CN102947067B - Improved polyolefin manufacturing process - Google Patents
Improved polyolefin manufacturing process Download PDFInfo
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- CN102947067B CN102947067B CN201180010392.4A CN201180010392A CN102947067B CN 102947067 B CN102947067 B CN 102947067B CN 201180010392 A CN201180010392 A CN 201180010392A CN 102947067 B CN102947067 B CN 102947067B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/005—Processes for mixing polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
- B29C48/10—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels flexible, e.g. blown foils
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to an improved process for compounding a polyolefin composition comprising providing feed components including one or more high molecular weight olefin polymer components and one or more low molecular weight polyolefin components. The high and low molecular weight components are then compounded together to create a molten homogeneous polyolefin mixture.
Description
Technical field
The present invention relates to a kind of improving one's methods for the manufacture of polyolefin blends, this polyolefin blends is made up of high molecular weight olefin copolymer and low molecular weight olefins copolymer.Particularly; the present invention relates to the balance optimized between dispersed mixing (dispersive mixing) and distributivity mixing (distributive mixing), keep product property simultaneously, improve the energy input entered in this product, guarantee to mix uniformity (consistency) and the productivity ratio realizing improvement.
Background technology
Polyolefin production process is known in the art, and it comprises the method preparing unimodal (monomodal) and multimodal (multimodal) polymer according to the requirement of final polyolefin products.
Particularly, multimodal polyethylene is known in the art, as U.S. Patent No. 6, and 730,751 and U.S. Patent No. 7,193, described in 017, therefore the disclosure of the two is merged in herein by reference.Term used herein " multimodal " refers to the peak that there is more than one regulation in graph of molecular weight distribution.When preparing polymer with sequential steps in the reaction vessel that two or more separate, the polymer with different molecular weight distribution and density can be obtained.
Although independent component can have monomodal molecular weight distribution, the effect of the rapid method of continuous steps of this order is the bimodal of molecular weight or multimodal distribution by a distribution superposition on the other-result.Alternatively, this polymer of preparation can be combined by the physical mixed of the different component of separately preparation and then.For some application as pressure pipe, recognize and used the blend be made up of low-molecular ethylene polymers and high molecular weight ethylene polymer to be favourable.
Multimodal polyolefin requires the specially treated in the end step manufactured, to realize desired final response, as the reduction gel of the outward appearance for improving and the dispersion of the operable additive of improvement and pigment.Can in various extrusion equipment compounded polymer, comprise mixer and add extruder structure, such as U.S. Patent No. 6,900, describedly in 266 add single screw extrusion machine at Farrel mixer, Farrel type mixer adds gear pump, independent double screw extruder or double screw extruder and add in gear pump, therefore the disclosure of this patent is incorporated herein by reference.
In the normally used art methods of one, add in single screw extrusion machine at Farrel type mixer and prepared pellet, it comprises feed column (feed tower) to introduce polymer flake and itself and the additive (it comprises antioxidant, plumper and polymer processing aids) being suitable for this application to be combined.This Farrel type mixer receives the mix flow of these materials and makes their fusings and mix them in the mixing chamber formed by rotor, mixing chamber and aperture restraint device.This single screw extrusion machine receives the melt from this mixer and is forced through granulation mouth template, this polymer flow is divided into independent logistics and is cut into pellet in comminutor under water at this place.Farrel company has delivered " Effect of rotor geometry and operating conditions on mixing performance in continuous mixers:an experimental study " in 1991 at SPE Antec, therefore its disclosure is incorporated herein by reference, and which describes the various rotor configurations for the processing of polymer melt in Farrel Continuous Mixers.
Various leaf design (lobe designs) for various compounding structure and extruder structure is disclosed in prior art document.Such as, U.S. Patent No. 6,783,270 disclose the double screw extruder with the new classification element (fractional element) that can provide different top cone angle (tip angles).But the rotor configuration of optimization for mixing and melt multimodal polyolefin all do not recorded by prior art document.
As U.S. Patent No. 6,900, shown in 266, also known during compounding process in this area, control to this polyolefin polymer energy input be important, therefore the disclosure of this patent is incorporated herein by reference.Too high energy level can make the mechanical performance of expectation demote, and too low energy level may be not enough to prepare the material application provided (as pipe) to required uniformity.
Hickie and gel are two performance indications of the uniformity for evaluating multimodal polyolefin.Undesirable gel or hickie level cause disabled polymeric articles.U.S. Patent application No. 2009/0198018 describes the method for the multimodal polymer for the preparation of the hickie with reduction, and therefore the disclosure of this application is incorporated herein by reference.
