hydrogen and the different catalysts ratio of in single reactor, using. When under polymerizing condition, increasing bed content, constantly from reactor, discharge this product with the form of granular or particle. Come the production control rate by regulating catalyst charge amount and/or ethylene partial pressure.

[00107] can regulate hydrogen: mol ratio and the temperature of reactor of ethene are controlled mean molecule quantity. Can regulate alpha-olefin: the mole of ethene is recently controlled resin density.

[00108] alpha-olefin (except ethene) can exist with maximum 15% total amount of copolymer weight, if use, the total amount that preferably comprises in copolymer is about 1 to about 12 % by weight, with the weighing scale of copolymer.

[00109] reactant, catalyst and the time of staying of resin blend thing in fluid bed that comprise gaseous state and liquid reactants can arrive within about 12 hours scope about 1, and preferably arrive in about 5 hours scope about 1.5.

[00110] if requirement, this reactor can move in the mode of condensation. This condensing mode is described in United States Patent(USP) Nos. 4,543, in 399,4,588,790 and 5,352,749.

[00111] this resin can be extruded in being suitable for the extruder commonly used of this purpose. The extruder and the method that are used for extruding are described in United States Patent(USP) Nos. 4,814, in 135,4,857,600,5,076,988 and 5,153,382. All introduce all these patents as a reference herein.

The reactor condition of blending ingredients

Product	Resin B	Resin A
			Temperature of reactor, ℃	88	102
Reactor pressure, psig	315	320
			C2PP，psig	100	155
H 2/C 2(molar flow ratio)	0.140	0.220
			C 6/C 2(molar flow ratio)	0.150	0.013
Al/Ti (mol ratio)	40	50
			I 2，g/10min	1.0	4.4
Density, g/cm3	0.918	0.952

[00112] comprises that the closure member of the present composition is passable, for example, according to United States Patent (USP) 6,139,931 (people such as Finkelstein), United States Patent (USP) 5,598,940 (people such as Finkelstein), United States Patent (USP) 6,382,445 (McCandless), United States Patent (USP) 5,000,992 (Kelch), United States Patent (USP) patent 4,744,478, United States Patent (USP) 4,744,478 (Hahn), United States Patent (USP) 4,807,772 (Schloss) and United States Patent (USP) 4, the instruction of 846,362 (Schloss) is produced. All introduce all these patents as a reference at this.

[00113] liner, if use according to the present invention, can be according to United States Patent (USP) 4,984,703 (Burzynski), United States Patent (USP) 5,137,164 (Bayer) and United States Patent (USP) 4,872,573 people such as () Johnson are produced. All introduce all these patents as a reference at this.

[00114] in one embodiment, for the component relative concentration of blend, this mixture can comprise (A) about 10 to the ethene polymers of about 90 % by weight, and it has about 0.947 to about 0.962g/cm³Density, arrived the melt index (MI) of about 7g/10min in about 1 to about 10g/10 minute, preferred about 2 to about 8g/10min, more preferably from about 3;

[00115] (B) about 90 to the ethene polymers of about 10 % by weight, it has about 0.912 to about 0.932g/cm³Density, arrived the melt index (MI) of about 3g/10min in about 0.25 to about 6g/10 minute, preferred about 0.5 to about 4 g/10min, more preferably from about 0.75; With

[00116] (C) additive of 0 to 6 % by weight, this additive is selected from color improvement agent, lubricant, filler, pigment, antioxidant and processing aid, and preferred scope is that 0.01 to 3 % by weight and most preferred scope are 0.015 to 0.5 % by weight;

[00117] wherein component (A) and density contrast (B) (Δ D=D (A)-D (B)) are equal to or greater than 0.03g/cm³。

[00118] intermediate range (namely) wherein component A be about 40 to 85 % by weight and B component be about 15 to 60 % by weight or wherein component A be that about 65 to 80 % by weight and B component are about 20 to 35 % by weight, be the part of specification clearly. The relative percentage that skilled person in the art will appreciate that A and B can change as required.

