CN102947067A - Improved polyolefin manufacturing process - Google Patents
Improved polyolefin manufacturing process Download PDFInfo
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- CN102947067A CN102947067A CN2011800103924A CN201180010392A CN102947067A CN 102947067 A CN102947067 A CN 102947067A CN 2011800103924 A CN2011800103924 A CN 2011800103924A CN 201180010392 A CN201180010392 A CN 201180010392A CN 102947067 A CN102947067 A CN 102947067A
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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
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 ofly for the manufacture of the improving one's methods of polyolefin blends, this polyolefin blends is made by high molecular weight olefin copolymer and low molecular weight olefins copolymer.Particularly; the present invention relates to optimize dispersed balance of mixing between (dispersive mixing) and the distributivity mixing (distributive mixing), the energy that keeps simultaneously product property, improvement to enter in this product is inputted, is guaranteed to mix uniformity (consistency) and realize improved productivity ratio.
Background technology
Polyolefin production process is known in the art, and it comprises that the requirement according to final polyolefin products prepares the method for unimodal (monomodal) and multimodal (multimodal) polymer.
Particularly, multimodal polyethylene is known in the art, such as U.S. Patent No. 6,730,751 and U.S. Patent No. 7,193,017 in put down in writing, therefore the disclosure of the two is merged in herein by reference.Term used herein " multimodal " refers to exist the peak more than a regulation in graph of molecular weight distribution.When preparing polymer with sequential steps in the reaction vessel that separates at two or more, can make and have that different molecular weight distributes and the polymer of density.
Although independent component can have monomodal molecular weight distribution, the effect of the rapid method of continuous steps of this order be a distribution is superimposed upon on another-result is that the bimodal or multimodal of molecular weight distributes.Alternatively, can also then make up this polymer of preparation by the physical mixed of separating the different component for preparing.Use such as pressure pipe for some, recognized that it is favourable using the blend of being made by low-molecular ethylene polymers and high molecular weight ethylene polymer.
Multimodal polyolefin requires the specially treated in the ending step of making, to realize desired final response, such as the reduction gel and the dispersion that improves operable additive and pigment for the outward appearance of improving.Can be in various extrusion equipments the compounding polymer, comprise that mixer adds the extruder structure, for example such as U.S. Patent No. 6,900, be documented in the Farrel mixer in 266 and add that single screw extrusion machine, Farrel type mixer add gear pump, independent double screw extruder or double screw extruder adds in the gear pump, therefore the disclosure of this patent is incorporated herein by reference.
In a kind of normally used art methods, add at Farrel type mixer and to have prepared pellet in the single screw extrusion machine, it comprises that feed column (feed tower) is to introduce polymer flake and with itself and additive (it comprises antioxidant, plumper and the polymer processing aids) combination that is suitable for this application.This Farrel type mixer receives the mix flow of these materials and makes their fusings and mix them in the mixing chamber that is formed by rotor, mixing chamber and aperture restraint device.This single screw extrusion machine receives from the melt of this mixer and with it and pressurizes by the granulation mouth template, at this place this polymer flow is divided into independent logistics and also is cut into pellet in the comminutor under water.Farrel company has delivered " Effect of rotor geometry and operating conditions on mixing performance in continuous mixers:an experimental study " at SPE Antec in 1991, therefore its disclosure is incorporated herein by reference, and it has put down in writing the various rotor configurations that are used in the processing of Farrel Continuous Mixers polymer melt.
The various leaf designs (lobe designs) and the extruder structure that are used for various compounding structures are disclosed in the prior art document.For example, U.S. Patent No. 6,783,270 disclose and have had the double screw extruder that the new classification element of different top cone angle (tip angles) (fractional element) can be provided.Yet the prior art document does not all have record to be used for mixing and melting the rotor configuration of the optimization of multimodal polyolefin.
Such as U.S. Patent No. 6,900, shown in 266, also to have known during the compounding process in this area, the energy input that is controlled to this polyolefin polymer is important, therefore the disclosure of this patent is incorporated herein by reference.Too high energy level can make the mechanical performance degradation of expectation, and excessively low energy level may be not enough to prepare for the application that provides (such as pipe) and has required inhomogeneity material.