Summary of the invention
The present invention relates to improving one's methods for compounding (compounding) polyolefin composition, the method comprises providing package containing the feed component of one or more high molecular weight olefin polymers compositions with one or more low-molecular-weight polyolefin components.Then to form the uniform polyolefm mixture of melting together with this HMW being compounded in low-molecular-weight component.Term used herein " uniform polymeric " refers to standby and identical toward each other by extrusion mechanism and has the pellet (pellets) of same viscosity and density characteristics.
Detailed description of the invention
Preferably, the present invention relates to for from compounding line with the method for the compounding multimodal polyolefm composition of high production rate, realize high-caliber uniformity (being confirmed by the hickie of the gel reduced and reduction) and minimized depolymerization (being confirmed by low color level) simultaneously, thus keep the physical property of polymer melt.
Major part polyolefin manufacturers is at packaging polymer and by the polymer prills of reactor manufacture before being delivered to client.The polymer melted of this reactor manufacture must be made and extrude to make this polymer uniform, melt to make it and it is mixed with the various additive usually existed with ppm level, and to obtain more tractable nominal 1/8 " pellet of diameter.
According to a preferred method of the present invention, one or more high molecular weight olefin polymers compositions and one or more low-molecular-weight polyolefin components are provided to as charging the continuous feed system described component be delivered in one or more reaction vessel.
Polymerization temperature for method of the present invention can be-60 DEG C to about 280 DEG C, preferably 50 DEG C to about 200 DEG C, and the pressure used can be that 1 atmospheric pressure is to about 500 atmospheric pressure or higher.
Polymerization comprises solution methods, gas phase process, slurry phase process (slurry phase process) and high pressure method or its combination.Particularly preferably be gas phase or the slurry phase polymerisation of one or more alkene (its at least one is ethene or propylene).
In one embodiment, method of the present invention relates to one or more and has 2-30 carbon atom, preferably 2-12 carbon atom and the more preferably solution of the olefinic monomer of 2-8 carbon atom, high pressure, slurry or gas phase polymerization process.The present invention is particularly suitable for the polymerization of two or more olefinic monomers, and described olefinic monomer is ethene, propylene, butene-1, amylene-1,4-methyl pentene-1, hexene-1, octene-1 and decylene-1.
Other monomer in method used in the present invention comprises ethylenically unsaturated monomers, has the alkadienes of 4-18 carbon atom, conjugation or unconjugated diene, polyenoid, vinyl monomer and cycloolefin.The styrene that the non-limiting monomer that can be used in the present invention can comprise ENB, norbornadiene, isobutene, isoprene, vinylbenzocyclobutane, styrene, alkyl replace, ethylidene norbornene, bicyclopentadiene and cyclopentene.
In the most preferred embodiment of method of the present invention, the copolymer of obtained ethene, wherein has at least one carbon number and is that 3-15, preferably carbon number are 4-12 and most preferably carbon number is that the comonomer of the alpha-olefin of 4-8 is polymerized with ethene in slurry phase process.
In the another embodiment of method of the present invention, by ethene or propylene different from least two kinds comonomer polymerization to form terpolymer, optionally the one of this comonomer can be diene.
In one embodiment, the mol ratio (C of comonomer and ethene
x/ C
2) be about 0.001-0.200, be more preferably about 0.002-0.008, wherein C
xfor the amount of comonomer, C
2for the amount of ethene.
In one embodiment, the present invention relates to a kind of polymerization, be in particular gas phase or slurry phase process, it is for being polymerized independent propylene or for polypropylene and one or more other monomers, comprise ethene, and/or other has the alkene of 4-12 carbon atom.Can use U.S. Patent No. 5,296,434 and No.5,278, the bulky ligand metallocene catalyst preparing polyacrylic polymer of special bridging described in 264, therefore the disclosure of described patent is incorporated herein by reference.
Usually, in gas phase polymerization process, use continuous circulation, wherein in a part for the circulation of reactor assembly, by cyclicity gas stream (or being called recirculation stream or fluidizing agent in addition) in the reactor by the heating of polymerization heat.In another part of this circulation, by the cooling system outside this reactor, this heat is removed from recirculation composition.Usually, for the preparation of in the gas fluidized bed process of polymer, at reaction conditions, the gaseous stream comprising one or more monomers is made to be continuously circulated through fluid bed in the presence of a catalyst.This gaseous stream is taken out from described fluid bed and recycles and gets back to this reactor.Meanwhile, polymer product taken out from this reactor and add new monomer to replace the monomer of polymerization.(for example, see United States Patent (USP) 4,543,399,4,588,790,5,028,670,5,317,036,5,352,749,5,405,922,5,436,304,5,453,471,5,462,999,5,616,661 and 5,668,228, therefore all these patents are all incorporated herein by reference).