Concrete catalyst description and the polymerizing condition of one pack system resin combination

[00119] single unimodal resin is by the following manner manufacturing: in the gas phase process of making polymer ethene is contacted with the catalyst system that comprises catalytic activity chromium or chromium-titanium complex in fluidized-bed reactor with the 1-hexene co-monomer, described complex is carried on the refractory oxide material, wherein the total pore volume of at least seven ten (70%) above-mentioned materials is in the hole of about 200 to 500 dust bore dia scopes, and the complex of carrying is by activating under the temperature of the sintering temperature of the complex of load from about 600 ℃ in the presence of oxygen.

[00120] can use with the O2/C2 molar flow ratio of maximum 250ppbm the oxygen that is added back in the polymer reactor to increase MI and resin density, then this requires to increase the comonomer of introducing to produce the density of equivalence. U.S. Patent No. 6,022,933 have described this method in detail, all introduce it as a reference at this. Usually, the character of this resin is (the improved ASTM D-1238 of Dow condition E) and 935-955gm/m in the scope of 0.3-1.2MI³Density (ASTM D-1505) in the scope. Use 1-hexene, 1-octene, 4-methyl-1-pentene or other molecular weight greater than the alpha-olefin comonomer of propylene. Select in an embodiment the ethene-hexene copolymer of 0.8MI and 945 density to assess. When in the pop bottle closure member is used, testing, adding the 200ppmw polyethylene glycol^TM 400(Carbowax ^TM400) satisfied afterwards all character that requires, it improves color and reaches satisfied degree. Randomly, can be with 1000 ppmw HPN^TM68 add in the resin sample as nucleator. In order to obtain processing characteristics and long-time stability, add general antioxidant.

[00121] can use additive with disclosed polymer resin herein. This additive can be used for improving different character (ESCR, color, taste, etc.). For example, (for example producing polyethylene with chrome catalysts, the ethylene/hexene copolymer) in the situation, when between polymerization period preferably with 10: 1 to 80: 1, more preferably 50: 1 to 70: 1 Zn: when the Cr mol ratio was added dialkyl zinc compounds such as diethyl zinc, it demonstrated significantly preferably environmental stress crack resistance (ESCR) and chromatic characteristic.

The reactor condition of the product of one pack system chromium catalysis

Reactor condition:

		Unit
			O2/C2 molar flow ratio	280	ppbm
The control temperature of fluid bed	103.7	℃
			The C6/C2 molar concentration rate	0.0040	mol/mol
C6/C2 molar flow ratio	0.020	mol/mol
			The gas velocity on surface	2.53	ft/sec
The isopentane molar concentration	2.7	mol％
			Catalyst Production power	3,800	lb/lb
The bulk density of top fluidisation (FBD)	15.5	lb/ft^3
			The bulk density of bottom fluidisation (FBD)	17.7	lb/ft^3
Fluid bed weight	132.2	Mpph
			Productivity ratio	64.8	Mpph

Character	Mean value	Unit
			Melt index (MI), the improved ASTM D-1238 of Dow condition E	0.86	dg/min
Melt flow index, the improved ASTMD-1238 condition of Dow F	59.6	dg/min
			The melt flows ratio, (I21/I12)	68.7	NA
Density, ASTM D-792	0.9453	g/cc
			Particle mean size, ASTM D-1921	0.021	Inch

[00122] will comprise that the parent of activation and ethene and optional alpha-olefin comonomer and the transition metal-based catalyst system of hydrogen constantly are fed in the reactor. The polyvinyl resin that produces part from reactor is removed continuously.

Additive:

The antioxidant prescription of blend includes but are not limited to:

The trisnonyl phenyl phosphite of 390ppm (trisnonylphenyl phospite) (being called WestonTM 399)

The zinc stearate of 750ppm

The octadecyl of 510ppm-3,5-two-tertiary butyl-4-hydroxy hydrogenated cinnamate

The zinc oxide of 210ppm

Many other stabilisation bags well known to those skilled in the art are arranged, and it realizes being applicable to the polymer stabilising of this application.