Hickie and gel are for inhomogeneity two performance indications of estimating multimodal polyolefin.Undesirable gel or hickie level cause disabled polymeric articles.U.S. Patent application No. 2009/0198018 has put down in writing the method for the preparation of the multimodal polymer 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 for the improving one's methods of compounding (compounding) polyolefin composition, the method comprises provides the feed component that comprises one or more high molecular weight olefin polymers compositions and one or more low-molecular-weight polyolefin components.Then this HMW and low-molecular-weight set of dispense are mixed to form the even polyolefin blend of melting.Term used herein " uniform polymeric " refers to and pellet (pellets) toward each other identical and that have same viscosity and density characteristics standby by extrusion mechanism.
The specific embodiment
Preferably, the present invention relates to for from the method for compounding production line with high production rate compounding multimodal polyolefin composition, realize simultaneously high-caliber uniformity (hickie by the gel that reduces and reduction confirms) and minimized depolymerization (being confirmed by low color level), thereby keep the physical property of polymer melt.
The polymer granulation of before major part polyolefin manufacturer delivers to the client at the packing polymer and with it reactor being made.Must make the polymer melted of this reactor manufacturing and extrude so that this polymer homogenising, so that its fusing and it is mixed with the various additives that usually exist with the ppm level, and to make 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 the continuous feed system that described component is delivered in one or more reaction vessels as charging.
The polymerization temperature that is used for method of the present invention can be-60 ℃ to about 280 ℃, preferred 50 ℃ to about 200 ℃, and employed pressure can be 1 atmospheric pressure about 500 atmospheric pressure or higher extremely.
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 (it is at least a to be ethene or propylene).
In one embodiment, method of the present invention relates to one or more and has 2-30 carbon atom, preferred 2-12 carbon atom, also more preferably solution, high pressure, slurry or the gas phase polymerization process of the olefinic monomer of 2-8 carbon atom.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-amylene-1, hexene-1, octene-1 and decylene-1.
Can be used for alkadienes, conjugation or unconjugated diene, polyenoid, vinyl monomer and cycloolefin that other monomer in the method for the present invention comprises ethylenically unsaturated monomers, has 4-18 carbon atom.The non-limiting monomer that can be used among the present invention can comprise styrene, ethylidene norbornene, bicyclopentadiene and the cyclopentene that ENB, norbornadiene, isobutene, isoprene, vinyl benzo cyclobutane, styrene, alkyl replace.
In the most preferred embodiment of method of the present invention, make the copolymer of ethene, wherein have at least a carbon number and be 3-15, preferred carbon number and be 4-12 and most preferably carbon number be comonomer and ethene polymerization in slurry phase process of the alpha-olefin of 4-8.
In the another embodiment of method of the present invention, the comonomer polymerization that ethene or propylene is different from least two kinds is to form terpolymer, and randomly a kind of 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, more preferably about 0.002-0.008, wherein C
xBe the amount of comonomer, C
2Amount for ethene.
In one embodiment, the present invention relates to a kind of polymerization, be in particular gas phase or slurry phase process, it is used for the independent propylene of polymerization or is used 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, the bulky ligand metalloscene catalyst of the special bridging of putting down in writing in 434 and No.5,278,264 prepares polyacrylic polymer, and therefore the disclosure of described patent is incorporated herein by reference.
Usually, in gas phase polymerization process, use continuous circulation, wherein in the part of the circulation of reactor assembly, cyclicity gas stream (perhaps being called in addition recirculation stream or fluidizing agent) is heated by the polymerization heat in this reactor.In another part of this circulation, the cooling system outer by this reactor removes this heat from the recirculation composition.Usually, in the gas fluidized bed process for the preparation of polymer, under reaction condition, in the presence of catalyst, make the gaseous stream continuous circulation that comprises one or more monomers pass through fluid bed.This gaseous stream is got back to this reactor from described fluid bed taking-up and recirculation.Simultaneously, polymer product is taken out and adds the monomer that new monomer is replaced polymerization from this reactor.(for example referring to 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 all are incorporated herein by reference).