Reactor pressure in gas phase process can from about 100 psig (690 kPa) to about 600 psig (4138 kPa), preferably about 200 psig (1379 kPa) to about 400 psig (2759 kPa), more preferably from about 250 psig (1724 kPa) to about 350 psig (2414 kPa) change.
Temperature of reactor in gas phase process can from about 30 DEG C to about 120 DEG C, preferably about 60 DEG C to about 115 DEG C, more preferably from about 70 DEG C to 110 DEG C, most preferably from about 70 DEG C to about 95 DEG C changes.
Other gas phase process that method of the present invention is considered comprises series or multi-stage polymeric process (series or multistage polymerization processes).The gas phase process that the present invention considers also comprises and is recorded in U.S. Patent No. 5,627,242, No.5,665,818 and No.5,677,375 and Europe open EP-A-0 794 200, EP-Bl-0 649 992, EP-A-0 802 202 and EP-B-634 421 in those, therefore all these documents are all incorporated herein by reference.
In a preferred embodiment, the reactor used in the present invention can and method of the present invention preparation be greater than 500 lbs polymer/hour (227 Kg/hr)-Yue 200, 000 lbs/hr (90, 900 Kg/hr) or more polymer, be preferably greater than 1000 lbs/hr (455 Kg/hr), more preferably greater than 10, 000 lbs/hr (4540 Kg/hr), even more preferably greater than 25, 000 lbs/hr (11, 300 Kg/hr), also more preferably greater than 35, 000 lbs/hr (15, 900 Kg/hr), even also more preferably greater than 50, 000 lbs/hr (22, 700 Kg/hr) and be most preferably greater than 65, 000 lbs/hr (29, 000 Kg/hr) to being greater than 100, 000 lbs/hr (45, 500 Kg/hr).
The pressure that slurry phase polymerisation process generally uses is about 1-about 50 atmospheric pressure and even larger, and temperature is 0 DEG C of-Yue 120 DEG C.In slurry polymerization, in liquid polymerization diluent medium, form the suspension of solid particle polymer, in this liquid polymerization diluent medium, be added with ethene and comonomer and usual hydrogen and catalyst.The suspension comprising diluent is shifted out from reactor off and on or continuously, wherein volatile component is separated with polymer and recycles (optionally, after distillation) to this reactor.Typically, be the alkane with 3-7 carbon atom for the liquid diluent in described polymerisation medium, preferred branched paraffin.The medium used should be liquid under polymerization conditions and be relative inertness.When a propane medium is used, the method must higher than reaction diluent critical-temperature and pressure operation.Preferably, hexane or iso-butane medium is used.A kind of preferred polymeric technology of the present invention is called particle form polymerization, or wherein temperature keeps below the slurry process that polymer enters the temperature in solution.Such technology is well known in the art, and is recorded in such as U.S. Patent No. 3,248, and in 179, it is all incorporated herein by reference.Other slurry process comprise use annular-pipe reactor those and use those of stirred reactor of multiple series, parallel or its combination.The not limiting example of slurry process comprises continuous print endless tube or agitator tank method.In addition, in U.S. Patent No. 4,613,484 and No.5,986, describe other example of slurry process in 021, described patent is all incorporated herein by reference.
In one embodiment, the reactor used in slurry process of the present invention can and method of the present invention preparation be greater than 2000 lbs polymer/hour (907 Kg/hr), more preferably greater than 5000 lbs/hr (2268 Kg/hr), and be most preferably greater than 10,000 lbs/hr (4540 Kg/hr).In another embodiment, the slurry-phase reactor preparation used in method of the present invention is greater than 15,000 lbs polymer/hour (6804 Kg/hr), be preferably greater than 25,000 lbs/hr (11,340 Kg/hr), and be most preferably greater than about 100,000 lbs/hr (45,500 Kg/hr).
The example of solution methods is recorded in U.S. Patent No. 4,271, and 060, No.5,001,205, No.5,236,998, No.5,589,555 and No.5,977,251 and PCT WO 99/32525 and PCT WO 99/40130 in, they are all incorporated herein by reference.