[00123] can use the fluoroelastomer processing additives with the amount of maximum about 500ppmw, such as Dynamar^TMFX-5911, with minimizing extrude with compression moulding during blemish and melt fracture.

The additive package of one pack system chromium catalysate

[00124] four suitable polyphenoils additive formulations for blend include, but are not limited to:

Prescription 1

The Igranox of 350ppm^TM 3114(I-3114)

The polyethylene glycol of 200ppm^TM 400(C-400)

Prescription 2

The Igranox of 350ppm^TM 1010(I-1010)

The polyethylene glycol of 200ppm^TM 400

Prescription 3

The Igranox of 350ppm^TM 3114，

The Irgafos of 400ppm^TM 168(I-168)

The polyethylene glycol of 200ppm^TM 400

Prescription 4

The Igranox of 350ppm^TM 1010

The Irgafos of 400ppm^TM 168

The polyethylene glycol of 200ppm^TM 400

[00125] for additive, skilled person in the art will appreciate that to be combined with one or more additive. In the embodiment of selecting, one or more additive can be that about 0.01 of composition arrives about 6 % by weight. In other embodiment, additive can exist with 0.01 amount to about 3 % by weight. In another one embodiment again, additive can exist with the amount of 0.015 to 0.5 % by weight. Yet, can use other amount of additive according to embodiment of the present invention, as long as the performance that keep to require.

[00126] for processing, it should be appreciated by those skilled in the art that polymer gel can form under some processing conditions. This can make the heavy polymer processing difficulties. A scheme is melting said composition (it can be aforesaid blend); With, extrude or granulation before, by one or more effective sieve, effectively in situations of sieve, series connection arranges at two or more with this melt blended material. In one embodiment, can use scalping (that is, 20 to 40 orders)). In embodiment optionally, can use dusting cover (250 to 325 order). In another embodiment, can be combined with thin and scalping. This method can be improved by using dynamic (CFD) model of Fluid Computation. CFD can be used for designing sieve so that the polymer gel drop can impact the net in the scalping, and this can cause drop separation. Those skilled in the art can approve, can use other filter (as effective " zero aperture (zero aperture) " filter screen (that is, and plane Dutch fabric, twill Dutch fabric, etc.)).

Method of testing

C13NMR

[00127] uses C13NMR to measure short-chain branch distribution content and co-monomer content, as be described in Randall, Rev.Macromol.Chem.Chys., C29 (2﹠3), 285-297 page or leaf, and US5, in 292,845, be incorporated herein their disclosure as a reference. The mixture of 50/50 tetrachloroethanes by adding about 3g in the 0.4g sample in 10mm NMR pipe-d2/ o-dichlorohenzene, described mixture is 0.025M in chromium acetylacetonate (relaxant). With sample dissolution and by managing and its content is heated to 150 ℃ and homogenizes. Use JEOL Eclipse 400MHzNMR spectrometer, corresponding to 13C resonant frequency 100.6MHz, collect data. Select acquisition parameter to guarantee 13C data acquisition quantitative in the presence of relaxant. Be heated at probe and use under 130 ℃ the condition that gate 1H uncouples, lax and 1.3 seconds the acquisition time, 24 of 4000 instantaneous/data files, 4.7 seconds, the file size of the spectrum width of 200Hz and 64K data point obtains data. This spectrum is with reference to the methylene peak value at 30ppm. D5017-91 comes result of calculation with the ASTM method.

[00128] measure and measure CRYSTAF (crystal analysis classification (crystallization analytical fractionation)) according to following publication:

[00129] experiment and the numeral of crystal analysis classification (crystaf) are studied (An experimental and numerical study on crystallization analysis fractionation (crystaf)). Anantawaraskul, Siripon; Soares, Joao B.P.; Wood-Adams, Paula M.Department of Chemical Engineering, McGill University, Montreal, QC, Can.Macromolecular Symposia (2004), 206 (Polymer Reaction Engineering V), 57-68.