Reactor pressure in the gas phase process can be from about 100 psig (690 kPa) to about 600 psig (4138 kPa), preferred about 200 psig (1379 kPa) are to about 400 psig (2759 kPa), and more preferably from about 250 psig (1724 kPa) change to about 350 psig (2414 kPa).
Temperature of reactor in the gas phase process can be from about 30 ℃ to about 120 ℃, and preferred about 60 ℃ to about 115 ℃, more preferably from about 70 ℃ to 110 ℃, most preferably from about 70 ℃ are arrived about 95 ℃ of variations.
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 all are incorporated herein by reference.
In a kind of preferred embodiment, among the present invention employed reactor can and method of the present invention preparation 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 most preferably greater than 65,000 lbs/hr (29,000 Kg/hr) extremely greater than 100,000 lbs/hr (45,500 Kg/hr).
The pressure of slurry phase polymerisation process normal operation for about 50 atmospheric pressure of about 1-with in addition larger, temperature is 0 ℃-Yue 120 ℃.In slurry polymerization, in the liquid polymeric diluent medium, form the suspension of solid particle polymer, in this liquid polymeric diluent medium, be added with ethene and comonomer and common hydrogen and catalyst.The suspension that will comprise diluent shifts out from reactor off and on or continuously, wherein volatile component is separated with polymer and recycles (randomly, after distillation) to this reactor.Typically, the liquid diluent that is used for described polymerisation medium is the alkane with 3-7 carbon atom, preferred branched paraffin.Employed medium should and be relative inertness for liquid under polymerizing condition.When using propane medium, the method must be higher than reaction diluent critical-temperature and pressure operation.Preferably, use hexane or iso-butane medium.A kind of preferred polymeric technology of the present invention is called the particle form polymerization, and perhaps wherein temperature keeps below the slurry process that polymer enters the temperature in the solution.Such technology is well known in the art, and for example is recorded in the U.S. Patent No. 3,248,179, and it all is incorporated herein by reference.Other slurry process comprise use annular-pipe reactor those and use those of stirred reactor of a plurality of series, parallel or its combination.The non-limiting example of slurry process comprises continuous endless tube or agitator tank method.In addition, in U.S. Patent No. 4,613, put down in writing other example of slurry process in 484 and No.5,986,021, described patent all has been incorporated herein by reference.
In one embodiment, the reactor that uses in the slurry process of the present invention can and method of the present invention preparation greater than 2000 lbs polymer/hour (907 Kg/hr), more preferably greater than 5000 lbs/hr (2268 Kg/hr), and most preferably greater than 10,000 lbs/hr (4540 Kg/hr).In another embodiment, employed slurry-phase reactor preparation is greater than 15 in the method for the present invention, 000 lbs polymer/hour (6804 Kg/hr), be preferably greater than 25,000 lbs/hr (11,340 Kg/hr), and 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 all are incorporated herein by reference.
The whole bag of tricks all is used to finish this process, but has all incorporated the continuous feed system of the constant ratio between the polyolefin component that can keep powdered and any other additive (the general part as the prescription logistics (recipe stream) of first step is merged in) into.In case all compositions are mixed to realize the ratio of wishing just to have made uniform prescription logistics.
Cause and mix and the entrance of melting unit with the constant rate of speed logistics of will filling a prescription.Then HMW and lower-molecular-weight component are compounded in together to form the even bimodal polyolefin mixture of melting, or " melt ".
Can in for example continuous mixer (such as Farrel Continuous Mixer (FCM)) or double screw extruder (such as Coperion ZSK), carry out this blend step.In a preferred embodiment, FCM is used to blend step and is used for afterwards fusing step.The mixer rotor with powder feed to the closed-chamber with this powder of compression between described rotor itself and between described rotor and locular wall.
This finishes by this way: the friction between powder particle and rotor and the wall is enough melted this polymer and is formed molten polymer and additive group.By this way polymer and additive are mixed and homogenising.