Various method has all been used to this process, but is all incorporated with the continuous feed system of the constant ratio that can keep between the polyolefin component of powdered and any other additive (the general part as the formula logistics (recipe stream) of first step is merged in).Once all compositions be mixed the ratio realizing wishing, just obtain uniform formula logistics.
With constant rate of speed, this formula logistics is caused the entrance of mixing and melting unit.Then to form homogeneous bi's polyolefin blend of melting together with HMW being compounded in lower-molecular-weight component, or " melt ".
This blend step can be carried out in such as continuous mixer (as Farrel Continuous Mixer (FCM)) or double screw extruder (as Coperion ZSK).In a preferred embodiment, FCM is used to blend step and for fusing step afterwards.Mixer rotor by powder feed to closed-chamber to compress this powder between described rotor itself and between described rotor and locular wall.
This completes by this way: powder particle and the friction between rotor and wall are enough melted this polymer and formed molten polymer and additive group.By this way by polymer and additive mixing also homogenising.
Than can (specific energy) be measuring of motor energy in the described mixer of input in melt, and kilowatt (" kW ") that be defined as motor power be divided by kg/hr polymer throughput of (" kg/h ").By changing this than energy, the time of staying of melt group in described mixer (melt pool) can be affected.
According to method of the present invention, find that the ratio changed in described mixer can change the melt behavior in described extruder.Connect with mixer, extruder behavior is optimized, and this provides the disposed of in its entirety rate of increase.Utilize mixer and the extruder of series connection, due to the friction of the increase of melt and extruder wall, the flow forward in extruder can be made to maximize, thus increase productivity ratio.In a preferred embodiment, described ratio can be remained on be less than 0.2 kWh/kg.
In described mixer, the time of staying of melt is subject to rotor type and some craft control appliance as the impact of discharge opening, radial gate valve (radial gate valves) or rotating rod (rotary bars).
The size of reduction holes opening has raising polymer-melt temperature and increases the effect that polymer spends in the time in this mixer.Described rotor type also affects incorporation time and its path of taking when polymer moves to the discharging opening of this mixing chamber from entrance.Such as, compared with style (style) 7/15 rotor combination, style 15/15 rotor combination used in described FCM all tends to produce the relatively large time of staying in this mixer at any hole opening size.
Except above-mentioned rotor style, compare with 15 single hop rotors with style 7, other useful pattern comprises style 22 and style 24 two-stage rotor.Section refers to the Mixed Zone separated in rotor.Style 7 and 15 only has feed flight (flight) region, is then interaction top (apex) region wherein occurring to melt and mix.Existence second, shorter secondary Mixed Zone in style 22 and 24.
According to an embodiment, use two dissimilar rotor designs (dissimilar rotor designs), thus the top of described rotor is offset from each other (offset from each other).This skew can be axial orientation or tangential orientation (axial or tangential in orientation).This makes product melt bypass (bypass) minimize and adds distributing mixing.Along with the mixing improved, in final products, gel reduces.Preferably, the gel area (gel area) of the film generated by polyolefin composition is less than 265/236 square inch.
According to this embodiment, in mixer combination unit (mixer assembly), rotor is equipped with leaf combination alternately, preferably staggered helical rotor (staggered helix rotors), to realize the speed of Billy with the lower energy in the cards of the mixer combination unit with similar rotor and Geng Gao.Prior art is taught in mixer combination unit and uses similar rotor, and this produces higher ratio energy, kWh/kg.As shown in this article, higher ratio can cause some degradeds of the increase of melt index (MI) and final granule product.
The use of dissimilar rotor allows more effective dispersion and the back mixing of described mixer interpolymer melt.Due to the improvement mixed and disperse, leave the final polymer melt of described mixer evenly and there is lower gel level.In addition, along with larger uniformity and less focus (hot spots), described mixer combination unit achieves the ratio energy lower than the commeasurable combination unit of the top rotor (apex rotors) with coupling, kWh/kg.
Selectively, an embodiment of described method utilizes the rotor run with friction speed.Use the rotor operated at the same rate according to the current practice of prior art.Use different spinner velocities to enable the operating personnel of the method accurately control energy and be input to optimal level, make melt treatment amount maximize simultaneously.This causes the method improved, and wherein, final granule product illustrates the gel of reduction and lower color, maintains the physical property of this final granule product simultaneously.Preferably, the color recorded by b-color standard will be less than 5.0.