[00130] to 13C NMR, GPC and DSC research (the 13C NMR of the propylene-ethylene that uses the classification of intensification elution fractionation method-1-butene terpolymers, GPC, and DSC study on a propylene-ethylene-1-butene terpolymer fractionated by temperature rising elution fractionation). Zhang, Yu-Dong; Gou, Qing-Qiang; Wang, Jun; Wu, Chang-Jiang; Qiao, Jin-Liang. Beijing Research Institute of Chemical Industry. SINOPEC, Beijing, Peop.Rep.China.Polymer Journal (Tokyo, Japan) (2003), 35 (7), 551-559.

[00131] molecular weight and average comonomer content are on the impact (Effect of molecular weight and average comonomer content on the crystallization analysis fractionation (Crystaf) of ethylene a-olefin copolymers) of the crystal analysis classification (Crystaf) of ethene a-olefin copolymer. Anantawaraskul, Siripon; Soares, Joao B.P.; Wood-Adams, Paula M.Monrabal Benjamin. Department of Chemical Engineering, McGill University, Montreal, QC, Can.Polymer (2003), 44 (8), 2393-2401.

[00132] with the synthetic ethene of the catalyst of unit point/1-hexene copolymer: crystal analysis classification, simulation and reactivity are measured (Ethylene/1-hexene copolymers synthesized with a single-site catalyst:Crystallization analysis fractionation, modeling, and reactivity ratio estimation) .Sarzotti, Deborah M.; Soares, Joao B.P.; Penlidis, Alexander.Institute for Polymer Research, Department of Chemical Engineering, University of Waterloo, Waterloo, ON, Can. Journal of Polymer Science, Part B:Polymer Physics (2002), 40 (23), 2595-2611.

[00133] color:

The ASTM method of testing that uses is D-1925-88. The YI=yellowness index.

[00134] tensile property:

When in the process of preparation plate, preparing sample according to ASTM D-4976, by ASTM-D638 model IV sample is measured.

[00135] melt index (MI) character:

It is measured according to the improved ASTM D-1238 of Dow condition (190,2.16) and (190,21.6).

[00136] the improved ASTM D-1238 of MFR=MI21/MI2 or Dow (190,2.16/ 190,21.6).

[00137] density:

It is measured according to ASTM D-792.

[00138] bending modulus:

When in this plate process of preparation, preparing this plate according to ASTM D-4976, measure according to ASTM D-790.

[00139] notch shock performance:

It is measured according to ASTM D-256, makes this plate according to ASTM D-4976 in the process of this plate of preparation.

[00140] particle mean size:

ASTM D-1921。

Embodiment

Embodiment 1-3: the character of blend composition.

Embodiment 1: the blend of 3: 1 ratios (75 % by weight Resin A and 25 % by weight resin B) of assessment Resin A and resin B. Embodiment 2 and 3 also is shown in the following table.

			75%: 25% Resin A of embodiment 1 (the 3rd blend): resin B
					Averag density	g/cm 3	0.9452
ESCR *-100% IGEPAL CO 630
					1 stFracture	hr	121
	2 ndFracture	hr	160
					3 rdFracture	hr	208
	4 thFracture	hr	215
					5 thFracture	hr	256
	6 thFracture	hr	329
					7 thFracture	hr	377
	8 thFracture	hr	nm
					9 thFracture	hr	nm
	10 thFracture	hr	496
					Elapsed time	hr	496
F 50Hour		hr	283.5
					Melt index (MI)-I2	G/10 minute	3.13
Stretching-moulded specimen is according to ASTM D-4976	Average thickness	Inch	0.067
					Mean breadth	Inch	0.25
	Average yield strain	％	5.868
					Average bending strength	psi	3271.5

^*Environmental stress crack resistance

The about 4g/10min melt index (MI) (I of Resin A=have₂), about 4 Mw/Mn and about 0.952g/cm³The ethene of density/1-hexene copolymer