Specific energy (specific energy) is the measuring of the motor energy in the melt in the described mixer of input, and kilowatt (" kW ") that be defined as motor power is divided by in kg/hr polymer throughput of (" kg/h ").By changing this specific energy, can affect the time of staying of melt group in the described mixer (melt pool).
The method according to this invention, the specific energy in the described mixer of discovery change has changed the melt behavior in the described extruder.Connect with mixer, the extruder behavior is optimized, and this provides the disposed of in its entirety rate that increases.The friction of the increase of melt and extruder wall utilizes mixer and the extruder of series connection, owing to can make the maximization of flowing forward in the extruder, thereby increase productivity ratio.In a preferred embodiment, described specific energy is remained on less than 0.2 kWh/kg.
The time of staying of melt is subjected to rotor type and some craft control appliance such as discharge opening, the radially impact of gate valve (radial gate valves) or rotating rod (rotary bars) in the described mixer.
The size that reduces the hole opening has the 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.For example, compare with style (style) 7/15 rotor combination, style 15/15 rotor combination that uses 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, to compare with 15 single hop rotors with style 7, other useful pattern comprises style 22 and style 24 two-stage rotors.Section refers to the Mixed Zone that separates in the rotor.Style 7 and 15 only has charging screw thread (flight) zone, then is the zone, interaction top (apex) of wherein melting and mixing.In style 22 and 24, have second, short secondary Mixed Zone.
According to an embodiment, use two dissimilar rotor designs (dissimilar rotor designs), thereby the top of described rotor is offset mutually (offset from each other).This skew can be axial orientation or tangential orientation (axial or tangential in orientation).This minimizes product melt bypass (bypass) and has increased the distributing mixing.Be accompanied by improved mixing, gel reduces in the final products.The gel area (gel area) of the film that preferably, is generated by polyolefin composition is less than 265/236 square inch.
According to this embodiment, in mixer composite set (mixer assembly), rotor is equipped with leaf combination alternately, preferred staggered helical rotor (staggered helix rotors) is to realize that Billy is with having the mixer composite set lower energy in the cards of similar rotor and the speed of Geng Gao.Prior art is taught in the similar rotor of use in the mixer composite set, and this produces higher specific energy, kWh/kg.Shown in herein, higher specific energy causes the increase of melt index (MI) and some degradeds of final granule product.
The use of dissimilar rotor allows more effective dispersion and the back mixing of described mixer interpolymer melt.Because the improvement that mixes and disperse, it is more even and have a lower gel level to leave the final polymer melt of described mixer.In addition, be accompanied by larger uniformity and focus still less (hot spots), described mixer composite set has been realized than the lower specific energy of commeasurable composite set with the top rotor (apex rotors) that mates, kWh/kg.
Selectively, described method rotor that the embodiment utilization moves with friction speed.Current practice according to prior art is to use the at the same rate rotor of running.Use different spinner velocities to make the operating personnel of the method accurately control energy and be input to optimal level, make simultaneously the maximization of melt treatment amount.This causes Innovative method, and wherein, final granule product has been showed the gel of reduction and lower color, has kept simultaneously the physical property of this final granule product.Preferably, the color that is recorded by the b-color standard will be less than 5.0.
According to this embodiment, when they rotated with identical speed, the orientation of a rotor and another rotor was fixed, and perhaps when they rotated with friction speed, orientation was constantly to change.In larger-diameter mixer, be general than low velocity.For two speed, according to the typical value of preferred embodiment for 12 " for the diameter FCM for about 258 rpm of about 228 rpm-, for being low to moderate 4 " diameter than small machine use higher rpm scope and for up to 21 " the lower speed of larger machine use of diameter.
According to the variable velocity embodiment, method of the present invention has realized lower specific energy (kWh/kg) use, makes the temperature of the melt that enters described extruder be in low temperature.The melt temperature that arrives the reduction of this extruder allows the melt of increase to the friction of extruder wall.The friction of this increase is crucial for improving moving forward of molten polymer.Remain minimum of a value by control inputs to the specific energy of this polymer melt and with it, therefore operating personnel can realize from the extruder of same size the productivity ratio of raising.And, as seem what whiter pellet confirmed, control specific energy to minimum ability so that described method minimizes depolymerization.