According to this embodiment, when they rotate with identical speed, the orientation of a rotor and another rotor is fixing, or when they rotate with friction speed, orientation is constantly change.General compared with low velocity in larger-diameter mixer.For two speed, typically be worth for 12 according to preferred embodiment " be about 228 rpm-about 258 rpm for diameter FCM, for being low to moderate 4 " diameter use higher rpm scope compared with small machine and for up to 21 " the larger machine of diameter uses lower speed.
According to variable velocity embodiment, The inventive method achieves lower ratio can (kWh/kg) use, and makes the temperature of the melt entering described extruder be in low temperature.Melt temperature to the reduction of this extruder allows the melt increased to the friction of extruder wall.The friction of this increase is crucial for moving forward of molten polymer of raising.By control inputs to this polymer melt ratio can and remained minimum of a value, operating personnel are therefore, it is possible to realize the productivity ratio improved from the extruder of same size.And, as seem whiter pellet confirm, to control than described method being made depolymerization to be minimized to minimum ability.
And then the actual Mixed Zone of method of the present invention starts after described feed flight end.It is made up of the district with the effect of moving forward and some reverse migration back to back.The motion of this conflict forces polymer to be compressed and melts and mix.
The third step of method of the present invention melt is forced through mouth template (die plate), and object is to prepare pellet.Those or the double screw extruder that comprise that FCM single screw extrusion machine (as mentioned above), gear pump produce as Maag for the suitable equipment in this step as Coperion produce.
The function of this pressurization steps after described molten polymer, produces enough pressure thus polymer is forced through granulation mouth template.Single screw extrusion machine used in the method is the single screw extrusion machine with variable speed drive motor.Governing speed thus the output of this extruder is mated with the output of mixer in second step.
Described extruder receives the molten polymer logistics as gravity charging in skewed slot, and this skewed slot is designed to hold this molten polymer logistics and it is guided to extruder screw in porch.This melt is directed to the screw thread place of this extruder screw.Reciprocating type plunger (ram) is installed in the side of the entrance feed hopper of this extruder screw, to assist this molten polymer to shift onto in screw flight.By regulating extruder screw revolution (" rpm ") per minute, make to mate with the output of mixer from the flowing of this extruder.
Then the melt of pressurization is transferred by granulation mouth template, at this place, described polymer flow is divided into independently logistics and is cut into uniform multimodal polyolefm composition pellet.
According to a kind of embodiment of the present invention, this uniform multimodal polyolefin granule product comprises the bimodal polyethylene blend be made up of higher molecular weight ethylene copolymer and lower molecular weight ethene polymers, its melt index (MI) (MI5) 190/5 is 0.15-0.45 g/10 min, density is 0.947-0.955 g/cc, environmental stress cracking resistance ESCR (PENT) >500 hr.MI5 and ESCR (PENT) is the ASTM test for measuring polyolefinic viscosity and stress cracking resistance.
The polymer obtained by method of the present invention may be used for large-tonnage product and terminal uses application.Polymer obtained by method of the present invention comprises LLDPE, elastomer, plastic body, high density polyethylene (HDPE), medium density polyethylene, low density polyethylene (LDPE), multimodal or bimodal high molecular weight polyethylene, polypropylene and polypropylene copolymer.
Depend on desired purposes, the density of described polymer (being generally polyvinyl) is 0.86 g/cc-0.97 g/cc.For some application, the density of 0.88 g/cc-0.920 g/cc is preferred, and in other application (as pipe, film and blowing), the density of 0.930 g/cc-0.965 g/cc is preferred.For low-density polymeric, as applied for film, the density of 0.910 g/cc-0.940 g/cc is preferred.According to ASTM-D-1238 density measurement.
Molecular weight distribution (ratio (the M of weight average molecular weight and number-average molecular weight of the polymer obtained by method of the present invention
w/ M
n)) can for being greater than 1.5 to about 70.In some embodiments, obtained polymer has the narrow M for about 1.5-15
w/ M
n, and in other embodiments, the M of obtained polymer
w/ M
nfor about 30-50.And, polymer of the present invention can have recorded by Composition Distribution Breadth Index (CDBI) narrow or wide form distribution.Other details determining the CDBI of copolymer is well known by persons skilled in the art.Such as, see PCT patent application WO 93/03093 (being disclosed on February 18th, 1993), it is all incorporated herein by reference.In some embodiments, the CDBI of obtained polymer can be 80% or larger or CDBI can be 50% or less.
In one embodiment, the CDBI of polymer of the present invention is generally and is greater than 50% to 100%, and preferably 99%, preferred 55%-85%, and be more preferably 60%-80%, be even more preferably and be greater than 60%, be also even more preferably and be greater than 65%.