The about 1g/10min melt index (MI) (I of resin B=have₂), about 4 Mw/Mn and about 0.918g/cm³The ethene of density/1-hexene copolymer

			Embodiment 1		Embodiment 2	Embodiment 3
										25: 75 resin B of blend data: Resin A		Blend 20: 80	Blend 30: 70
	Test condition#	Unit	Initial mixed blend	The second blend	Resin B: Resin A	Resin B: Resin A
							Density	ASTM D 792	g/cm 3	0.944	0.945	nm	nm
I 2	The improved ASTM D 1238 (190/2.16) of DOW	g/10min	3.4	2.9	nm	nm
							ESCR	ASTM D-1693 condition B 10%IGEPAL	50% probability destroys (hr)	168	＞172	＞172	＞172
	ASTM D-1693 condition B 100%IGEPAL	50% probability destroys (hr)	nm	＞172	＞172	＞172
							Stretch	Surrender	psi	3160	3100	nm	nm
	Elongation at yield	％	6.2	7.7	nm	nm
							Crooked	Tangent modulus	psi	nm	162,000	nm	nm
	1% secant modulus	psi	nm	131,000	nm	nm
								2% secant modulus	psi	nm	110,000	nm	nm
Notched Izod impact strength	ASTM D-256	Ft-lbs/in	nm	7.7	nm	nm
							DSC	Tm	℃	nm	130	nm	nm
Atref HD fraction (%)				72.4
							ATref purifies fraction (%)				12.4
ATref SCBD fraction (%)				15.2
							Add up to				100.0
The solvable fraction of Crystaf (%)				3.0

Nm=does not measure

Embodiment 4: single resin combination:

			Embodiment 4	The product that competitiveness is arranged
					Additive package			350ppm Irganox 3114 and 200ppm PEG400	Samsung   C430A
Character	The ASTM test	Client's target
					MI2(g/10min)	D-1238 condition E (DOW is improved)		0.69	1.65
Density ASTM (g/cc)	D-792		0.9465	0.9574
					ESCR F 50(hrs) 10%Igepal is under 50C	D-1693 condition B		187	61.7
Repeat ESCR F50(hrs) 10%Igepal is under 50C	D-1693 condition B			59.7
					ESCR F 50(hrs) 100%Igepal is under 50C	D-1693 condition B	＞80	3248	74.3
Repeat ESCR F50(hrs) 100% Igepal is under 50C	D-1693 condition B	＞80		57.1
					Hot strength@Bk (psi)	D638 to model IV sample		2217	3014
% percentage elongation@Bk	D638 to model IV sample		543	935
					Yield strength (psi)	D638 to model IV sample	3000-4000	3482	4345
The % elongation at yield	D638 to model IV sample		6.6	7.7
					Atref HD fraction (%)	The DOW method		78.2	85.4
Atref purifies fraction (%)	The DOW method		8.3	7,2
					Atref SCBD fraction (%)	The DOW method		13.5	7.4
Add up to			100.0	100.0
					The solvable fraction of Crystaf (%)	The DOW method		2.9	1.4
Color	ASTM   D-1925-88		YI＝-2.47
					Taste	The DOW method		Product has the taste less than the tester of rice modification.

The color data result of embodiment 4 resins. Prescription B, the D, F and the H that comprise the 200ppm PEG400 have preferably color. The YI=yellowness index

Additive YI reading in PPM

	Additive in ppm						The YI reading
										Prescription	I-1010	C-400	I-168	I-3114	Average YI	Standard deviation	1	2	3
A   B   C   D   E   F   G   H	350   350   350   350	200     200     200     200	400   400       400   400	350   350   350   350	0.97   -2.37   0.78   -2.35   1.56   -2.47   1.68   -2.28	0.042   0.020   0.052   0.042   0.046   0.026   0.046   0.020	0.94   -2.35   0.84   -2.38   1.52   -2.49   1.69   -2.30	1.02   -2.39   0.75   -2.36   1.61   -2.44   1.63   -2.28	0.96   -2.37   0.75   -2.30   1.55   -2.48   1.72   -2.26

[00141] it will be understood by those skilled in the art that the facilitated method that to use any use compound disclosed herein that forms closure member.