And then the actual Mixed Zone of method of the present invention begins after the described charging screw tip.It is comprised of the district with the effect of moving forward and back to back some reverse migration.The motion of this conflict forces polymer compressed and fusing and mixing.
The third step of method of the present invention is that mouth template (die plate) is passed through in the melt pressurization, and purpose is to prepare pellet.Those that the suitable equipment that is used for this step comprises that FCM single screw extrusion machine (as mentioned above), gear pump such as Maag produce or double screw extruder are produced such as Coperion.
Thereby the function of this pressurization steps is to produce enough pressure in described molten polymer back polymer is promoted by the granulation mouth template.Employed single screw extrusion machine is the single screw extrusion machine with variable speed drive motor in the method.Thereby governing speed makes the output coupling of mixer in the output of this extruder and the second step.
Described extruder receives the molten polymer logistics as the gravity charging in skewed slot, this skewed slot is designed to hold this molten polymer logistics and it is guided to extruder screw in the 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, with assistance this molten polymer is shifted onto in the screw flight.By regulating the extruder screw revolution (" rpm ") of per minute, make from flowing of this extruder and mate with the output of mixer.
Then the melt of pressurization is transferred by the granulation mouth template, described polymer flow is divided into independently logistics at this place and is cut into uniform multimodal polyolefin composition pellet.
According to a kind of embodiment of the present invention, this uniform multimodal polyolefin granule product comprises the bimodal polyethylene blend of being made by 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) are be used to the ASTM test of measuring polyolefinic viscosity and stress cracking resistance.
The polymer that is made by method of the present invention can be used for large-tonnage product and terminal use application.Comprise 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 by the prepared polymer of method of the present invention.
Depend on desired purposes, the density of described polymer (being generally polyvinyl) is 0.86 g/cc-0.97 g/cc.Use for some, the density of 0.88 g/cc-0.920 g/cc is preferred, and in other application (such as pipe, film and blowing), the density of 0.930 g/cc-0.965 g/cc is preferred.For low-density polymeric, as using for film, the density of 0.910 g/cc-0.940 g/cc is preferred.According to the ASTM-D-1238 density measurement.
By the molecular weight distribution of the prepared polymer of the method for the present invention (ratio (M of weight average molecular weight and number-average molecular weight
w/ M
n)) can be for greater than 1.5 to about 70.In some embodiments, prepared polymer has the narrow M for about 1.5-15
w/ M
n, and in other embodiments, the M of obtained polymer
w/ M
nBe about 30-50.And polymer of the present invention can have by what Composition Distribution Breadth Index (CDBI) recorded and narrow or wide forms distribution.Other details of determining the CDBI of copolymer is well known by persons skilled in the art.For example, referring to PCT patent application WO 93/03093 (being disclosed on February 18th, 1993), it all is incorporated herein by reference.In some embodiments, the CDBI of prepared polymer can for 80% or larger or CDBI can be 50% or less.
In one embodiment, the CDBI of polymer of the present invention is generally greater than 50% to 100%, and is preferred 99%, and preferred 55%-85%, and 60%-80% more preferably, even more preferably greater than 60% are also even more preferably greater than 65%.
In another embodiment, utilize the CDBI of the polymer that the present invention makes for less than 50%, more preferably less than 40%, and most preferably be less than 30%.
In one embodiment, polymer of the present invention is by melt index (MI) (MI) or (I of ASTM-D-1238-E measurement
2) be 0.01 dg/min-1000 dg/min, about 100 dg/min of about 0.01 dg/min-more preferably, even about 50 dg/min of about 0.01 dg/min-more preferably, and most preferably be about 10 dg/min of about 0.1 dg/min-.
In one embodiment, the melt index (MI) of polymer of the present invention is than (I
21/ I
2) (I
21Recorded by ASTM-D-1238-F) for 10-less than 25, more preferably about 15-is less than 25.