In another embodiment, the CDBI of the polymer utilizing the present invention to obtain, for being less than 50%, being more preferably and being less than 40%, and most preferably is and is less than 30%.
In one embodiment, the melt index (MI) (MI) measured by ASTM-D-1238-E of polymer of the present invention or (I
2) be 0.01 dg/min-1000 dg/min, be more preferably about 0.01 dg/min-about 100 dg/min, be even more preferably about 0.01 dg/min-about 50 dg/min, and most preferably be about 0.1 dg/min-about 10 dg/min.
In one embodiment, the melt index (MI) ratio (I of polymer of the present invention
21/ I
2) (I
21recorded by ASTM-D-1238-F) for 10-is less than 25, is more preferably about 15-and is less than 25.
In a preferred embodiment, the melt index (MI) ratio (I of polymer of the present invention
21/ I
2) (I
21recorded by ASTM-D-1238-F) for being preferably greater than 25, more preferably greater than 30, even more preferably greater than 40, be also even also most preferably greater than 65 more preferably greater than 50.In one embodiment, polymer of the present invention can have Narrow Molecular Weight Distribution and the distribution of wide composition or vice versa, and can be U.S. Patent No. 5, and 798, those polymer described in 427, its disclosure is incorporated herein by reference.
Embodiment
Provide the following examples for explaining explanation various embodiments of the present invention.They are not intended to represent all embodiments of the present invention and should be interpreted as limiting described claimed scope of the present invention herein.All numerical value described herein are all approximations and can change in its true scope.
Embodiment 1
Utilize a style 7 to add style 15 rotor (being abbreviated as 7/15) and various handling rate and temperature and complete a series of test, and then on same equipment but adopt two style 15 rotors (being abbreviated as 15/15) implement one group of experiment.Use bimodal polyethylene polymer.The energy measurement consumed by mixer is kWh/kg and measures b-color and the gel of pellet.The result of these tests is shown in figure below.
B-color is the standard A STM test of measuring polymer yellowing.The product of the yellowing that less numeric representation is lower and better quality.As shown in following table, the dissimilar rotor orientation of the application of the invention, the b-color of pellet is reduced to 2.5 from 11.7 when using Farrell 15/15 rotor of coupling.When multimodal polyethylene pellet, be preferred lower than the b-color of 4.0.
Gel area is the test of the amount measuring non-molten material in the film that obtained by this material.As for b-color, numerical value is lower, and the quality of final products is better.As shown in following table, gel area drops to 265/236 square inch from 555/236 square inch.
Test in this embodiment 4 " Farrel mixer adds 4 " extruder carries out under Farrel, various spinner velocity carry out evaluation and adjustment hole with realize target energy level.Utilize style 7 rotor to add style 15 rotor and carry out first group of experiment.Two style 15 rotors are utilized to carry out second group of experiment and utilize these rotors to repeat same battery of tests.
The test matrix often organizing experiment is shown in following table.
For the test matrix tested
| Run # | Center Pt | Rotor | Speed | Rotor rpm |
| 1 | 1 | Style 7/15 | 667 | 383 |
| 2 | 0 | Style 7/15 | 556 | 418 |
| 3 | 1 | Style 7/15 | 444 | 383 |
| 4 | 1 | Style 7/15 | 667 | 453 |
| 5 | 0 | Style 7/15 | 556 | 418 |
| 6 | 1 | Style 7/15 | 444 | 453 |
| 7 | 1 | Style 7/15 | 519 | 383 |
| 8 | 0 | Style 7/15 | 444 | 418 |
| 9 | 1 | Style 7/15 | 519 | 453 |
| 10 | 1 | Style 7/15 | 370 | 383 |
| 11 | 1 | Style 7/15 | 370 | 453 |
| 12 | 0 | Style 7/15 | 444 | 418 |
| 1 | 1 | Style 15/15 | 667 | 383 |
| 2 | 0 | Style 15/15 | 556 | 418 |
| 3 | 1 | Style 15/15 | 444 | 452 |
| 4 | 1 | Style 15/15 | 667 | 452 |
| 5 | 1 | Style 15/15 | 444 | 383 |
| 6 | 0 | Style 15/15 | 556 | 418 |
| 7 | 1 | Style 15/15 | 519 | 452 |
| 8 | 0 | Style 15/15 | 444 | 418 |
| 9 | 1 | Style 15/15 | 519 | 383 |
| 10 | 0 | Style 15/15 | 444 | 418 |
| 11 | 1 | Style 15/15 | 370 | 383 |
| 12 | 1 | Style 15/15 | 370 | 452 |
For all tests utilizing 15/15 rotor to carry out, by the cigarette that sends from mixer discharging and from two of mixer melt band not same district confirm degraded.The result obtained is shown in Fig. 1,2 and 3.