[00142] advantageously, the embodiment of the present invention's selection provides the polymer composition with effective character. Especially, in the embodiment of selecting, the polymer composition that forms is according to an embodiment of the present invention compared the favourable character that has as closure member with the prior art composition.

Claims (24)

1. composition, it comprises:

(A) about 10 ethene polymers to about 90 % by weight, it has about 0.947 to about 0.962g/cm³Density, about 1 to about 10g/10 minute melt index (MI);

(B) about 90 ethene polymers to about 10 % by weight, it has about 0.912 to about 0.932g/cm³Density, about 0.25 to about 6g/10 minute melt index (MI); With

Wherein component (A) and (the Δ D=D of density contrast (B)_(A)-D _(B)) be equal to or greater than 0.03g/cm³。

2. composition according to claim 1, wherein component A exists with the amount of about 40 to 85 % by weight, and B component exists with the amount of about 15 to 60 % by weight.

3. composition according to claim 2, wherein component A exists with the amount of about 65 to 80 % by weight, and B component exists with the amount of about 20 to 35 % by weight.

4. composition according to claim 1, it further comprises at least a additive of 0 to 6 % by weight, this additive is selected from lubricant, filler, pigment, antioxidant and processing aid.

5. composition according to claim 4, wherein at least a additive exists with the amount of about 0.01 to 3 % by weight.

6. composition according to claim 4, wherein at least a additive exists with the amount of about 0.015 to 0.5 % by weight.

7. composition, it comprises:

The resin of one pack system, this resin has 0.935-0.955g/cm³Density in the scope and the melt index (MI) in the 0.3-1.2g/10 minute scope, and wherein this resin comprises polyethylene polymer.

8. composition according to claim 7, wherein the scope of melt index (MI) is 0.4-1.1 g/10 minute.

9. composition according to claim 7, wherein the scope of melt index (MI) is 0.5-1.0 g/10 minute.

10. composition according to claim 7, wherein the scope of density is about 0.938 to 0.952g/cm³。

11. composition according to claim 7, wherein the scope of density is about 0.942 to 0.950g/cm³。

12. composition according to claim 7 comprises at least a additive of 0 to 6 % by weight, this additive is selected from color improvement agent, lubricant, filler, pigment, antioxidant and processing aid.

13. composition according to claim 12, wherein at least a additive exists with the amount of about 0.01 to 3 % by weight.

14. composition according to claim 12, wherein at least a additive exists with the amount of about 0.015 to 0.5 % by weight.

15. a closure member, it comprises claim 1 or 7 described compositions.

16. a closure member, it comprises at least a ethene polymers, it is characterized by to have to be equal to or greater than about 8% to about 25% short-chain branch distribution content.

17. according to claim 1 or 7 described compositions, wherein this ethylene polymer composition comprises the high density fraction less than about 80%.

18. according to claim 1 or 7 described compositions, wherein this ethylene polymer composition is characterised in that to have about 0.5 % by weight to the 1-hexene content of about 4 % by weight.

19. according to claim 1 or 7 described compositions, wherein this ethylene polymer composition is characterised in that the solvable fraction (measuring by CRYSTAF) that has greater than about 1.75%.

20. composition according to claim 7, it comprises 100ppm to the PEG400 of 1000ppm.

21. according to claim 1 or 7 described compositions, it has and surpasses 80 hours the ESCR that measures with 100%Igepal according to ASTM D-1693 method B.

22. according to claim 1 or 7 described compositions, it has and surpasses the ESCR that measured with 100%Igepal according to ASTM D-1693 method B in 150 hours.

23. according to claim 1 or 7 described compositions, wherein Mw/Mn is between 3 to 20.

24. a method that forms closure member comprises that change claim 1 or 7 described compositions are to form closure member.