In a preferred embodiment, the melt index (MI) of polymer of the present invention is than (I
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, and even more preferably greater than 50 and most preferably greater than 65.In one embodiment, polymer of the present invention can have Narrow Molecular Weight Distribution and wide composition distributes or vice versa, and can be U.S. Patent No. 5,798, those polymer described in 427, its disclosure is incorporated herein by reference.
Embodiment
Provide the following examples and be used for explaining various embodiments of the present invention.They are not intended to represent all embodiments of the present invention and should not be interpreted as limiting the claimed scope of the present invention of putting down in writing herein.All numerical value described herein all are approximations and can change in its accurate scope.
Embodiment 1
Utilize a style 7 to add style 15 rotors (being abbreviated as 7/15) and various handling rate and temperature and finished a series of tests, and then on same equipment but adopt two style 15 rotors (being abbreviated as 15/15) to implement one group of experiment.Use the bimodal polyethylene polymer.To be kWh/kg and b-color and the gel of having measured pellet by the energy measurement of mixer consumption.The results are shown in figure below of these tests.
The b-color is the standard A STM test of measuring polymer Huang degree.The yellow degree that less numeric representation is lower and the product of better quality.As shown in following table, the dissimilar rotor of the application of the invention orientation, the b-color of pellet is from 11.7 being reduced to 2.5 when using Farrell 15/15 rotor that mates.In the situation of multimodal polyethylene pellet, it is preferred being lower than 4.0 b-color.
The gel area is to measure the not test of the amount of molten material in the film that is made by this material.As for the b-color, numerical value is lower, and the quality of final products is better.As shown in following table, the gel area drops to 265/236 square inch from 555/236 square inch.
The test matrix of every group of experiment is shown in the following table.
The test matrix that is used for test
| Operation # | Center P t | 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 that utilizes 15/15 rotor to carry out, by the cigarette that sends from the mixer discharging and from two of mixer melt band not the same district confirmed degraded.What obtain the results are shown among Fig. 1,2 and 3.
Estimated the difference between the mixer of the mixer of constant speed operation and the operation of non-constant speed.Compared the commodity production line that moves same multimodal polyethylene, mixer 1 moves 7/15 rotor with 300 identical rpm speed, and the second mixer moves 7/15 rotor, one with 258 rpm operation another moves with 228 rpm.Express down the difference of the energy that consumes under the same speed.
| ? | Mixer 1 | |
| 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 the mixer, wherein specific energy is 0.20-0.23, and then wherein energy drop to 0.17-0.19 kWh/kg.In two kinds of situations, rotor is with the running of different speed, and one with 258 rpm, and another is with 228 rpm, and polymer feed is the multimodal polyethylene thin slice.As shown in following table, method of the present invention causes under lower mixer energy high 50% speed.The key component of this raising is because the melt in described mixer applies less energy, makes described extruder process more tacky melt.In fetching the viscous melt charging, single screw extrusion machine is more effective, and melt less is bonded in screw rod, and extruder barrel is cooled and melt is bonded in this machine barrel, and viscous flow is stronger with respect to pressure current.Simultaneously, polymer stuffing plunger (stuffer ram) gap (clearance) is from about 0.75 " drop to less than 0.5 ".
| ? | Situation 1 | |
| 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 |
Use mixer/extruder 4 " implementation evaluation on diameter half active line (semi works line) and the commodity production line, with productivity ratio and the specific energy performance of evaluation bimodal polyethylene resins.The result shows that utilize different rotors to melt the required specific energy of described polymer is reduced to less than 0.25 kWh/kg, and when moving similar rotor design take identical speed as 0.29.On the commodity production line, utilize the energy of dissimilar rotor to drop to and be lower than 0.2 kWh/kg, and 12 " mixer adds 12 " productivity ratio is raised to 13,500 lbs/hr from 10,500 lbs/hr in the extruder.