Embodiment 2
Have rated the difference between the mixer of constant speed operation and the mixer of non-constant speed operation.Compare the commodity production line running same multimodal polyethylene, mixer 1 runs 7/15 rotor with 300 identical rpm speed, and the second mixer runs 7/15 rotor, and one with 258 rpm operations, another runs with 228 rpm.Under indicate same speed under the difference of energy that consumes.
| Mixer 1 | Mixer 2 | |
| Rotor | 7/15 | 7/15 |
| Speed lbs/hr | 13600 | 13500 |
| Mixer energy kWh/kg | 0.205 | 0.165 |
| Spinner velocity rpm | 300 and 300 | 258 and 228 |
Embodiment 3
12 " test in mixer, wherein than being 0.20-0.23, and then wherein energy drop to 0.17-0.19 kWh/kg.In both cases, rotor is with the running of different speed, and one with 258 rpm, another is with 228 rpm, and polymer feed is multimodal polyethylene thin slice.As shown in following table, method of the present invention causes the speed of under lower mixer energy high 50%.The key component of this raising is owing to applying less energy to the melt in described mixer, makes the melt that described extruder process is more tacky.Fetching in viscous melt charging, single screw extrusion machine is more effective, and melt is less bonded in screw rod, and extruder barrel is cooled and melt is bonded in this machine barrel, and viscous flow is stronger relative to pressure current.Meanwhile, polymer stuffing plunger (stuffer ram) gap (clearance) is from about 0.75 " drop to be less than 0.5 ".
| Situation 1 | Situation 2 | |
| Mixer energy kWh/kg | 0.221 | 0.186 |
| Gross energy kWh/kg | 0.302 | 0.267 |
| Sizer gap (crammer clearance), in. | 0.75 | <0.50 |
| Speed lbs/hr | 8870 | 13362 |
Embodiment 4
Using 4 of mixer/extruder " implementation evaluation on diameter half active line (semi works line) and commodity production line, with evaluate bimodal polyethylene resins productivity ratio and than energy performance.Result display utilizes the different rotors ratio melted needed for described polymer to be reduced to be less than 0.25 kWh/kg, and when running similar rotor design with identical speed for 0.29.On commodity production line, the energy of dissimilar rotor is utilized to drop to lower than 0.2 kWh/kg, and 12 " mixer adds 12 " productivity ratio is from 10 in extruder, 500 lbs/hr are raised to 13,500 lbs/hr.
The evaluation of performance that the mixer combination unit of 1500 lbs/hr scales is implemented, that evaluate the various rotor configurations for granulation bimodal polyethylene shows the benefit of the inventive method.Use wherein in the structure of same style rotor and observe higher ratio energy.Viewed mixer above described extruder molten polymer display Liang Ge different melt district out.A district has than another region and significantly improves in yellowing.When with when long style rotor do not replaced by rotor in specie, observe directly the reduction of every kWh/kg energy ezpenditure and whiter melt color.
Although present invention is described about a limited number of embodiment, the specific features of an embodiment should not belonged to other embodiment of the present invention.Neither one embodiment represents all aspects of the present invention.And, there is the distortion and change that obtain from them.Such as, described multimodal polyolefin feed component can comprise three components (Alathon or copolymer), and it makes composition be three peaks in whole molecular weight distribution.Similarly, the 4th, the 5th or the 6th component can also be added to regulate the physical property of said composition.
Also various additive can be used to strengthen one or more performances further.In other embodiments, described feed component is made up of LMW component described herein and HMW component substantially.In some embodiments, feed composition is substantially free of any additive specifically do not listed herein.In certain embodiments, feed composition is substantially free of nucleator.By physics or chemical method carry out crosslinked can be the mode of alternative change feed composition.Appended claim is intended to contain and falls into all such distortion in the scope of the invention and change.
Claims (15)
1., for the preparation of the method for uniform polyolefin composition, it comprises the following steps:
A., one or more high molecular weight olefin polymers compositions and one or more low-molecular-weight polyolefin components are provided;
B. this high molecular weight olefin polymers compositions compounding and this low-molecular-weight polyolefin component in continuous mixer, this mixer comprises two or more dissimilar rotors offset each other on top, to produce uniform multimodal polyolefin melt;
C. this melt is moved to extruder or gear pump from this mixer; With
D. this melt is pressurizeed to move by granulation mouth template by it from this extruder or gear pump, wherein polymer flow be divided into logistics separately and be cut into uniform multimodal polyolefm composition pellet.
2. the process of claim 1 wherein that described low-molecular-weight polyolefin component is polymerized in a reactor, described high molecular weight olefin polymers compositions is polymerized in different reactors, and wherein this two reactor serial operations or parallel operation.
3. the process of claim 1 wherein that described high molecular weight olefin polymers compositions is selected from ethene, propylene, butene-1, amylene-1,4-methyl pentene-1, hexene-1, octene-1 and decylene-1.
4. the process of claim 1 wherein that described low-molecular-weight polyolefin component is selected from ethene, propylene, butene-1, amylene-1,4-methyl pentene-1, hexene-1, octene-1 and decylene-1.
5. the process of claim 1 wherein described low-molecular-weight polyolefin component and the ethene polymers of described high molecular weight olefin polymers compositions separately for utilizing slurry phase polymerisation process to be polymerized.
6. the method for claim 5, wherein each slurry phase polymerisation process carries out in slurry loop or slurry autoclave.
7. the method for claim 5, wherein said polymerization operation in tandem.
8. the process of claim 1 wherein described low-molecular-weight polyolefin component and the ethene polymers of described high molecular weight olefin polymers compositions separately for utilizing gas phase polymerization process to be polymerized.
9. the method for claim 8, wherein said polymerization operation in tandem.
10. the method for claim 1, wherein this uniform multimodal polyolefm composition granule product comprises bimodal polyethylene blend, this bimodal polyethylene blend is by the ethylene copolymer of higher molecular weight and the ethene polymers preparation of lower molecular weight and melt index (MI) (MI5) 190/5 is 0.15-0.45 g/10 min, density is 0.947-0.955 g/cc, and environmental stress crack resistance ESCR (PENT) is greater than 500 hr.
11. the process of claim 1 wherein and make described rotor with different speed operations.
The method of 12. claims 11, wherein spinner velocity is 228 rpm-258 rpm.
13. the process of claim 1 wherein that the gel area of the film generated by described polyolefin composition is less than 265/1523 square centimeter.
14. the process of claim 1 wherein that the b-color of polyolefin composition is less than 5.0, and wherein this b-color is tested by the standard A STM measuring polymer yellowing to obtain.
15. the process of claim 1 wherein in the mixer, and the ratio on described polyolefin composition can be less than 0.2 kWh/kg.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US33870010P | 2010-02-22 | 2010-02-22 | |
| US61/338,700 | 2010-02-22 | ||
| US61/338700 | 2010-02-22 | ||
| PCT/EP2011/052425 WO2011101438A1 (en) | 2010-02-22 | 2011-02-18 | Improved polyolefin manufacturing process |
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| CN102947067A CN102947067A (en) | 2013-02-27 |
| CN102947067B true CN102947067B (en) | 2015-06-03 |
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| CN201180010392.4A Expired - Fee Related CN102947067B (en) | 2010-02-22 | 2011-02-18 | Improved polyolefin manufacturing process |
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|---|---|
| EP (1) | EP2539123A1 (en) |
| JP (1) | JP2013520525A (en) |
| CN (1) | CN102947067B (en) |
| RU (1) | RU2573325C2 (en) |
| WO (1) | WO2011101438A1 (en) |
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| CA2847628A1 (en) | 2014-03-28 | 2015-09-28 | Nova Chemicals Corporation | Improved extrusion process |
| WO2016087566A1 (en) | 2014-12-04 | 2016-06-09 | Basell Polyolefine Gmbh | Process for preparing a polyolefin composition |
| CN111902467B (en) | 2018-02-05 | 2022-11-11 | 埃克森美孚化学专利公司 | Processability of LLDPE enhanced by addition of ultra high molecular weight high density polyethylene |
| CN108943655B (en) * | 2018-06-05 | 2020-10-02 | 宁波大学 | Extrusion molding method of high-strength bimodal polyethylene/chitin nanocrystalline composite material |
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| CN102947067A (en) | 2013-02-27 |
| WO2011101438A1 (en) | 2011-08-25 |
| RU2573325C2 (en) | 2016-01-20 |
| RU2012140373A (en) | 2014-03-27 |
| EP2539123A1 (en) | 2013-01-02 |
| JP2013520525A (en) | 2013-06-06 |
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