The evaluation of implementing at the mixer composite set of 1500 lbs/hr scales, estimate the performance of the various rotor configurations that are used for the granulation bimodal polyethylene has shown the benefit of the inventive method.Use therein in the structure of same style rotor and observe higher specific energy.Viewed mixer molten polymer out from described extruder top shows two different melt districts.A district has at Huang Dushang than another zone and significantly improves.When in specie rotor is not replaced long style rotor, observe directly reduction that every kWh/kg energy consumes 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.The neither one embodiment has represented all aspects of the present invention.And, there are the distortion and the change that obtain from them.For example, described multimodal polyolefin feed component can comprise the 3rd component (Alathon or copolymer), and it is so that composition is three peaks in whole molecular weight distribution.Similarly, can also add the 4th, the 5th or the 6th component to regulate the physical property of said composition.
Also can further strengthen one or more performances with various additives.In other embodiments, described feed component is comprised of LMW component described herein and HMW component basically.In some embodiments, feed composition is substantially free of any additive of specifically not listing 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 all such distortion and the change that falls in the scope of the invention.
Claims (15)
1. for the preparation of the method for uniform polyolefin composition, it may further comprise the 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 of compounding and this low-molecular-weight polyolefin component in mixer, this mixer comprises the dissimilar rotor that two or more are offset each other on the top, to produce uniform multimodal polyolefin melt;
C. this melt is moved to the extruder from this mixer; With
D. this melt is pressurizeed so that it is moved through the granulation mouth template from this extruder, wherein polymer flow is divided into logistics separately and is cut into uniform multimodal polyolefin composition pellet.
2. the process of claim 1 wherein the polymerization in a reactor of described low molecular weight olefin polymerization thing component, the polymerization in different reactors of described high molecular weight olefin polymers compositions, 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-amylene-1, hexene-1, octene-1 and decylene-1.
4. the process of claim 1 wherein that described low molecular weight olefin polymerization thing component is selected from ethene, propylene, butene-1, amylene-1,4-methyl-amylene-1, hexene-1, octene-1 and decylene-1.
5. the process of claim 1 wherein that described low molecular weight olefins component and described high molecular weight olefin component are respectively done for oneself utilizes the ethene polymers of slurry phase polymerisation process polymerization.
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 that described low molecular weight olefins component and described high molecular weight olefin component are respectively done for oneself utilizes the ethene polymers of gas phase polymerization process polymerization.
9. the method for claim 8, wherein said polymerization operation in tandem.
10. the method for claim 1, wherein this uniform multimodal polyolefin granule product comprises the bimodal polyethylene blend, this bimodal polyethylene blend is 0.15-0.45 g/10 min by the ethylene copolymer of higher molecular weight and ethene polymers preparation and the melt index (MI) (MI5) 190/5 of lower molecular weight, 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.
12. the method for claim 11, wherein spinner velocity is about 258 rpm of about 228 rpm-.
13. the process of claim 1 wherein that the gel area of the film that generated by described polyolefin composition is less than 265/236 square inch.
14. the process of claim 1 wherein that the b-color of polyolefin composition of the present invention is less than 5.0.
15. the process of claim 1 wherein that in described mixer, the specific energy on the described polyolefin composition is 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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| Publication Number | Publication Date |
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| CN102947067A true CN102947067A (en) | 2013-02-27 |
| CN102947067B 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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| Country | Link |
|---|---|
| EP (1) | EP2539123A1 (en) |
| JP (1) | JP2013520525A (en) |
| CN (1) | CN102947067B (en) |
| RU (1) | RU2573325C2 (en) |
| WO (1) | WO2011101438A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108943655A (en) * | 2018-06-05 | 2018-12-07 | 宁波大学 | A kind of extruding forming method of high strength bimodal polyethylene/chitin nanocrystalline composite material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2847628A1 (en) | 2014-03-28 | 2015-09-28 | Nova Chemicals Corporation | Improved extrusion process |
| RU2696257C2 (en) | 2014-12-04 | 2019-08-01 | Базелл Полиолефин Гмбх | Method of producing 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 |
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| RU2573325C2 (en) | 2016-01-20 |
| WO2011101438A1 (en) | 2011-08-25 |
| RU2012140373A (en) | 2014-03-27 |
| CN102947067B (en) | 2015-06-03 |
| EP2539123A1 (en) | 2013-01-02 |
| JP2013520525A (en) | 2013-06-06 |
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